JP2020119901A - Ultra compact size accelerator, ultra compact size mass spectroscope, and ion implantation device - Google Patents

Abstract

To provide an accelerator and a mass spectroscope, which can be miniaturized and manufactured in a low cost, and are available by anyone.SOLUTION: In each of a mass spectroscope and an accelerator, which is structured by a plurality of substrates containing a first main substrate, a first upper substrate adhered onto an upper face of the first main substrate, and a first lower substrate adhered onto a lower face of the first main substrate, a penetration chamber is formed in the first main substrate, and is penetrated to the lower face of the first main substrate from the upper face of the first main substrate, a vertical direction (a Z direction) of the substrate surface is surrounded by an upper substrate and a lower substrate, and both sides which are a right angle direction with the Z direction and of a charged particle and a traveling direction (an X direction) of a charged particle are surrounded by the first main substrate, and both side faces which have a right angle direction (a Y direction) to the Z direction and the X direction are surrounded by the first main substrate. A central hole of a first main substrate side board, which is incident to the charged particle is opened, and the charged particle is incident to a mass analysis chamber or an acceleration chamber from the central hole formed on the first main substrate side board.SELECTED DRAWING: Figure 1

Description

The present invention relates to an accelerator using an accelerator and a manufacturing method thereof. For example, it relates to a synchrotron, a microtron, a linear accelerator, a mass spectrometer, and an ion implanter.

The accelerator is used to detect the formation of a substance by colliding protons with each other, to form a fine pattern using synchrotron radiation generated when an accelerated particle orbit is bent, and to use ions on the surface of a semiconductor. Used for human disease treatment such as implanting ion implantation to modify the active layer and surface, mass spectrometric analysis of the ions emitted from the substance to investigate the composition and structure of the substance, and implanting and destroying charged particles in cancer cells It is used in various fields such as
However, ultra-vacuum (10 ^-3 to 10 ^-6 torr or less) is required for the motion of the accelerating particles, and a cavity of a considerably large size (for example, 500 mm or more) is required for the high-speed accelerating particles. To accelerate, bend, or converge the accelerated particles that pass through, an electric field generator or a magnetic field generator that generates a large electric field or a large magnetic field is required. For example, an electrostatic lens is used to accelerate charged particles, but several electrostatic lenses (accelerating electrodes) must be precisely parallel to align the holes through which charged particles pass, so a large size Electrodes (for example, a hole size of 20 mm or more and an electrode size of 300 mm or more) are required, and they must be placed in an ultra-vacuum cavity. Therefore, the vacuum system becomes large, and it is necessary to use a vacuum pump having a large size and good performance. Further, since the magnetic field generator cannot be made large enough to fit in the cavity (vacuum line), and since the side wall surrounding the cavity also exists, the distance to the target charged particle becomes long (for example, 500mm or more), so a large magnetic field generator is required. Even if such a large magnetic field generator is reduced in size by using an electromagnet made of a superconducting material, the size of the entire magnetic field generator is hardly changed because the cooling system becomes large.
In recent years, there is a plan to build an International Linear Collider (ILC) in Japan, but this construction will cost more than 1 trillion yen, and the maintenance cost will also be 50 billion yen/year, so I decided to build it. I can't.

Furthermore, although food safety has been sought in recent years, it is difficult to know the substances contained in food and drinking water easily, quickly, and individually. There is no way for an individual to grasp how close environmental pollution such as soil due to the Fukushima nuclear accident is approaching. Unknowingly, humans are often contaminated with radioactivity and poisons, and when they become aware, they are often in serious trouble. In the current state of the art, there is no precision analyzer that is large in size, heavy and portable. Moreover, since the device price is high, it is difficult to obtain.
Crime becomes complicated and it takes a long time to identify the cause and the criminal, but if a quick analysis is performed at the crime scene, it is often resolved quickly. For example, although accidents and crimes due to illegal drugs have become a problem these days, the reason why the detection of dealers can not catch up is that the actual thing cannot be suppressed on site. Therefore, there is a demand for a measuring device that can perform accurate and highly accurate analysis on the spot.
In the field of advancing scientific research while conducting field research such as archeology and environmental science, if mass spectrometry with high accuracy for portable use is carried out, the research will advance dramatically. Further, if the device is inexpensive and small, it becomes possible to process a large amount of samples in a short time.

JP2003-036996 Japanese Patent Fair 5-36902

Conventional accelerators use large-sized electric field generators and magnetic field generators for accelerating, bending, and converging charged particles. The technology for precisely aligning them has become quite sophisticated, and the accelerator is made by hand, so it was impossible to make it in large quantities cheaply and quickly.
Also provided is a mass spectrometer that is ultra-compact, lightweight, portable, and capable of performing simple and quick measurement on site. Moreover, the price is much cheaper than the conventional product, and the measurement accuracy is equal to or higher than the conventional one. Specifically, using a semiconductor/MEMS technology, a 4 to 8 inch substrate (a substrate larger than this size may be used), and a sample supply unit, an ionization unit, an extraction electrode unit, a mass analysis unit (double (Focusing type) ・High-performance, high-accuracy, ultra-compact mass spectrometer with an ion detector is manufactured. It is ultra-compact, lightweight, portable, and capable of in-situ analysis, so it is possible to quickly perform on-site measurement of radioactive elements such as 137Cs and food/drinking water analysis at home. Since the cost will be 1/10 to 1/100 of that of the conventional type, it is required to realize an era with one mass spectrometer for one person and to create a safe and secure society.

According to the present invention, the upper and lower sides of a penetration chamber formed in a semiconductor substrate such as a Si substrate are covered with an insulating substrate such as a glass substrate or a quartz substrate, and the penetration chamber is used as a path for charged particles such as accelerated ions and the penetration of In a chamber, necessary components for an accelerator such as an extraction electrode, an acceleration electrode, an acceleration cavity, a quadrupole electrode, a quadrupole trap, a mass spectrometer, etc. are formed by using an LSI process.
Specifically, the present invention has the following features.
(1)
The present invention is a mass spectrometer including a plurality of substrates including a first main substrate, a first upper substrate attached to the upper surface of the first main substrate, and a first lower substrate attached to the lower surface of the first main substrate. So, the mass spectrometry room is <after this>
A through-chamber formed on the first main substrate from the upper surface of the first main substrate to the lower surface of the first main substrate, the direction perpendicular to the substrate surface (Z direction) being the Z direction to the upper substrate and the lower substrate. Both sides in the direction perpendicular to each other and in the traveling direction (X direction) of the charged particles are surrounded by the first main substrate side plate, and both sides in the directions perpendicular to the Z direction and the X direction (Y direction) are surrounded by the first main substrate. In the mass spectrometer, the first main substrate side plate on which the charged particles are incident has a central hole, and the charged particles are incident on the mass analysis chamber through the central hole formed in the first main substrate side plate. Yes,
The first main substrate is an insulator substrate, a semiconductor substrate, a conductor substrate, or a laminated substrate thereof,
The upper substrate and the lower substrate are glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates of these,
When the main substrate is an insulating substrate, a glass substrate, a quartz substrate, a plastic substrate, an alumina substrate, an AlN substrate, a ceramic substrate, a polymer substrate, or a laminated substrate of these,
When the main substrate is a semiconductor substrate, it may be a Si substrate, a SiC substrate, a C substrate, a GaAs substrate, an InP substrate, a GaN substrate, a CdS substrate, a binary compound semiconductor, a ternary compound semiconductor, or a laminated substrate thereof. Characterized by
When the main substrate is a semiconductor substrate, and when it is a conductor substrate, it is Cu, Al, Ti, Zn, Fe, an alloy containing these metals, or a laminated substrate thereof.

(2)
In the present invention, the mass spectrometer is a quadrupole mass spectrometer, and in the mass spectrometer,
Two quadrupole electrodes attached or formed on the lower surface of the upper substrate and two quadrupole electrodes attached or formed on the upper surface of the lower substrate;
A contact wiring (upper substrate contact wiring) formed on the upper substrate connected to the two quadrupole electrodes arranged on the lower surface of the upper substrate, and an electrode formed on the upper surface of the upper substrate connected to the upper substrate contact wiring. Wiring (upper substrate upper surface electrode/wiring), contact wiring (lower substrate contact wiring) formed on the lower substrate connected to two quadrupole electrodes arranged on the upper surface of the lower substrate, and the lower substrate contact wiring Has electrodes/wirings (lower board lower surface electrodes/wirings) formed on the lower board lower surface to be connected,
A mass spectrometer characterized by applying a high-frequency voltage and/or a DC voltage from the upper electrode/wiring and the lower electrode/wiring,
Of the two quadrupole electrodes arranged on the lower surface of the upper substrate and the two quadrupole electrodes arranged on the upper surface of the lower substrate, two quadrupole electrodes which are not adjacent to each other have substantially the same distance. Yes, and the midpoints between them are almost the same,
Of the two quadrupole electrodes arranged on the lower surface of the upper substrate and the two quadrupole electrodes arranged on the upper surface of the lower substrate, the distances between two adjacent quadrupole electrodes are substantially the same. It is characterized by

(3)
According to the present invention, the second main substrate is attached on or above the upper substrate (first upper substrate), and the second upper substrate (second upper substrate) is attached on the second main substrate, and the through chamber ( A through chamber (second through chamber) penetrating from the second upper substrate to the first upper substrate is formed on the second main substrate in the upper part of the (first through chamber), and between the first through chamber and the second through chamber. An opening is provided in a part of the first upper substrate, and the opening is formed between two quadrupole electrodes arranged on the lower surface of the first upper substrate. The electrode/wiring formed on the first upper substrate connected to the quadrupole electrode arranged in the above is connected to the wiring (second wiring) formed on the side surface of the second penetration chamber, and the second wiring is the second upper portion. The electrode/wiring formed on the lower surface of the substrate is further connected to the contact wiring (second upper substrate contact wiring) formed on the second upper substrate, 2. The upper substrate contact wiring is connected to an electrode/wiring (second upper electrode/wiring) formed on the second upper substrate,
A third main substrate is attached to or below the lower surface of the lower substrate (first lower substrate), and a second lower substrate (second lower substrate) is attached to the lower surface of the third main substrate, and the through chamber (first (1st penetration chamber), a penetration chamber (third penetration chamber) penetrating from the second lower substrate to the first lower substrate is formed in the third main substrate, and a first penetration chamber between the first penetration chamber and the third penetration chamber is formed. 1. An opening is provided in a part of the lower substrate, and the opening is formed between two quadrupole electrodes arranged on the upper surface of the first lower substrate,
The electrode/wiring formed on the lower surface of the first lower substrate connected to the quadrupole electrode arranged on the upper surface of the first lower substrate is connected to the wiring (third wiring) formed on the side surface of the third penetration chamber. , The third wiring is connected to an electrode/wiring formed on the upper surface of the second lower substrate, and the electrode/wiring formed on the upper surface of the second lower substrate is a contact wiring (second lower substrate). Contact wiring), and the second lower substrate contact wiring is connected to an electrode/wiring (second lower electrode/wiring) formed on the lower surface of the second upper substrate,
A mass spectrometer characterized by applying a high-frequency voltage and/or a DC voltage from the second upper electrode/wiring and the second lower electrode/wiring,
The second upper substrate and the second lower substrate are glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates thereof,
When the second main substrate and the third main substrate are insulator substrates, they may be glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates thereof. Characteristic,
When the second main substrate and the third main substrate are semiconductor substrates, Si substrate, SiC substrate, C substrate, GaAs substrate, InP substrate, GaN substrate, CdS substrate, binary compound semiconductor, ternary compound semiconductor, or Characterized by being a laminated substrate of these,
When the second main substrate and the third main substrate are semiconductor substrates, when they are conductor substrates, they are Cu, Al, Ti, Zn, Fe, alloys containing these metals, or laminated substrates thereof. It is characterized by

(4)
In the present invention, the mass analysis chamber is a quadrupole mass analysis chamber, one quadrupole electrode is arranged on the upper surface of the upper substrate attached to the upper part of the mass analysis chamber, and the lower portion attached to the lower part of the mass analysis chamber. One quadrupole electrode is arranged on the lower surface of the substrate, and one quadrupole electrode is arranged on each of the left and right penetration chambers formed on the main substrate adjacent to the mass analysis chamber. A characteristic mass spectrometer,
The left and right penetration chambers formed on the main substrate next to the mass analysis chamber are characterized in that the substrate sidewall exists between the mass analysis chamber and
The quadrupole electrode is a rod, and is characterized in that the rod is attached to a predetermined portion of the upper substrate, the lower substrate, and the main substrate,
The quadrupole electrode is laminated on the upper substrate or the lower substrate by a CVD method, a PVD method, a plating method, an electroforming method, a screen printing method, a squeegee method, a spin coating method, a dispensing method, or a combination thereof to form a predetermined shape Characterized in that it is a processed conductor film electrode,
The mass spectrometry chamber is a quadrupole mass spectrometry chamber, and two quadrupole electrodes attached or formed on the lower surface of the upper substrate attached to the upper portion of the mass spectrometry chamber and on the surface on the mass spectrometry chamber side are arranged. A mass spectrometer characterized in that two quadrupole electrodes attached to the upper surface of a lower substrate attached to or formed on the lower portion of the mass analysis chamber and attached to the surface on the mass analysis chamber side are arranged.
A through chamber (second through chamber) is further formed above the upper substrate (first upper substrate) having two quadrupole electrodes attached or formed thereon, and the second upper substrate is attached above the second through chamber. A part of the first upper substrate between the mass analysis chamber (first penetration chamber) and the second penetration chamber is removed, and the pressures of the first penetration chamber and the second penetration chamber are substantially the same. Characterized by
A penetration chamber (third penetration chamber) is further formed below the lower substrate (first lower substrate) having the two quadrupole electrodes attached or formed thereon, and the second lower substrate is adhered to the lower portion of the third penetration chamber. A part of the first lower substrate between the mass analysis chamber (first penetration chamber) and the third penetration chamber is removed, and the pressures of the first penetration chamber and the third penetration chamber are substantially the same. It is characterized by
(5)
In the present invention, the mass spectrometry chamber includes one quadrupole electrode (first quadrupole electrode) attached or formed on the lower surface of the upper substrate, and one quadrupole electrode attached or formed on the upper surface of the lower substrate. (Second quadrupole electrode), a part of the substrate on one side surface of the mass analysis chamber extends in the Y direction in the mass analysis chamber, and one of the four electrodes attached or formed on the upper or lower surface of the substrate on the extended side surface. A part of the quadrupole electrode (third quadrupole electrode) and the substrate on the other side surface of the mass analysis chamber extends in the Y direction in the mass analysis chamber, and is attached or formed on the upper surface or the lower surface of the substrate on the extended side surface. Characterized by including one quadrupole electrode (fourth quadrupole electrode),
The upper substrate has a contact wiring (first upper substrate contact wiring) connected to the first quadrupole electrode and an electrode/wiring (first upper substrate electrode/wiring) connected to the first contact wiring on the upper surface thereof. ,
The lower substrate has a contact wiring (first lower substrate contact wiring) connected to the second quadrupole electrode and an electrode/wiring (first lower substrate electrode/wiring) connected to the second contact wiring on the lower surface thereof. ,
The side substrate on which the third quadrupole electrode is attached or formed has a wiring for connecting to the third quadrupole electrode, and the wiring is connected to the wiring formed on the side surface of the main substrate and further formed on the side surface. The formed wiring is connected to the wiring formed on the upper substrate or the lower substrate, and the wiring is further connected to the contact wiring (the second upper substrate contact wiring or the second lower substrate contact wiring) formed on the upper substrate or the lower substrate. In addition, the second upper substrate contact wiring or the second lower substrate contact wiring is an electrode/wiring (second upper substrate electrode/wiring or second lower substrate electrode/wiring) formed on the upper surface of the upper substrate or the lower surface of the lower substrate. ) Is connected to.

(6)
According to the present invention, a penetration chamber (second penetration chamber) is further formed above the upper substrate (first upper substrate), a second upper substrate is attached to an upper portion of the second penetration chamber, and the mass analysis chamber (first (1 through chamber) and a portion of the first upper substrate between the second through chamber are removed, the pressure of the first through chamber and the second through chamber is substantially the same,
A through chamber (third through chamber) is further formed below the lower substrate (first lower substrate), a second lower substrate is attached to a lower portion of the third through chamber, and the mass spectrometry chamber (first through chamber) is formed. A part of the first lower substrate between the first and third through chambers is removed, and the pressures of the first and third through chambers are substantially the same,
The mass spectrometer is a quadrupole mass spectrometer, and in the mass spectrometer,
A quadrupole electrode (first quadrupole electrode) attached or formed on the lower surface of the upper substrate, and a quadrupole electrode (third quadrupole electrode) attached or formed on the upper surface of the lower substrate,
Contact wiring (upper substrate contact wiring) formed on the upper substrate connected to the quadrupole electrode (first quadrupole electrode) arranged on the lower surface of the upper substrate and an upper substrate upper surface connected to the upper substrate contact wiring The formed electrodes/wirings (upper substrate upper surface electrodes/wirings) and contact wirings (lower substrate) formed on the lower substrate connected to the quadrupole electrode (third quadrupole electrode) arranged on the upper surface of the lower substrate. Contact wiring) and electrodes/wirings (lower substrate lower surface electrodes/wirings) formed on the lower substrate lower surface connected to the lower substrate contact wiring,
A quadrupole electrode (second quadrupole electrode and fourth quadrupole electrode) formed on two side surfaces of the main substrate in the Y direction,
The second quadrupole electrode and the fourth quadrupole electrode are the contact wiring formed on the upper substrate and/or the lower substrate, and the electrode/wiring formed on the upper surface of the upper substrate and/or the lower surface of the lower substrate ( Upper substrate upper surface electrode/wiring and/or lower substrate lower surface electrode/wiring)),
A high frequency voltage and/or a DC voltage is applied from the upper substrate upper surface electrode/wiring and the lower substrate lower surface electrode/wiring.

(7)
In the present invention, the second quadrupole electrode and the fourth quadrupole electrode are conductor films stacked in a through chamber formed in the main substrate, and a part of the conductor film is a plating film. Characterized by
The mass spectrometric chamber is of a magnetic field application type and includes one or more coils arranged above the upper substrate attached to the upper part of the main substrate forming the mass spectrometric chamber and/or of the main substrate forming the mass spectrometric chamber. It was used that the orbit of charged particles was changed by generating a magnetic field in the direction perpendicular to the substrate surface of the main substrate by one or more coils arranged on the lower side of the lower substrate attached to the lower portion. Characterized by
The mass spectrometric chamber is of a magnetic field application type and includes an electromagnet disposed above the upper substrate attached to the upper part of the main substrate forming the mass spectrometric chamber and/or below the lower substrate attached to the lower part of the main substrate. , Characterized in that the orbit of the charged particles is changed by generating a magnetic field in a direction perpendicular to the substrate surface of the main substrate,
One or more coils arranged on the upper side of the upper substrate and/or the lower side of the lower substrate are formed on the second main substrate by lamination,
The charged particles are emitted from the charged particle extraction chamber or the charged particle acceleration chamber to the mass analysis chamber, and a substrate side wall plate (front substrate) having a central hole between the charged particle extraction chamber or the charged particle acceleration chamber and the mass analysis chamber. A side wall plate) is disposed, and the charged particles are emitted to the mass analysis chamber through a central hole of the front side plate.
The charged particles that have left the mass analysis chamber are subjected to ion detection in the ion detection chamber, and the ion detection chamber is a penetration chamber formed in the main substrate, and has a central hole between the mass spectrometry chamber and the ion detection chamber. A substrate side wall plate (rear substrate side wall plate) is arranged, and the charged particles are emitted to the ion detection chamber side through a central hole of the rear substrate side wall plate,
The charged particles are characterized by being bent in a 360-degree direction by a magnetic field, and a plurality of ion detection chambers are arranged in a 360-degree region.

(8)
In the present invention, the mass spectrometric chamber is a double-focusing type in which an electric field application type is further added, and a region in the electric field application type through which charged particles pass is formed on a main substrate, and an upper surface (Z direction) is an upper substrate. The lower surface (Z direction) is a penetration chamber (electric field application type penetration chamber) including a fan-shaped penetration chamber (fan-shaped region penetration chamber) surrounded by a lower substrate and a side surface (Y direction) surrounded by the main substrate side surface, The X-direction of the electric field type penetration chamber is surrounded by a substrate side wall plate having a central hole, and charged particles enter through the central hole of one of the substrate side wall plates, and the orbits of the charged particles are bent in the electric field type penetration chamber. And the light is emitted from the central hole of the other side wall plate of the substrate, and the electric field application type penetration chamber has a central orbit of radius R0, a central angle α, and a constant distance d0 from the central orbit on both sides of the facing main substrate. An electrode is formed, and the charged particles are bent by an electric field generated by a voltage applied to the electrodes formed on both sides,
The side electrode in the electric field application type penetration chamber is characterized in that a plating film is further laminated on a conductor film laminated by a CVD method or a PVD method,
The contact wiring connected to the side surface electrode is formed on the upper substrate attached to the upper surface of the electric field type penetration chamber, is connected to the electrode/wiring formed on the upper surface of the upper substrate, and/or is the lower surface of the electric field type penetration chamber. It is characterized in that it is formed on the lower substrate attached to the substrate and is connected to the electrodes and wiring formed on the lower surface of the lower substrate.

(9)
The through chamber (ICR chamber) in which charged particles enter and perform cyclotron motion is provided in a substrate side wall plate (substrate side wall plate for extraction electrode) having a central hole which is an entrance of charged particles from an ion source, and in a traveling direction of charged particles. Yes, the substrate side wall facing the extraction electrode substrate side wall, the side wall of the substrate on which the cyclotron-moved charged particles collide (trap electrode substrate side wall), the upper substrate attached to the upper part of the ICR chamber, and the lower substrate attached to the lower part of the ICR chamber. , Is surrounded by two substrate side walls (receiver electrode substrate side walls) substantially parallel to the charged particles, and the surface of the extraction electrode substrate side wall plate serves as an extraction electrode for drawing the charged particles from the central hole to the ICR chamber. A conductor film electrode is formed, a conductor film electrode to which a voltage for trapping the charged particles is applied is formed on the surface of the side wall of the trap electrode substrate, and the upper substrate and the lower substrate excite the charged particles. Characterized in that a conductor film electrode to which a voltage is applied is formed,
In the ICR chamber, a magnetic field parallel to the direction from the extraction electrode to the trap electrode, which is the traveling direction of the charged particles, is applied,
The coil wiring for generating the magnetic field is formed in close contact with the upper substrate and the lower substrate and further formed in close contact with the outer side surface of the main substrate, or formed inside the main substrate, the upper substrate and the lower substrate. Is characterized by
The support substrate is attached on the upper substrate, the second upper substrate is further attached on the support substrate, the support substrate is attached on the lower substrate, and the second lower substrate is further attached on the support substrate. The coil wiring for generating the magnetic field is formed in close contact with the upper substrate and the lower substrate, and further formed in close contact with the outer side surface of the main substrate,
Further, the electrode wirings connected to the extraction electrode, the trap electrode, the two opposing ion excitation electrodes, and the two opposing receiver electrodes in the ICR chamber are formed on the upper substrate and/or the lower substrate, and the upper substrate and the pillar It exists in the space surrounded by the substrate and the second upper substrate, and/or in the space surrounded by the lower substrate, the pillar substrate, and the second lower substrate, and their electrode wirings are 2 is connected to the electrode wiring formed on the upper substrate and/or the second lower substrate, and the electrode connected to the coil is the electrode wiring formed on the second upper substrate and/or the second lower substrate. It is characterized by being connected.

(10)
The charged particle generating chamber for generating charged particles includes two through chambers (charged particle generating chambers 1 and 2) formed on a main substrate having an upper portion on an upper substrate and a lower portion on a lower substrate. 1 and the charged particle generation chamber 2 are adjacent chambers separated by a substrate side wall plate (first substrate side wall plate) having a central hole, and the sample plate inserted from the opening formed in the upper substrate is a charged particle generation chamber. 1, the laser beam is applied to the sample attached to the sample plate from the opening formed in the upper substrate, and the sample is decomposed into particles, and the decomposed particles (decomposed particles) are the side walls of the substrate. The ionization beam selected from laser light, electron beam, synchrotron radiation, and X-rays passes through the central hole of the plate and enters the charged particle generation chamber 2 from the outside of the upper substrate or the lower substrate. Characterized in that charged particles are generated by irradiating the decomposed particles present in the inside,
Next to the charged particle generation chamber 2, there is an extraction electrode/acceleration chamber separated by a substrate side wall plate having a central hole (second substrate side wall plate),
The extraction electrode/acceleration chamber is a penetration chamber formed on the upper substrate on the upper side and on the lower substrate on the lower side.
In the inner surface of the charged particle generation chamber 2, the upper substrate and the lower substrate, and/or the side surface of the first substrate side wall plate, and/or the side surface of the second substrate side wall plate, and/or the side surface of the other two substrate side walls are electrically conductive. Body membrane electrodes are formed,
The conductor film electrode is connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is connected to a conductor film electrode/wiring formed on the outer surface of the upper substrate and/or the lower substrate. Characterized by
The charged particles having the same sign as the voltage applied to the conductor film electrode are attracted to the extraction electrode/acceleration chamber through the central hole of the second substrate side wall plate by the extraction electrode arranged in the extraction electrode/acceleration chamber. Characterized by
The charged particles that have entered the extraction electrode/acceleration chamber are mass spectrometers that are characterized in that they exit the extraction electrode/acceleration chamber and enter the mass analysis chamber,
In the charged particle generating chamber 1, the back surface of the sample plate is arranged in close contact with the side surface of the substrate side wall, the substrate side wall is provided with a central hole, and the central hole is connected to the opening of the upper substrate or the lower substrate. It is characterized in that cavities in the thickness direction of the main substrate are connected to each other, and the sample plate is sucked to the side surface of the substrate side wall by being evacuated from the opening of the upper substrate or the lower substrate.

(11)
According to the present invention, a charged particle generation chamber for generating charged particles includes two through chambers (charged particle generation chambers 1 and 2) formed on a main substrate having an upper portion attached to an upper substrate and a lower portion attached to a lower substrate, The charged particle generation chamber 1 and the charged particle generation chamber 2 are adjacent chambers separated by a substrate side wall plate (first substrate side wall plate) having a central hole,
The sample plate inserted from the opening formed in the upper substrate is arranged in the charged particle generation chamber 1,
In the charged particle generating chamber 1, the back surface of the sample plate is arranged in close contact with the side surface of the substrate side wall, the substrate side wall is provided with a central hole, and the central hole is connected to the opening of the upper substrate or the lower substrate. The cavities in the thickness direction of the main substrate are connected, and the sample plate is sucked to the side surface of the substrate side wall by being evacuated from the opening of the upper substrate or the lower substrate.
A conductive film is formed on the side surface of the side wall of the substrate, and the conductive film formed on the side surface of the side wall of the substrate is connected to the conductive film formed on the surface of the upper substrate and/or the lower substrate on the charged particle generation chamber 1 side. , The conductor film is further connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is further connected to a conductor film electrode wiring formed on the outer surface of the upper substrate and/or the lower substrate. Then
A voltage is applied to the sample plate, which is a conductor, from the conductor film electrode wiring,
By irradiating the sample attached to the sample plate with a laser beam from the opening formed in the upper substrate, the sample is decomposed into particles and charged particles are generated,
Charged particles with the same sign as the charge of the sample plate jump out of the sample plate,
A substrate side wall plate (third substrate side wall plate) having a central hole in a direction facing the sample plate is arranged, a conductor film is formed on the surface of the third substrate side wall plate, and is formed on the surface of the third substrate side wall plate. The formed conductor film is connected to the conductor film formed on the surface of the upper substrate and/or the lower substrate on the charged particle generation chamber 1 side, and the conductor film is further formed on the upper substrate and/or the lower substrate. Connecting to a contact wiring, and the contact wiring is further connected to a conductor film electrode wiring formed on the outer surface of the upper substrate and/or the lower substrate,
A voltage opposite to the voltage applied to the sample plate is applied to the conductor film formed on the surface conductor of the third side wall plate from the conductor film electrode wiring, and the charged particles jumping out of the sample plate are extracted,
The charged particles pass through the central hole formed in the side wall plate of the third substrate and further enter the charged particle generating chamber 2 through the central hole of the side wall plate of the first substrate.
On the inner surface of the charged particle generating chamber 2, the upper substrate and the lower substrate, and/or the side surface of the first substrate side wall plate, and/or the side surface of the second substrate side wall plate, and/or the side surface of the other two substrate side wall plates, and / Or a conductor film electrode is formed on the inner surface of the central hole of the first substrate side wall plate,
The conductor film electrode is connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is connected to a conductor film electrode/wiring formed on the outer surface of the upper substrate and/or the lower substrate. Characterized by
The voltage applied to the conductor film electrode has the same sign as that of the charged particles, and by adjusting the voltage, the charged particles are converged and the side wall plate of the substrate (second part) separating the charged particle generation chamber 2 from the adjacent chamber is formed. Incident on the adjacent chamber through a central hole of the substrate side wall plate),
The charged particle that has passed through the central hole of the side wall plate of the second substrate enters the mass analysis chamber.

(12)
According to the present invention, an upper substrate is attached to an upper surface of a main substrate, a lower substrate is attached to a lower surface of the main substrate, a through chamber formed in the main substrate is used as an ionization chamber, and a central hole is connected to the ionization chamber. Is connected to a vertical hole (perpendicular to the substrate surface) formed in the main substrate that connects to the opening (sample introduction opening) of the upper or lower substrate,
A conductor film (second conductor film) is formed on the inner surface of the central hole, a conductor film (first conductor film) is formed on the inner surface of the ionization chamber, and the first conductor film and the second conductor film are formed in the ionization chamber. The first conductor film is connected by a conductor film formed on the side surface of the main substrate, and the first conductor film is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Characterized by
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the ionization chamber as a spray gas at the outlet to the ionization chamber,
By applying a voltage from the outer electrode formed on the upper substrate and/or the lower substrate, a voltage is applied to the conductor film formed on the inner surface of the central hole, and the gas (spray gas) ejected at the outlet of the ionization chamber is thereby generated. ) Is an ionization method characterized by ionization.
(13)
According to the present invention, an upper substrate is attached to an upper surface of a main substrate, a lower substrate is attached to a lower surface of the main substrate, a through chamber formed in the main substrate is used as an ionization chamber, and a central hole is connected to the ionization chamber. Is connected to a vertical hole (perpendicular to the substrate surface) formed in the main substrate that connects to the opening (sample introduction opening) of the upper or lower substrate,
Parallel plate conductor film electrodes were formed on the upper and lower sides of the inner surface of the central hole, or parallel plate conductor film electrodes were formed on two side surfaces of the inner surface of the central hole, and each parallel plate conductor film electrode was formed on the inner surface of the ionization chamber. The conductor film is connected to the conductor films formed on the upper substrate and the lower substrate in the ionization chamber, and the outer side is formed on the upper substrate and/or the lower substrate through the contact wiring formed on the upper substrate and/or the lower substrate. Characterized by connecting to electrodes,
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the ionization chamber as a spray gas at the outlet to the ionization chamber,
By applying a high-frequency voltage from the outer electrode formed on the upper substrate and/or the lower substrate, a high-frequency voltage is applied to the conductor film formed on the inner surface of the central hole, which causes gas (gas) ejected at the outlet of the ionization chamber ( Spray gas) is an ionization method characterized by being ionized.

(14)
According to the present invention, a recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and / Or a mass spectrometer characterized by cooling or heating the central hole,
Characterized by heating a part of the conductor film formed on the upper substrate and/or the lower substrate to heat the ionization chamber, and heating a part of the conductor film formed on the central hole in the ionization chamber age,
A conductive film electrode is provided on a substrate side wall plate or a substrate side wall facing the extraction electrode chamber, and a voltage having the same sign as the ion is applied to the conductive film electrode to push out the ions into the extraction electrode chamber. To do.
(15)
According to the present invention, an upper substrate is attached to the upper surface of the main substrate and a lower substrate is attached to the lower surface of the main substrate, and one penetration chamber formed in the main substrate is used as an ionization chamber, and a penetration chamber formed in the main substrate next to the ionization chamber is used. A heating chamber is provided, and the ionization chamber and the heating chamber are partitioned by a substrate side wall plate having a central hole (second central hole), or the ionization chamber and the heating chamber are the same through chambers, and the partitioned substrate side wall plate is Or not
There is a central hole (first central hole) connected to the heating chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
A conductor film (second conductor film) is formed on the inner surface of the central hole, a conductor film (first conductor film) is formed on the inner surface of the heating chamber, and the first conductor film and the second conductor film are formed in the heating chamber. The first conductor film is connected by a conductor film formed on the side surface of the main substrate, and the first conductor film is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Characterized by
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the heating chamber as a spray gas at the outlet to the heating chamber,
A heating chamber is heated by applying a voltage from an outer electrode formed on the upper substrate and/or the lower substrate and flowing a current to the first conductive film to heat the first conductive film.
In the ionization chamber, a steeple electrode is arranged on the upper substrate and/or the lower substrate, and the steeple electrode is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Then, by applying a voltage to the outer electrode, the spray gas heated by being discharged at the steeple electrode is ionized, which is an ionization method.

(16)
According to the present invention, a recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and / Or a mass spectrometer characterized by cooling or heating the central hole,
Characterized in that the ionization chamber is heated by using a part of the conductor film formed on the upper substrate and/or the lower substrate,
The ionization chamber is heated by using a part of the conductor film formed in the central hole, and a conductor film electrode is provided on the substrate side wall plate or the substrate side wall facing the extraction electrode chamber. It is characterized in that ions are pushed out to the extraction electrode chamber by applying a voltage having the same sign as that of the ions.
(17)
The present invention, an upper substrate on the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, the penetration chamber formed in the main substrate is an ionization chamber,
There is a central hole (first central hole) connected to the ion chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
The sample solution is introduced from the sample introduction opening, the matrix is formed at the outlet to the ionization chamber through the vertical hole and the central hole, and the matrix is formed from the outside through the opening formed on the upper substrate or the lower substrate to the laser or It is an ionization method characterized by irradiating a fast atom beam and as a result, the molecules in the matrix are ionized.
The upper substrate is attached to the upper surface of the main substrate, the lower substrate is attached to the lower surface of the main substrate, and the penetration chamber formed in the main substrate is used as the ionization chamber,
There is a central hole (first central hole) connected to the ion chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
The sample solution is introduced through the sample introduction opening, passes through the vertical hole and the central hole, and a matrix is formed at the outlet to the ionization chamber,
Ionization, characterized in that a laser or fast atom beam chamber is placed next to the ionization chamber, the laser or fast atom beam chamber irradiates the laser or fast atom beam chamber onto the matrix, which results in the molecules in the matrix being ionized. Is the law.

(18)
According to the present invention, the penetrating chamber formed adjacent to the ionization chamber on the main substrate is the extraction electrode chamber, and the extraction electrode chamber and the ionization chamber are partitioned by the substrate side wall plate having the central hole (second central hole), A conductor film electrode is formed on the side surface of the substrate side wall facing the substrate side wall plate, a voltage having the same sign as that of the ions is applied to the conductor film, and the generated ions are pushed out by the conductor film electrode to cause the substrate side wall plate to move. It is characterized in that it is emitted to the extraction electrode chamber through the second central hole,
A recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and/or the central hole. Characterized by cooling or heating,
The present invention is characterized in that a conductor film is formed on the inner surface of the central hole and/or the inner surface of the penetration chamber, and a current is passed through the conductor film to generate heat to heat the central hole and/or the penetration chamber.
(19)
The present invention, an upper substrate on the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, a ring electrode is formed on the main substrate, the penetration chamber formed in the center of the ring electrode is an ion trap chamber, An upper electrode (ion trap upper electrode) formed on the upper substrate is arranged on an upper portion of the ion trap chamber, and a lower electrode (ion trap lower electrode) formed on a lower substrate is arranged on a lower portion of the ion trap chamber,
The ring electrode forms a conductor film (ring conductor film electrode) in a ring shape of the main substrate, and the ring conductor film electrode passes through the contact wiring formed on the upper substrate and/or the lower substrate to the upper substrate and/or the lower substrate. Connect to the outer electrode formed on the lower substrate,
The ion trap upper electrode and the ion trap lower electrode are connected to the outer electrodes formed on the upper substrate and the lower substrate through the contact wirings formed on the upper substrate and the lower substrate, and the ring electrode is a main substrate having a central hole. , One of the penetration chambers adjacent to the ion trap chamber is the ionization chamber or between the extraction electrode/accelerating electrode chamber and the ion trap chamber, and the other penetration chamber adjacent to the ion trap chamber. Located between an ion detection chamber and an ion trap chamber, one central hole connects from the ionization chamber to the ion trap chamber, the other central hole connects from the ion trap chamber to the ion detection chamber,
By applying a predetermined voltage to the ring conductor film electrode, the ion trap upper electrode, and the ion trap lower electrode, the ion trap chamber is passed through the central hole connected from the ionization chamber or the extraction electrode/acceleration electrode chamber to the ion trap chamber. The ion that entered is trapped in the ion trap chamber, and the trapped ion is emitted from the ion trap chamber through the central hole connected to the ion detection chamber to the ion detection chamber and is detected. , An ion trap mass spectrometer.

(20)
The present invention, an upper substrate on the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, a ring electrode is formed on the main substrate, the penetration chamber formed in the center of the ring electrode is an ion trap chamber, An upper electrode (ion trap upper electrode) formed on the upper substrate is arranged on an upper portion of the ion trap chamber, and a lower electrode (ion trap lower electrode) formed on a lower substrate is arranged on a lower portion of the ion trap chamber,
The ring electrode forms a conductor film (ring conductor film electrode) in a ring shape of the main substrate, and the ring conductor film electrode passes through the contact wiring formed on the upper substrate and/or the lower substrate to the upper substrate and/or the lower substrate. Connect to the outer electrode formed on the lower substrate,
The ion trap upper electrode and the ion trap lower electrode are connected to the outer electrodes formed on the upper substrate and the lower substrate through the contact wirings formed on the upper substrate and the lower substrate, and the ring electrode is a main substrate having a central hole. ,
One of the penetration chambers located above the ion trap chamber is the ionization chamber or between the extraction electrode/acceleration electrode chamber and the ion trap chamber, and the other penetration chamber adjacent to the ion trap chamber. It is arranged between the ion detection chamber and the ion trap chamber, one central hole is connected from the ionization chamber to the ion trap chamber, the other central hole is connected from the ion trap chamber to the ion detection chamber,
By applying a predetermined voltage to the ring conductor film electrode, the ion trap upper electrode, and the ion trap lower electrode, the ion trap chamber is passed through the central hole connected from the ionization chamber or the extraction electrode/acceleration electrode chamber to the ion trap chamber. The ion that entered is trapped in the ion trap chamber, and the trapped ion is emitted from the ion trap chamber through the central hole connected to the ion detection chamber to the ion detection chamber and is detected. , An ion trap mass spectrometer.

(21)
The present invention relates to a main substrate having a plurality of through chambers penetrating from the upper surface to the lower surface, an upper substrate attached to the upper surface of the main substrate, a lower substrate attached to the lower surface of the main substrate, and a substrate side wall plate having a central hole separating the through chambers. Wherein the charged particles pass through the through hole and the central hole of the side wall of the substrate.
The accelerating device includes a charged particle generation mechanism and a linear acceleration mechanism, and the charged particle generation mechanism and the linear acceleration mechanism are formed in the through chamber,
The electrodes and wirings formed in the penetrating chamber are conductor films laminated by one or more methods selected from a CVD method, a PVD method, a plating method, and an electroforming method, and the upper substrate and/or the lower substrate. Characterized in that it is connected to the outer electrode formed on the upper substrate and/or the lower substrate through the contact wiring formed on
The linear acceleration mechanism is configured by arranging a plurality of electrodes (substrate side wall plate electrodes) having a conductor film formed on a substrate side wall plate having a central hole, and applying a static voltage or a high frequency voltage to the substrate side wall plate electrodes. , Characterized by accelerating or decelerating (focusing) charged particles,
The accelerating device further has a deceleration (focusing) mechanism, and the deceleration (focusing) mechanism is configured by arranging a plurality of electrodes (substrate sidewall plate electrodes) having a conductor film formed on a substrate sidewall plate having a central hole. The charged particles are decelerated (focused) by applying a reverse voltage to the charged particles on the substrate side wall plate electrode.

(22)
The present invention further has a deceleration (focusing) mechanism, and the deceleration (focusing) mechanism is an accelerating device characterized by being performed by a quadrupole magnet,
The quadrupole magnet has electromagnets arranged vertically in the vertical direction (perpendicular to the substrate surface) from the outside of the substrate having a through-hole formed in the substrate which is the passage of the charged particles. Characterized in that electromagnets are arranged on both sides in a lateral direction (a direction perpendicular to the vertical direction) from the outside of the substrate having a through chamber formed inside,
When arranging the electromagnets in the lateral direction, the substrate area at the location where the electromagnets are arranged is cut, and the electromagnets are arranged in the openings,
The cutting method is characterized by laser dicing or high pressure liquid jet dicing,
Characterized in that the coil is arranged in the main substrate on both sides of the penetration chamber,
For the coil, a conductor film (through-hole wiring) is formed in through holes penetrating the upper and lower substrates and the main substrate, and wiring for connecting the through-hole wiring is formed on the upper and lower substrates to form coil wiring. The electrodes are formed on the upper substrate and/or the lower substrate.
(23)
The present invention forms a through chamber (through chamber for coil placement) on both sides of the through chamber (through chamber for focusing charged particles), inserts a coil into the through chamber for coil placement, and inserts the coil into the through chamber for focusing charged particles. Characterized by placing on both sides,
The coil is characterized in that the coil attached to the support substrate is inserted and arranged in a through chamber for coil arrangement,
Characterizing that the coils are arranged in the upper and lower parts of the coil-arranging penetration chamber,
The coil is arranged in close contact with or close to the upper substrate and the lower substrate,
It is characterized in that a coil-formed substrate (coil-forming substrate) is attached to the upper substrate and the lower substrate to arrange the coils.

According to the present invention, the functions required for the accelerator and the mass spectrometer are formed at once in the substrate by using the LSI or the MEMS process. Therefore, the positional relationship between the functional portions (for example, the acceleration electrodes) is extremely high. Accurately formed. Moreover, since the distance between the electrodes and the passage through which the charged particles pass can be precisely formed on the order of mm or μm, the size becomes extremely small. For example, as the distance between the electrodes decreases, the electric field strength increases, and the acceleration and deceleration of charged particles can be efficiently controlled. Further, since the frequency of the high frequency supplied to the electrodes can be increased, it is possible to perform greater acceleration in a short distance. Furthermore, since each functional component can be manufactured at once, the manufacturing cost is dramatically reduced.

When the present invention is applied to a mass spectrometer, it is 4 inches to 8 inches like the present invention {diameter 100 mm to 200 mm, thickness 3 mm or less (Si substrate 2 mm, glass substrate 0.3 mm x 2), 8 inches or more} It has not been reported that a minute sample supply unit, an ionization chamber, an extraction electrode/acceleration chamber, an electric field chamber, a magnetic field chamber, and an ion detection chamber (these are referred to as functional units) were produced using a substrate. In addition, no idea such as a patent has been found. Furthermore, it has not been reported that they are implemented on the same substrate all at once, and it has novelty, inventive step, and superiority.

This mass spectrometer is ultra-compact {main body: size 6 inch wafer (50 cm ³ ) or less, weight 130 g or less} and it is a batch manufacturing, so the manufacturing cost is 100,000 yen or less {main body: size 6 inch wafer} it can. With the same performance, the conventional products are 50 cm x 50 cm x 50 cm or more and 20 kg or more, so the size (volume) is 1/2500 or less, the weight is 1/100 or less, and the price is 1/20 or less. There is enough advantage. (Of course, larger size is also possible.) Since each functional part can be manufactured collectively and with high accuracy (1 μm or less), it can be manufactured much more accurately than other parts assembly method, The detection accuracy can be expected to be more than that of the conventional one. Since the present invention is ultra-compact and lightweight, it can be carried, so that in-situ observation is possible. However, in-situ observation is extremely difficult because conventional products can hardly be carried, and this is also a great advantage.

Further, in this mass spectrometer, a coil for making a substrate is used in the magnetic field chamber. Since the coils are arranged by aligning between the substrates, the arrangement accuracy is 10 μm or less, which is very good. Moreover, the size of the coil is as small as 1 mm to 10 mm, so the overall size does not increase. A magnetic field chamber using such a substrate coil is highly novel and innovative. The price and size are small and the accuracy is high, so it has a significant advantage over conventional products. The coil is also used in the electron ionization method. This is also highly novel and inventive.

FIG. 1 is a diagram showing an example of an embodiment of a micro-accelerator of the present invention. FIG. 2 is a diagram showing an example of the particle generator 11 of the present invention. FIG. 3 is a diagram showing the structure of a linear accelerator for charged particles. FIG. 4 is a diagram showing an example of a charged particle accelerator tube using a high frequency waveguide. FIG. 5 is a diagram showing an accelerator in which a plurality of charged particle accelerators of the present invention are connected. FIG. 6 is a diagram showing an example of a method of manufacturing the charged particle accelerator of the present invention. FIG. 7 is a diagram showing an example of a method of manufacturing the charged particle accelerator according to the present invention, which is a diagram showing a process from the formation of the side wall of the substrate to the patterning of the conductor film. FIG. 8 shows a charged particle accelerator in which a glass substrate 251 is sandwiched between an upper substrate (main substrate 201U, upper substrate 202) and a lower substrate (main substrate 201B, lower substrate 203) to be attached by electrostatic coupling. It is a figure which shows the manufacturing method. FIG. 9 is a diagram showing another embodiment of the extraction electrode structure. FIG. 10 is a view showing an accelerating cavity chamber in which a plurality of substrate side wall electrodes having a central hole are arranged. FIG. 11 is an embodiment showing a method for producing an electromagnet (coil). FIG. 12 is a diagram showing a method for producing a high-performance coil in which a core having a high relative permeability μ is inserted. FIG. 13 is a diagram showing a method of manufacturing the coils arranged on the upper and lower substrates. FIG. 14: is a figure which shows the quadrupole electromagnet structure produced by the coil (electromagnet) of this invention. FIG. 15 is a view showing charged particle passage cavities such as the deflection electromagnets 25, 30, 34, 37 in FIG. 1 and electromagnets arranged therein. FIG. 16 is a diagram in which the micro-accelerator 10-1 having the circular accelerator (synchrotron) 8-1 shown in FIG. 1 is connected to the circular accelerator 8-2 which is one size larger, and is a double synchrotron (or 2). It is a figure which shows a cycle synchrotron. FIG. 17 is a diagram showing a schematic diagram in the case where the circular accelerator 8 is divided and manufactured on a substrate. FIG. 18 is a diagram showing a microwave ion source of the present invention. FIG. 19 is a diagram showing an embodiment of the mass spectrometry of the present invention. FIG. 20 is a diagram showing an example of a method for manufacturing a quadrupole mass spectrometer. FIG. 21 is a diagram illustrating an example of a structure and method for attaching a quadrupole electrode to a substrate. FIG. 22 is a diagram illustrating another example of the structure and method for attaching the quadrupole electrode to the substrate. FIG. 23 is a diagram showing a method for producing a quadrupole electrode of the present invention. FIG. 24 is a diagram illustrating a method of attaching the quadrupole electrode rod 407 to the substrate. FIG. 25 is a diagram illustrating a method of arranging a quadrupole electrode inside a mass spectrometry chamber using a thin film forming method. FIG. 26 is a diagram showing an octopole electrode type structure. FIG. 27 is a schematic diagram showing a fan-type magnetic field type mass spectrometer having a penetration chamber, which is a mass analysis chamber in which a fan-shaped magnetic field acts, on the main substrate of the present invention. FIG. 28 is a diagram showing a mass spectroscope for detecting ions with an ion detector arranged in multiple directions for ions that have been subjected to a magnetic field in the mass spectroscope. FIG. 29 is a diagram showing a double-focusing mass spectrometer of the present invention. FIG. 30 is a diagram showing one design guideline for the single-focusing sector magnetic field analyzer and the double-focusing sector magnetic field analyzer. FIG. 31 is a diagram showing the FTICR of the present invention. FIG. 32 is a diagram showing a structure for increasing the size of the ICR chamber. FIG. 33 shows an FTICR in which the coil of the present invention is arranged. 34 is an FTICR in which the coil of the present invention different from that of FIG. 33 is arranged. FIG. 35 is a diagram showing an ionization method different from that described in FIG. FIG. 36 is a diagram showing another embodiment of the ionization method. FIG. 37 is a diagram for explaining the atmospheric pressure chemical ionization method. FIG. 38 is a diagram showing a method for manufacturing an ionization chamber having a steeple electrode. FIG. 39 is a diagram showing an embodiment in which continuous flow (CF)-FAB ionization, which is a type of fast atom bombardment method (FAB), is applied to the present invention. FIG. 40 is a diagram showing a method for manufacturing an ion trap mass spectrometer. FIG. 41 is a diagram showing an ion trap mass spectrometer in which charged particles pass through the end cap electrode 609. FIG. 42 is a diagram showing an ion detection chamber in which a large number of dynodes according to the present invention are arranged. FIG. 43 is a diagram showing one embodiment of a method for producing the parallel plate electrode shown in FIG. 42. FIG. 44 is a diagram showing an embodiment in which the central hole of the present invention is applied to a channel type secondary electron multiplier. FIG. 45 is a schematic diagram (cross-sectional view perpendicular to the substrate surface) of the mass spectrometer of the present invention. FIG. 46 is a diagram showing a double-focusing mass spectrometric section (electric field section+magnetic field section) (plan view) and (b) multiple ion simultaneous detection method (plan view). FIG. 47 is a diagram showing an electron ionization section (cross-sectional view). FIG. 48 is an image completed drawing of the final product (only the main body) of the present invention. FIG. 49 is a diagram showing an ion trap mass spectrometer formed in the vertical direction. FIG. 50 is a diagram showing a method or apparatus for forming a pattern on a side wall of a substrate through hole or a substrate recess. FIG. 51 is a diagram showing a through hole side wall etching apparatus. FIG. 52 is a diagram showing a method of producing a through chamber of an accelerator or a mass spectrometer of the present invention using a mold. FIG. 53 is a diagram showing an exposure apparatus in which light emitters are arranged on the front surface and the rear surface. FIG. 54 is a diagram showing a method of forming a central hole using the mold ingot method. FIG. 55 is a diagram showing a method of forming a central hole in a substrate cut at a position approximately half the height of the central hole in the portion where the central hole is formed. FIG. 56 is a diagram ((b), (c)) for explaining a method for polishing the inner wall of the through-hole to obtain a smooth and smooth surface ((a)) and a method for transferring a pattern to the inner wall of the through-hole. is there. FIG. 57 is a plan view of the synchrotron system substrate type ion implantation apparatus of the present invention viewed parallel to the substrate surface. FIG. 58 is a diagram (plan view) showing a synchrotron type ion implanter having two orbits. FIG. 59 is an enlarged view of a state of a connection region between the ion emission line 2143 and the second-stage annular orbit 2145 (a plan view parallel to the substrate). FIG. 60 is a view showing a cross section of the track connecting portion of the ion implantation apparatus stacked in two stages. FIG. 61 is a diagram showing an example of an RFQ (Radio Frequency Quadrouple) type linear accelerator. FIG. 62 is a diagram showing a method of manufacturing the RFQ linear accelerator shown in FIG. FIG. 63 is a diagram showing another acceleration method (IH type) of the linear accelerator. FIG. 64 is a diagram showing an acceleration method in another linear acceleration chamber.

According to the present invention, in a substrate or a thin plate (main substrate or first substrate), a through groove (also referred to as a recess) or a through hole (hereinafter also referred to as a cavity) is formed in a thickness direction thereof, and electrons or This is an accelerator in which charged particles such as ions move at high speed. A substrate or a thin plate (second substrate) is adhered on the cavity above the side walls of the substrate on both sides of the cavity, and a substrate or a thin plate (third substrate) (main substrate in the case of a through groove) is also formed under the cavity. The bottom surface of the substrate) is attached below the sidewalls of the substrate on both sides of the cavity. Therefore, the cavity is an airtight space in which the upper and lower sides are sandwiched by the second substrate and the third substrate, and the lateral side is sandwiched by the first substrate side walls. In a part of the cavity which is an airtight space, part or all of the substrate side wall above and/or below and/or on both sides of the cavity is hollowed out (or a hole is formed), and the hollowed out part or hole is formed. Gas (air, oxygen, nitrogen, etc.) in the cavity is exhausted from (hereinafter, also referred to as a vacuum transmission hole), and the cavity is in a predetermined low pressure state (for example, a low pressure state close to vacuum).

Electrons and ions (hereinafter, charged particles) that pass through the inside of the cavity due to the magnetic field created by the coil, etc., where coils, electromagnets, and permanent magnets are placed above and/or below the cavity in part of the inside (or outside of the cavity). Receives a force to accelerate and/or deflect. And/or in a part of the cavity (or outside of the cavity), a coil is arranged on one side and/or the other side of the cavity, and a magnetic field generated by the coil causes charged particles passing through the cavity to generate a force. Receive, accelerate and/or deflect. Alternatively and/or in some part (or outside of the cavity), electrodes are arranged above and/or below the cavity, and the electric field created by the electrodes causes the charged particles passing through the cavity to receive a force to accelerate and/or accelerate. To deflect. And/or in a part of the cavity (or outside of the cavity), electrodes are arranged on one side and/or the other side of the cavity, and the electric field created by the electrodes causes charged particles passing through the cavity to generate force. Receive, accelerate and/or deflect.

A charged particle generation part (chamber) is formed in the first substrate, and charged particles generated in the charged particle generation part are formed in the first substrate (this may be referred to as a (charged particle) introduction cavity). ), it is also possible to lead to a cavity capable of accelerating charged particles (this is also called a (charged particle) accelerating cavity). Alternatively, an entrance to the outside of a cavity (which may be referred to as a (charged particle) (external) introduction cavity) in which an external charged particle generator is formed in the first substrate (this is referred to as (charged particle) (external)) It may be referred to as an introduction cavity inlet), and charged particles can be guided to the cavity in the main substrate or the acceleration cavity through the external introduction cavity. The charged particles moving in the accelerating cavity go out from a charged particle discharge outlet (which may be referred to as a (charged particle) discharge outlet) connected to the first substrate and the outside. The charged particle discharge outlet and the acceleration cavity are connected by a cavity formed in the first substrate (this is also called a (charged particle) discharge cavity). The accelerated charged particles exit from the charged particle discharge outlet and can be applied to various purposes such as medical use, analytical use, and product reforming use. Alternatively, there is no charged particle discharge outlet, and ion analysis is performed in an analysis room or the like formed in the main substrate.

The accelerator of the present invention (this may be referred to as a substrate accelerator) can be produced by using a photolithography method, a laser patterning method, a die forming method using a die, a punching method produced by punching, or the like. Therefore, if the cavity width or cavity depth is 0.1 mm to 0.5 mm, or 0.5 mm to 1.00 mm, or 1.0 mm to 10 mm, or 1 cm to 2 cm, or 2 cm to 10 cm, or 10 cm or more is extremely accurate. Also, linear, polygonal, circular, elliptical, hyperbolic, or other curvilinear shaped accelerators can be fabricated with desired dimensions. For example, in the case of a linear shape, a large number of linear cavities are formed in one substrate, the linear cavities are cut out in the length direction of the cavity (for example, by the dicing method), and the cutouts are used as cavities. If they are connected to each other, a linear accelerator of arbitrary length can be manufactured.

For example, the first substrate is a Si substrate, the acceleration cavity width is 5 mm, the acceleration cavity depth is 5 mm, and multiple coils (10 mm in length) are formed in the first substrate on both lateral sides of the acceleration cavity to accelerate the acceleration. In the case where glass substrates (second substrate and third substrate) having a thickness of 0.5 mm are attached to the first substrate above and below the cavity and a plurality of coils (20 mm in length) are arranged above and below the first substrate, When the substrate size is 500 mm × 500 mm (or when it is a circular wafer (diameter 500√2=707 mm or more) that can be manufactured in this size), one linear accelerator has a length of 500 mm, a width of 15 mm, and a height of 15 mm. The length is about 6 mm, and from one board (the second board and the third board are attached to the first board, and the coils are arranged on the top and bottom and/or the left and right of the first board), about 33 pieces (each one is a unit) Called accelerator) can be taken. When 10 unit accelerators are connected, a linear accelerator of 5 m is formed, and thus a 16.5 m linear accelerator can be formed from one substrate. Therefore, if it is a 1 km accelerator, 61 substrates are enough.

In the case of a circular accelerator as well, in the case of a microminiature accelerator that can be manufactured using only one substrate, a large number of circular orbits (circular cavities) of different sizes are manufactured and cavities that connect them are formed (this is also called a connection cavity). ) Is produced, the velocity is increased stepwise, the orbit is moved accordingly, and the final orbit (usually the outermost) is accelerated to the final velocity to discharge the charged particles to the outside. In the present invention, since all the patterns of cavities, coils, electrodes, etc. can be formed at the same time, the number of process steps (the number of manufacturing steps) does not change regardless of the number of circular orbits, and the cost hardly changes. For example, a circular orbit with a radius of 10 mm is first used, the width of the cavity is 5 mm, the size of the next circular orbit is 25 mm, the size of the next circular orbit is a radius of 40 mm, and the radius is increased by 15 mm. When the circular accelerator is used (the cavity widths are all 5 mm and the space between the cavities is 10 mm), 16 circular orbits can be made in a 500 mm circular wafer. These are connected in sequence and accelerated in each circular orbit. Circular motion at a speed of 10 m/sec in the first small circular orbit, quadruple speed in the next circular orbit, and 10 × 4 ^n-1 m/sec at the ^nth , the final 16th circular orbit. Can reach 100,000 km/sec, which is 1/3 the speed of light. Ultrafast charged particles can be produced with one wafer.

When the size of the circular accelerator is large, the substrates can be connected to each other to fabricate the same as in the linear accelerator. For example, if the size of one substrate is 500 mm × 500 mm, and the diameter of the circular accelerator is 1000 mm (1 m), make 1/4 yen for each of 4 substrates and Just connect the sheets. When manufacturing a larger circular accelerator, for example, in the case of a 10000 mm (10 m) circular accelerator, a substrate of 1000 mm×1000 mm may be connected to about 100 substrates.

The present invention is one in which an accelerator is formed on a substrate, and a cavity through which charged particles such as an acceleration cavity passes, an electrode for generating an electric field for accelerating/decelerating or deflecting charged particles, and a magnetic field for accelerating/decelerating or deflecting charged particles. It is equipped with a coil and electromagnet that generate it. FIG. 1 is a diagram showing an example of an embodiment of a micro-accelerator of the present invention. The micro-accelerator is mounted on one substrate 9, a charged particle generator 11, a linear (type) accelerator 13, and various types. Electromagnets 15, 17, 19, 21, 22, 23, 26, 28, 29, 31, 32, 35, 36, deflection electromagnets 25, 30, 34, 37, cavities 12, 14, 16, 18, through which charged particles pass. It has 20, 24, 27, 33, 38, 40 and a linear accelerator 39. Since these are examples, those described here may be omitted, further added, or one having another function may be added.

The charged particles generated by the charged particle generation device 11 pass through the cavity 12 and are accelerated by the linear acceleration device 13, pass through the cavity 14 and are deflected by the deflection electromagnet 15, and further pass through the cavity 16 and are deflected by the deflection electromagnet 17. And/or converge and further deflects the trajectory through the cavity 18 with the deflection electromagnet 19, passes through the next cavity 20, and through the inflector 21 to the storage ring 24 which is the cavity through which charged particles pass in the circular accelerator 8. Incident. A linear accelerator 42 may be provided in the middle of the cavity 20 to control the velocity of charged particles entering the inflector 21. Further, another deflecting electromagnet, an accelerating electrode, a decelerating electrode, a linear accelerating device, etc. may be provided on the way from the charged particle generator 11 to the inflector 21. In addition, another deflection electromagnet, an acceleration electrode, a deceleration electrode, a linear acceleration device, a focusing electromagnet, etc. may be provided on the way.

The charged particles that have entered the storage ring 24 of the circular accelerator 8 from the inflector 21 are converged by the focusing electromagnet 22 (for horizontal direction) and the focusing electromagnet 22 (for vertical direction), and are deflected/accelerated by the deflection electromagnet 25. After entering the storage ring 27, the high frequency accelerating cavity 29 again accelerates the beam, and the focusing electromagnet 26 (for the vertical direction) and the focusing electromagnet 28 (for the horizontal direction) converge and the deflection electromagnet 30 deflects and accelerates the next storage. It enters the ring 33, and again, it is converged by the focusing electromagnet 31 (for vertical direction) and the focusing electromagnet 32 (for horizontal direction), deflected and accelerated by the deflection electromagnet 34, and enters the next storage ring 38, and again (vertical direction). Focusing electromagnet 35 (for horizontal direction) and focusing electromagnet 36 (for horizontal direction) are used for focusing, then deflection electromagnet 37 is used for deflection/acceleration, and then the next storage ring 24 is entered. In this way, the charged particles continue to rotate while accelerating in the storage rings 24, 27, 33, 38, and when the desired velocity and the desired number of charged particles are obtained, the charged particles are guided to the outside. (Also referred to as charged particle discharge cavity) 40, and is taken out from the outlet 41 of the charged particle discharge cavity 40. A linear accelerator 39 may be provided in the middle of the charged particle discharge cavity 40 to further accelerate the charged particles. In addition, another deflection electromagnet, an acceleration electrode, a deceleration electrode, a linear acceleration device, a focusing electromagnet, etc. may be provided on the way.

As described above, the storage rings 24, 27, 33, and 38 form a connected annular passage. Further, various cavities have holes formed at various places, the holes are connected to a vacuum drawing line, and the vacuum drawing line is further connected to an external vacuum pump, and the pressure of each of the various cavities is reduced to a state close to a vacuum. Further, various cavities have holes formed at various places, and a gas such as an inert gas such as nitrogen, He, Ar or the like can be introduced through the holes, and the inside of the cavities can be appropriately cleaned or gas purged.

As shown in FIG. 1, the present invention also arranges an electron or ion particle generator 11 in the main substrate (first substrate) 9. An example of this particle generator 11 is shown in FIG. The particles shown in FIG. 2 (the ion generator is an ion generator having a parallel plate type electrode. FIG. 2A is a sectional structure perpendicular to the substrate plane (in the substrate thickness direction), and FIG. Is a plan view of the structure.In the main substrate 51, a cavity 76 which is a plasma generation chamber, and charged particles such as electrons, protons and various ions generated in the plasma generation chamber 76 are taken out and guided to an accelerator (13 in FIG. 1). A cavity 77 is formed, and a second substrate (upper substrate) 53 is attached to the upper surface of the main substrate 51, and a third substrate (lower substrate) 52 is attached to the lower surface of the main substrate 51.

In the plasma generation chamber 76, a (lower) electrode 54 is formed on the lower substrate 52, and the periphery thereof is covered with an insulating film 55 such as a silicon oxide film (or a silicon nitride film or a silicon oxynitride film) which is laminated. .. An (upper) electrode 58 is formed on the upper substrate 53, and an insulating film 59 such as a silicon oxide film (or a silicon nitride film or a silicon oxynitride film) is laminated and covered (protected) around the (upper) electrode 58. These electrodes 54 and 58 are patterned and arranged so as to face each other, and the second substrate 53 and the third substrate 52 are attached to the upper and lower surfaces of the main substrate 51. A contact hole is formed in the lower substrate 52, a contact electrode (conductor film) 56 is formed in the contact hole, and an extraction electrode 57 is formed on one surface of the lower substrate 52. Contact holes are also formed in the upper substrate 53, contact electrodes 60 are formed in the contact holes, and lead electrodes 61 are formed on one surface of the upper substrate 53. These electrodes 57 and 61 are arranged outside when the upper and lower substrates 52 and 53 are attached to the main substrate 51, a matching circuit 78 and an AC or high frequency electrode 79 are connected between these electrodes, and one electrode Is grounded.

The upper substrate 53 is provided with a gas introduction hole 71, gas exhaust holes 72, 73 for exhausting gas in the plasma generation chamber 76 to lower the pressure, and gas exhaust to the cavity 77 on the accelerator side to lower the gas pressure. The hole 74 is opened. A seal portion 62 is formed on the upper surface side of the upper substrate 53 in each of the gas introduction hole 71 and the gas exhaust holes 72, 73 and 74, and the gas introduction line 63 and the gas exhaust lines 64 and 65 are formed in the seal portion 62. , 66 are connected, and are hermetically sealed so that an external gas (air or the like) does not enter the plasma generation chamber 76 or the cavity 77 from the outside. The gas exhaust lines 64 and 65 are connected to vacuum pumps 68 and 69, the plasma generation chamber 76 is lowered to a predetermined pressure (for example, 0.1 atm to 0.001 atm), and in that state, the upper and lower electrodes 54 and 61 are passed through the extraction electrodes 57 and 61. When a high-frequency voltage is applied to 58, the gas is plasma-ionized to generate electrons or ions to generate charged particles. For example, when argon gas (Ar) is introduced, Ar+, electrons, etc. are generated. When methane (CH4) gas is introduced, various ions (C-, CH+, CH2+, CH3+, CH4+, etc.) are generated. If Arsenic gas (As) is introduced, As+ and electrons will be generated.

The inter-electrode distance d1 between the electrodes 54 and 58 is almost the same as the thickness of the main substrate 51 (strictly speaking, the thickness of the main substrate minus the upper and lower electrode thicknesses). Since a high electric field of 1 KV/cm can be applied by applying, plasma can be generated at a low voltage. In order to apply a higher electric field, in addition to applying a high voltage, the thickness of the main substrate can be reduced, or if the thickness of the main substrate (whole) cannot be reduced, the distance d1 only between the electrodes is reduced. For this purpose, the main substrate may be etched by a predetermined thickness to form an electrode on the bottom thereof, or a protrusion may be provided on the upper substrate or the lower substrate and the electrode may be formed on the protrusion. The protrusion may be manufactured by attaching another substrate to the upper substrate or the lower substrate, and the upper substrate or the lower substrate having the protrusion may be attached above and below the main substrate.

The gas exhaust line 66 is also connected to the accelerator side cavity 77 and connected to the vacuum pump 70, but the pressure in the accelerator side cavity 77 is considerably lower than that in the plasma generation chamber 76 (for example, 10 ^{−3 ).} atm to ^10-12 atm). Therefore, a part of the plasma generated in the plasma generating chamber 76 is introduced into the accelerator cavity 77. Further, since the accelerator cavity is connected to the accelerator cavity 77, charged particles are attracted to the accelerator cavity 77. Although the plasma generation chamber 76 is described as being larger than the cavity 77 on the accelerator side, the cavity 77 on the accelerator side may be large because it may have an area where plasma can be generated. In that case, since the pressure in the accelerator-side cavity 77 is lower, an opening/closing valve may be provided between the plasma generation chamber 76 and the accelerator-side cavity 77, or between the plasma generation chamber 76 and the accelerator-side cavity 77. May be partly narrowed. The plasma flow flows in the direction of 80 and enters the accelerator side.

The extraction electrode 83 may be disposed between the plasma generation chamber 76 and the cavity 77 on the accelerator side to extract the ions generated in the plasma generation chamber 76. The lead electrode 83 has a structure in which the periphery of the substrate side wall 81 of the main substrate 51 having the central hole 84 is covered with a conductor film 82. The substrate side wall 81 of the main substrate 51 is formed so as to project around the inner surface of the accelerator cavity 77 as can be seen from the sectional view (elevation view) 2(a) and plan view 2(b), and the central hole 84 is formed in the center. Has been formed. Further, a conductor film wiring 85-1 is formed on the lower surface of the upper substrate 53 (upper surface of the inner side surface of the cavity 77 on the accelerator side), and the conductor film wiring 85-1 is connected to the conductor film 82. The contact hole formed in the upper substrate 53 and the conductor film 86 formed therein are connected to the conductor film wiring 85-1, and the conductive film 86 in the contact hole is the outer electrode/wiring 87 formed on the upper surface of the upper substrate 53. Connect to. As a result, a voltage for extracting ions or electrons from the outer electrode/wiring 87 can be applied to the extraction electrode 83.

A voltage having an opposite charge to that of the ions guided to the addition device side is applied to the extraction electrode 83 of FIG. 2, but since the extraction electrode 82 in the case of FIG. 2 directly faces the ions, it enters the central hole 84 and is accelerated. In addition to the ions, many ions collide with the side surface of the extraction electrode 82, so that the extraction efficiency of the ions may deteriorate. Therefore, the size of the central hole 84 may be adjusted to facilitate passage of ions. For example, the hole size is the same as the cavity 77 on the accelerator side, that is, the substrate side wall 81 is not provided, and the peripheral electrode 85 of the cavity 77 on the accelerator side (electrode wiring 85-1 on the lower surface of the upper substrate, side electrode 85- of the main substrate 51- 2. If only the annular (rectangular band) electrode in which the electrode wiring 85-3 on the lower surface of the lower substrate and the side surface electrode 85-4 of the main substrate 51 are continuously connected) is provided, the central hole 84 is provided in the substrate side wall 82. This is the case, for example, when the size of the central hole is changed to an optimum value and the conductor film 82 is formed thereon. In addition, before the extraction electrode 83, a substrate side wall having a central hole not provided with a conductor film is provided on the side of the ion generating chamber 76 to block the vertical wall electrode on the front side of the extraction electrode 83 so that ions are directed toward the central hole. There is also a way to go to.

In addition, there is a method shown in FIG. FIG. 9 is a diagram showing another embodiment of the extraction electrode structure. 9A is a vertical sectional view, and FIG. 9B is a plan sectional view. In FIG. 9, a focusing electrode 89 exists before the extraction electrode 83 and between the ion generating electrodes 54 and 58. Although the substrate side wall 81 of the extraction electrode 83 in FIG. 2 is substantially vertical to the side faces of the upper and lower substrates 53, 52 and the main substrate 51, in the present embodiment, the substrate side wall is inclined and the accelerator side cavity 77-2. (Cavity on the right side (acceleration cavity side) with the substrate side wall 81 sandwiched) is gradually narrowed and connected to the central hole 84. It can be said that the size of the central hole 84 gradually decreases toward the cavity 77-2 on the accelerator side. It can also be said that, when this portion is the entrance 88 of the cavity 77-2 on the accelerator side, the entrance 88 becomes gradually smaller toward the cavity 77-2 on the accelerator side. On the contrary, the size of the central hole 84 is increased by tapering toward the accelerator cavity 77-1 (cavity on the left side (on the side of the electrode for ion generation) with the substrate side wall 81 interposed). Can also It can be said that the substrate side wall 51-2 is gradually thickened toward the accelerator cavity 77-2. Further, as shown in FIG. 9B, when the exit of the plasma (ion) generation chamber 76 is larger than the entrance of the accelerator-side cavity 77, the exit 48 is gradually narrowed in plan view. Is formed in. (In the case shown in FIG. 2, the exit size of the plasma (ion) generation chamber 76 and the entrance size of the cavity 77 on the accelerator side are suddenly changed as shown in FIG. 2B.) A conductor film electrode 89 is formed on the inclined main substrate side surface of the entrance portion 88 of the cavity 77, and the conductor film electrode 89 is connected to the conductor film wiring 45 formed on the upper substrate 53 or the lower substrate, and its conductivity The body film wiring 45 is connected to the outer electrode 47 through the contact hole formed in the upper substrate 53 or the lower substrate and the conductor film wiring 46 therein.

The conductor film electrode 89 is also formed so as to extend to the side surface (inclined in plan view) of the main substrate at the exit of the plasma (ion) generation chamber 76. A conductor film electrode 82 is formed on a part of the central hole and on the side surface of the substrate side wall 81 of the cavity 77-2 on the accelerator side, and is connected to the outer electrode 87. Since the conductor film 89 and the conductor film 82 are not connected, different voltages can be applied from the outer electrodes 47 and 87. That is, a voltage having the same charge as that of the ions is applied to the conductor film 89 so that the ions converge on the central portion of the cavity. Further, since a voltage having a charge opposite to that of the ions is applied to the extraction electrode 82, the ions are attracted to the extraction electrode 82 and accelerated, and pass through the central hole 84 of the cavity 77-1 to the adjacent acceleration cavity 77-2. enter. If the acceleration is weak, an acceleration electrode (electrostatic lens) having a conductor film laminated on the side wall of the substrate having a central hole is further provided in the acceleration cavity 77-2 to accelerate the ions. If it is accelerated too much, a reverse potential may be applied to form a deceleration electrode. According to the present invention, a large number of accelerating electrodes and decelerating electrodes can be provided even at a short distance, and the outer electrodes can be easily produced respectively, so that ions are passed through the accelerating cavity side cavities 77-1 and 77-2 at a desired velocity. be able to. As described above, according to the structure shown in FIG. 9, the extraction electrodes attract ions to the cavity 77 on the accelerator side, and the ions are converged by the same potential as the ions applied to the exit portion and the entrance portion (that is, toward the center side). Since the exit portion and the entrance portion are gradually narrowed, the number of ions that repel and are pushed back even if the exit portion and the entrance portion have the same potential as the ions is small. Most of the potential (reverse potential of the extraction electrode) enters the cavity 77-2 on the accelerator side, and further accelerates to the accelerator side because it is accelerated. It is also possible to divide the tapered conductor film 89 into several parts in the ion traveling direction and apply different voltages to the respective electrodes. For example, if the voltage is gradually weakened in the traveling direction of the ions, the electric field applied to the ions can be made constant or can be weakened little by little. (The distance between the ion and the electrode is smaller when viewed from the ion traveling direction, so the electric field becomes stronger when the same voltage is applied.) As a result, the ion is stably propagated in the traveling direction (acceleration cavity 77-2 side). Can be sent to. Alternatively, the focusing voltage and the accelerating voltage may be selected and applied to the divided conductor film 89 electrodes to accelerate the ions while focusing. As described above, by applying the voltage while dividing the electrode of the conductor film 89 and adjusting the electrodes individually, it becomes possible to efficiently send out the ions to the acceleration cavity 77-2 side.

Alternatively, a large number of ions can be guided to the cavity 77-2 on the accelerator side by applying a potential having a reverse potential to the ions to the inclined electrode 89 and further applying a potential having a reverse potential higher than the potential to the extraction electrode. it can. That is, since the electric field increases as the ions 49 advance, the ions 49 gather in the center and proceed.

Next, the processes of the plasma (ion) generator, the cavity on the acceleration cavity side, the extraction electrode, and the acceleration (deceleration) electrode shown in FIGS. 2 and 9 will be described. First, a plasma (ion) generator having a cavity without a central hole will be described. As the main substrate (first substrate) 51, a conductor substrate (metal such as Cu, Al, Ti, Zn or an alloy thereof, conductive C (including carbon nanotube, graphene, etc.), conductive plastic, conductive ceramic, etc. (Including also), semiconductors such as Si, SiC, C, compound semiconductors, plastics, glass, quartz, alumina (Al ₂ O ₃ ), AlN, polymer resins, insulators such as ceramics, and the like, and composites thereof can be used. .. Optimal substrates for the upper substrate (second substrate) and lower substrate (third substrate) have contact holes inside, so plastic, glass, quartz, alumina (Al ₂ O ₃ ), AlN, polymer resin Although it is an insulator such as ceramic, the same material as the main substrate 51 can be used.

A photosensitive film is attached on the main substrate 51 by a coating method, a sticking method, or the like, and the photosensitive film is patterned by an exposure method. The photosensitive film may be attached after the insulating film, the material for the etching stopper or the adhesion improving film with the photosensitive film is attached between the main substrate 51 and the photosensitive film. The main substrate 51 is removed by etching using the patterned photosensitive film as a mask to form a through chamber penetrating from the upper surface to the lower surface of the main substrate 51. In order to form the through chamber according to the dimensions, it is desirable that the side surface with small side etching is substantially vertical, but it may not be vertical if side etching can be controlled. When the main substrate is a Si substrate, the surface is oxidized or nitrided, a photosensitive film sheet is attached after laminating an insulating film such as a SiO2 film or SiN film, or a resist is applied, followed by an appropriate heat treatment (prebaking, etc.). ) And open a predetermined portion of the window by an exposure method. The insulating film or the like is vertically etched (anisotropic etching) from this window, and the window opening portion is vertically etched (there are various types such as anisotropic etching, DRIE, and Bosch method) using these as masks to form the through chamber. Create. When the conductor film pattern is formed in the penetration chamber, it may be performed here. When the main substrate is a semiconductor substrate or a conductor substrate, the conductor film is formed after forming the insulating film on the surface of the main substrate and the side surface of the through chamber. A photosensitive film is formed on the surface and side surfaces of the main substrate 51 by a method of attaching a photosensitive film sheet to the main substrate 51, a resist coating method, an electrodeposition method of the photosensitive film, or the like. Next, the photosensitive film patterning on the surface and the side surface of the main substrate 51 is performed by an exposure method (oblique exposure method, using an exposure apparatus having a deep depth of focus). Next, the conductor film is etched by a wet etching method or an isotropic dry etching method using the pattern of the photosensitive film as a mask to form a desired conductor film pattern. After this, if necessary, a protective film for an insulating film is formed on the conductive film pattern. For the portions of the upper and lower substrates to be connected to the conductor films later, the conductor film of the connection portions is opened by using the same photolithography method+etching method. Next, in order to improve the connection with the conductor films on the upper and lower substrates, the portions where the windows are opened may be made convex (raised up a little) with the conductor films. As this method, the conductor film is laminated again and the same photolithography method + etching method is used to leave the conductor film only in the connection portion, or the metal is formed on the connection portion by the selective CVD method or the plating method. Etc. may be laminated.

A conductor film pattern serving as an electrode is previously formed on the upper substrate and the lower substrate. When the upper and lower substrates are insulating substrates such as a glass substrate, a quartz substrate, and a plastic substrate, the conductor film can be directly laminated, but the conductor film may be laminated after the insulating film is laminated to improve the adhesion. The conductor film is Cu, Al, Ti, W, Mo, Au, Cr, Ni, conductive C, conductive PolySi, conductive plastic, or an alloy of these, a composite film, a laminated film, or the like. A CVD method, a PVD method, a plating method, a coating method, a screen printing method, a combination thereof, or the like can be used. After stacking the conductor films, a photosensitive film pattern is formed by using a photosensitive film by an exposure method or the like, and the conductor film electrodes and necessary wirings are formed using the photosensitive film pattern as a mask. As the etching of the conductor film, dry etching or wet etching can be used. After forming the conductor film pattern, it may be covered with an insulating film or the like to form a protective film. When covered with an insulating film or the like, the same photolithography method+etching method is used for the connection portion with the conductor film pattern formed on the upper and lower substrates to open the conductor film of the connection portion. Next, in order to improve the connection with the conductor films on the upper and lower substrates, the portions where the windows are opened may be made convex (raised up a little) with the conductor films. As this method, the conductor film is laminated again and the same photolithography method + etching method is used to leave the conductor film only in the connection portion, or the metal is formed on the connection portion by the selective CVD method or the plating method. Etc. may be laminated. After that, the contact hole, the conductor film in the contact hole, and the conductor film and the electrode on the contact hole and other portions may be formed. In addition, a gas introduction hole or an opening for vacuuming may be provided in the upper and lower substrates. This opening can be formed by dry etching or wet etching.

Next, the upper and lower substrates are attached to the main substrate on which the penetrating chamber and the conductor film wiring pattern are formed while pattern matching. In the connection between the conductor film of the main substrate and the conductor films of the upper and lower substrates, if the conductor film patterns are formed so that the connection regions of the main substrate and the conductor films of the upper and lower substrates are overlapped with each other, the connection is facilitated. A conductive adhesive (adhesive also includes a low melting point solder alloy) is attached and bonded to the connection portion between the conductor films. After the bonding, a predetermined heat treatment is performed to ensure the connection. Even if an adhesive is not used, the connection can be surely made by a heat treatment or a fusion method around the melting point of the conductor film. If pressure is applied, the conductor films can be connected to each other even by heat treatment below the melting point. Other parts can also be bonded by a bonding method using an adhesive, a room temperature bonding method, a diffusion bonding method, or a high temperature bonding method. When the main substrate 51 is a semiconductor substrate such as Si or a conductor substrate, and the upper and lower substrates are glass substrates, quartz substrates, alumina substrates, etc., they can be bonded by using the anodic bonding method. It is also possible to connect to the conductor film of the main substrate through the contact holes provided in the upper and lower substrates. With or without an adhesive, after joining, use the openings provided in the upper and lower substrates to stack a conductor film on the connection using selective CVD, plating, or electroforming. it can. Furthermore, since the conductor film can be laminated on the conductor film portion not covered with the protective film or the like, reliable connection can be performed. For example, connect a quartz tube, a glass tube, a heat-resistant plastic tube, or a metal tube such as SUS to the opening (a heat-resistant plastic packing may be interposed in the contact part), and then a reactive gas (for example, WF6 gas). ) Is introduced into the penetrating chamber of the main substrate, and a reactive gas is caused to flow through the penetrating chamber of the main substrate while being pumped from another opening, and heat treatment is performed at a predetermined temperature, thereby connecting the conductor films to each other. A conductor film (for example, a W film) can be selectively stacked on the exposed portion of the conductor film. Further, by flowing a plating solution (copper or various solder plating solutions) through these tubes and energizing from the outer electrode, the plating film can be laminated on the exposed portion of the conductor film (copper or various solder plating films). Then, if a predetermined heat treatment is performed, the connection of the connection portion becomes more reliable.

In the above, the supporting substrate is not used for forming the penetrating chamber of the main substrate 51, but the penetrating chamber can be formed by using the supporting substrate. When the substrate is deformed due to stress or the like after the penetration chamber of the main substrate 51 is formed, a supporting substrate may be used. A support substrate is attached to the main substrate, and a surface of the support substrate and the main substrate surface on the side of the body are patterned with a photosensitive film or the like, and the main substrate is etched to form a through chamber in the main substrate. It suffices to etch until it reaches the supporting substrate. When the support substrate is later removed, the support substrate and the main substrate may be attached using a softening adhesive or a low melting point metal (alloy) (adhesive A). After the main substrate and the supporting substrate are attached, the through chamber is formed in the main substrate by the method described above. At this time, the supporting substrate is also etched, but the etching of the supporting substrate can be reduced if an etching method with a high selection ratio is used. After that, the insulating film, the conductor film, the protective film, and the patterning thereof are the same, but since the supporting substrate is removed, it is desirable to remove the film at the connecting portion by etching. Next, the upper substrate or the lower substrate is attached to the opened main substrate while aligning the patterns. When using an adhesive or the like (referred to as the adhesive B), it is necessary to select an adhesive or the like that does not come off or shift at the temperature at which the supporting substrate is removed. For example, the curing temperature T _B of the adhesive _B may be a thermosetting adhesive lower than the softening temperature (melting point) T _A of the adhesive (metal) A. After bonding the upper substrate or the lower substrate in the main board, it is possible to separate the supporting substrate from the main substrate by heat treatment at T _A or higher. Alternatively, the adhesive A may be used as a light release adhesive, the adhesive B may be used as a thermosetting adhesive, and the upper substrate or the lower substrate may be bonded with the adhesive B, and then the support substrate may be peeled off by light irradiation. Then, the other substrate (upper substrate or lower substrate) is attached.

It is also possible to attach the upper substrate or the lower substrate from the beginning instead of the supporting substrate. The upper substrate and the main substrate are attached to each other, and patterning of the main substrate and a through chamber are formed from the opposite side. At this time, it is desirable to set etching conditions with a high selection ratio so that the upper substrate is not etched much. When patterns such as a conductor film are required on the upper substrate or the lower substrate, these patterns are formed and then attached to the main substrate. In particular, when the pattern formation surface faces the main substrate side, a pattern such as a conductor film is previously formed on the upper substrate or the lower substrate. The pattern surface of the upper substrate or the lower substrate is attached to match the pattern surface of the main substrate. The pattern surface of the main substrate matches the pattern of the through chamber when the through chamber is formed in advance, and the pattern surface of the conductive film when the main substrate has a pattern surface such as the conductive film. May be. If the through chamber is formed after deposition, less precise pattern alignment is required during deposition. After the through chamber is formed, an insulating film, a conductor film, and a protective film are stacked and these are patterned. At this time, since it is necessary to form electrodes/wirings on the upper substrate and/or electrodes/wirings are formed on the sidewalls of the through chamber, a photosensitive sheet method, an electrodeposition resist method, an exposure method with a high depth of focus, or a rotary exposure method. Then, a photosensitive film pattern is formed using a diagonal exposure method or the like, and a pattern of a conductor film or the like is formed by wet etching or dry etching. After that, the upper substrate or the lower substrate on which the electrode/wiring pattern is formed is attached to the main substrate.

In the above, an electrode/wiring pattern prepared in advance is prepared for the upper substrate, and a concave portion for escaping the pattern portion of the upper substrate is formed in the main substrate in advance. The upper substrate and the main substrate are attached by aligning the concave portion of the main substrate and the pattern of the upper substrate. Then, a penetration chamber is formed in the main substrate. At this time, since the electrode/wiring pattern is already formed on the upper substrate, the through chamber is formed under the condition that the electrode/wiring pattern is not (or is not) easily etched. For example, if the main substrate is Si, Si can be etched at a high speed with a CF-based gas, but if electrodes and wiring of Al or copper are formed on the upper substrate, a condition is selected in which these are hardly etched by the CF-based gas. it can. After that, after forming the insulating film and the conductor film, the conductor film can be patterned only on the side surface of the main substrate. A conductor film is also formed on the upper substrate, but since the photosensitive film does not cover the upper substrate, the conductor film on the upper substrate can be etched, and the electrodes/wirings on the already patterned upper substrate cannot be removed. Since it is covered with the insulating film, it is not etched. The electrodes/wirings of the upper substrate and the conductor film of the main substrate may be connected by patterning after removing the insulating film after the insulating film is formed. After that, the conductor films are laminated, so that the connection is sufficiently possible. Alternatively, all (most) of the insulating film on the electrode/wiring portion of the upper substrate may be removed. At the time of patterning the conductor film, it may be formed by patterning it on the electrode/wiring portion of the upper substrate.

Next, a method for forming the central hole will be described. The main substrate is divided (a main substrate having a thickness half that of the main substrate is used, which is referred to as a semi-main substrate), and patterning is performed to form a central hole. At this time, an insulating film or the like is formed on the main substrate, a film for adhering a photosensitive film is formed, or a mask for an etching stopper (for preventing the main substrate from being etched when the resist is scraped) A film may be formed. A central hole is formed in the pattern. When it is desired to form a curve, side etching such as wet etching or dry etching is used. For vertical patterns, anisotropic etching is performed. Next, patterning for forming the through chamber and forming the substrate side wall (including the central hole) is performed. When there is a portion for forming a vertical pattern and a portion for forming an inclined main substrate side surface as shown in FIG. 9A, patterning is performed separately. Further, when a plurality of tilt angles are provided, patterning is performed each time, and the vertical etching, the tilt etching 1, the tilt etching 2,... The same applies when a part of the main substrate is left. Basically, a penetration chamber is formed in the main substrate. As a result, a central hole (also half), a substrate side wall having the central hole (also half), and a through chamber (also half) are formed in the semi-main substrate. The size of the central hole can be freely changed depending on the etching conditions. Further, the inclination angle can be freely selected depending on the etching conditions. Further, the pattern of the outlet portion inclined in the plane direction of FIG. 9B can be freely changed by using a mask. Therefore, any desired shape can be produced. After that, an insulating film is formed, a conductor film is formed, and the conductor film can be patterned. Since the height is halved, film formation and patterning become easier. Of course, an insulating film and a conductor film can be formed in the central hole, and they can be removed by etching. In the present invention, since the LSI process is used, the size of the side wall of the substrate and the size of the through chamber can be formed very accurately. In the patterning of the conductor film, patterning of the through chamber may be difficult at deep places, but since it can be processed with an accuracy within 1 μm to 10 μm, there is almost no problem with the accuracy of the accelerator of the present invention.

Two identical semi-main substrates may be prepared and they may be attached so that the central holes are aligned. The attachment method can be performed by the method described above, and when electrostatic anodic bonding is performed, a thin glass substrate, a quartz substrate, or the like may be interposed therebetween. A conductive film may be formed on the glass substrate or the like with the same size in the through chamber, the side wall of the substrate, the central hole, and a required portion, and the conductive film may be sequentially or simultaneously attached to the semi-main substrate. The same is possible when the supporting substrate is used as the semi-main substrate. In this case, for example, a method of attaching the semi-main substrate to the upper substrate, removing the supporting substrate, then further attaching the semi-main substrate, removing the supporting substrate, and finally attaching the lower substrate can be adopted. .. Alternatively, it is also possible to attach the half substrates to the upper substrate, remove the supporting substrate, attach the half substrates to the lower substrate, remove the supporting substrate, and attach them to each other. Finally, a contact hole, a conductor film therein, and an outer electrode can be formed in the upper substrate and the lower substrate. Alternatively, these contact holes and outer electrodes can be formed in advance. Furthermore, when it is desired to increase the depth of the penetration chamber, the above process may be repeated many times. If the same thing is made several times at the same time and they are further stacked and adhered, the process does not become long, and the thing with a deep penetration chamber can be easily made freely. For example, if the main substrates of 0.5 mm to 1 mm are sequentially stacked, the accelerator having the penetration chamber of 8 mm to 16 mm can be manufactured by stacking four times.
<Other plasma generation methods>

FIG. 3 is a diagram showing the structure of a linear accelerator for charged particles. In FIG. 1, it can be used for 13 and 39, and can also be used alone or as a linear accelerator. FIG. 3A is a sectional view in the thickness direction of the substrate (the second substrate (upper substrate) 92 is attached to the upper surface of the main substrate 91 and the third substrate (lower substrate) is attached to the lower surface) (the traveling direction of the acceleration cavity 99, That is, FIG. 3B is a plan view parallel to the substrate surface, and FIG. 3C is a sectional view in the thickness direction (the traveling direction of the acceleration cavity 99, that is, the traveling direction of the charged particles G). Vertical direction).

The accelerating cavity 99 through which the charged particles G pass in the accelerating device has a second substrate (upper substrate) 92 at the upper part of a through hole (chamber) 99 (width a1) formed in a main substrate (first substrate) 91 (thickness h1). The lower portion is attached by the third substrate (lower substrate) 93, and the through hole (accelerating cavity) 99 inside is an airtight space. In the acceleration cavity 99, continuous (electrically connected) electrodes are formed in the longitudinal direction (the traveling direction of the charged particles) on the annular electrodes (the sidewall of the through hole 99, the lower surface of the upper substrate 92, and the upper surface of the lower substrate 93). ) Electrodes) 94 are spaced apart and formed in large numbers. (94-1, 2,...) For example, in the annular electrode 94-1, the conductor electrodes 94S1 and 94S2 are formed on the side wall of the through hole 99 in the through hole 99 having the depth h1 and the width a1. A conductor electrode 94U is formed on the lower surface of the upper substrate 92 and a conductor electrode 94B is formed on the upper surface of the lower substrate 93. The conductor electrodes 94S1, 94S2, 94U and 94B are electrically connected to each other and have a length (acceleration cavity). 99 longitudinal direction) k1, and a more accurate shape is a rectangular shape. When the thickness of the conductor electrodes is t1 (all are assumed to be constant), the distance b1 between the conductor electrodes 94S1 and 94S2 is a1-2t1, and the distance d4 between the conductor electrodes 94U and 94B is h1-2t1. For example, if ai=1 mm, h1=1 mm, and the thickness of the conductor film is 10 μm, then bi=0.98 mm and di=0.98 mm.

Next to this annular electrode 94-1 is formed an annular electrode 94-2 having a length k2 spaced apart by a distance j1, and next to it is formed an annular electrode 94-3 having a length k3 spaced apart by a distance j2. And a large number of annular electrodes 94 are formed in the acceleration cavity 99. In the traveling direction of the charged particles G, the length of the i-th annular electrode 94-i is ki, and the distance to the next i+1-th annular electrode 94-(i+1) is j i. A contact hole is formed in the upper substrate 92 of the annular electrode 94 (94-i: i=1, 2,...) And a contact electrode 95 (95-i:i=1, 2,...) Is formed in the contact hole. ) Is formed, and an upper electrode 96 (96-i: i=1, 2,...) Connected to the contact electrode 95 is formed, and the upper electrode 96 is a conductive layer formed on the lower surface of the upper substrate 92. It is electrically connected to the body electrode 94U. Further, a contact hole is formed in the lower substrate 93 of the annular electrode 94 (94-i: i=1, 2,...) And the contact electrode 97 (97-i:i=1, 2,... .) is formed, and a lower electrode 98 (96-i: i=1, 2,...) Connected to the contact electrode 97 is formed, and the lower electrode 98 is formed on the upper surface of the lower substrate 93. It is electrically connected to the existing conductor electrode 94B.

Thus, the voltage is applied to each annular electrode 94 (94-i) formed on the inner surface of the main substrate 91 of the cavity 99 from the outer electrodes 96 (96-i) and 98 (98-i) formed on the upper and lower substrates. Can be applied, but only one of them may be applied. Therefore, only one of them may be applied, but if they are applied simultaneously, the inside of the annular electrode 94 (94-i) is effectively and immediately brought to the same potential. When a voltage having a potential opposite to that of the ion G is applied to each annular electrode 94 (94-i), the ions are accelerated and proceed by the potential Vi of each electroannular electrode 94 (94-i). For example, if the mass of ions is m and the speed of increase in each annular electrode 94 (94-i) is Δui, then 1/2 m(Δui) ² =zeV holds. Therefore, if a large number of ions are arranged, the ions can be made very fast. For example, if m=10 ⁻²⁵ kg, z=1, and V=10 V, Δui=5.6 km/sec (per electrode), and if 10,000 pieces are lined up, it will be 56,000 km/sec. That is, if ki=10 μm and ji=5 μm, an acceleration cavity having a length of 15 cm may be produced. Thus, ultrafast ions can be realized in a very short distance. However, since the ions are also attracted to the annular electrode and diverge, it is necessary to converge. To focus the ions, an electrode for applying a voltage having the same potential as the ions is arranged or a quadrupole magnetic field is applied. Ions having a desired velocity can be obtained by combining these. Further, in the acceleration chamber shown in FIG. 3, one or a plurality of openings 100 are vacant in the upper substrate 92 and/or the lower substrate 93, and the cavity 99 is vacuumed through the openings 100, or an inert gas or the like is used. The inside can be cleaned and purged.

The acceleration cavity chamber can also be produced by disposing a plurality of substrate side wall electrodes having a central hole. FIG. 10 is a view showing an accelerating cavity chamber in which a plurality of substrate side wall electrodes having a central hole are arranged. 10A is a cross-sectional view perpendicular to the substrate surface, FIG. 10B is a plan view parallel to the substrate surface, and FIG. 10C is a cross-sectional view taken along line A1-A2 of FIG. FIG. 11 is a view seen from the left and right direction in FIG. As shown in FIG. 10, the main substrate 101 is formed with a through chamber 104 penetrating from the upper surface to the lower surface, the upper substrate 102 is attached to the upper portion of the main substrate 101, and the lower substrate 103 is attached to the lower portion thereof. It is the side surface of the substrate 101. Charged particles G (indicated by a dashed arrow) such as ions generated in the plasma generation chamber or the ionization chamber 104-1, which is a penetration chamber, penetrates through a central hole 105-0 provided in the central portion of the substrate side wall 101-0. Enter the acceleration cavity chamber 104-2 which is a chamber. A plurality of substrate side walls 101-1 (101-1,..., 4,...) Having a central hole 105 (105-1,..., 4,...) In the acceleration cavity chamber 104-2. Are arranged. Conductor film electrodes 106 (106-1,..., 4,...) Are formed around the substrate side walls 101 (101-1,..., 4,... ). The conductor film electrodes 106 (106-1,..., 4,...) Are the central holes 105 (105-1,..., 1) of the substrate side walls 101 (101-1,. (4,...) is also laminated on the inner surface. The conductor film electrodes 106 (106-1,..., 4,...) Have conductor film wirings 107 (107-1,..., 4,...) Formed on the lower surface of the upper substrate 102. .) and/or the conductor film wiring 108 (108-1,..., 4,...) Formed on the upper surface of the lower substrate 103. The conductor film wirings 107 (107-1,..., 4,...) Outer electrodes/wirings 110 formed on the upper substrate 102 through the contact holes and the contact wirings 109 formed in the upper substrate 102. (110-1,..., 4,...). Further, the conductor film wiring 108 (108-1,..., 4,...) is an outer electrode formed under the lower substrate 103 through a contact hole and a contact wiring 111 formed in the lower substrate 103. The wiring 112 (112-1,..., 4,...) Is connected.

A voltage can be applied to the substrate sidewall electrode/wiring 106 from the outer electrode/wiring 112. Normally, this voltage is applied with a voltage opposite to the charge of the charged particles, so that the charged particles G that have entered the accelerating cavity are drawn by the first substrate side wall electrode wiring 106-1 and accelerated to be centered on the side wall of the substrate. It passes through the hole 105-1 and is drawn by the next substrate side wall electrode wiring 106-2 to be accelerated and passes through the substrate side wall central hole 106-1, and this is repeated to accelerate the last substrate side wall. It is drawn by the electrode wiring 106-n and accelerated, passes through the substrate side wall central hole 106-n, and is emitted to the adjacent chamber 104-3 which is a penetration chamber (assuming that there are n substrate side wall electrode wirings). The adjacent chamber 104-3 is, for example, the cavity chamber 14 or the deflection electromagnet chamber 15 in FIG. There is also a substrate side wall 101-5 having a central hole 105-5 between the acceleration cavity chamber 104-2 and the adjacent chamber 104-3, and charged particles enter the adjacent chamber 104-3 through the central hole 105-5. Since the substrate side wall electrode having the central hole has a narrow region through which the charged particles G pass, the charged particles G pass through the vicinity of the center without spreading very much. However, since some of the charged particles are also attracted to the electrode side, it is desirable to apply a voltage having the same potential (plus or minus) as the charged particles in some places to converge the charged particles. Here, the potential is the same as that of the charged particles, so the speed is slowed down a little, but it is accelerated again by the next acceleration electrode. While repeating the convergence/divergence and the acceleration/deceleration, the substrate side wall electrode having a large number of central holes is arranged to greatly accelerate the whole. Since the present invention uses the LSI process, it is possible to use a very small central hole and a substrate side wall with a short distance, which cannot be realized conventionally, so that a large number of substrate side wall electrodes can be arranged even with a short distance and a large distance can be achieved with a short distance. Can be accelerated to speed. Further, since the applied voltage can be small, a large power source is not needed. In addition, a large power source can be used to apply a large voltage, and in that case, a large acceleration can be obtained.

Further, a voltage can be gradually applied to each substrate side wall electrode in the traveling direction of the charged particles G, and large acceleration can be obtained in a short distance in a short time. Alternatively, if a high frequency voltage is applied to each substrate side wall electrode so that they are synchronized with each other, it is possible to obtain large acceleration as a whole while repeating convergence and divergence, and acceleration and deceleration. An opening 113 may be provided in the upper substrate or the lower substrate in the acceleration cavity chamber 104-2 to perform evacuation, cleaning, or purging. Further, the openings 113 may be provided between the side walls of the respective substrates to perform vacuuming or the like.

The substrate side walls 105-0 and 105-5 between the adjacent chambers may be omitted if not necessary. For example, when the charged particles G from the adjacent chamber 104-1 collide with the front side surface of the first substrate side wall electrode 106-1 without any problem, or when the pressure in the adjacent chamber 104-1 is the same, the charged particles For example, G can be sufficiently accelerated and converged to pass through the central hole 105-1 of the first substrate sidewall electrode 106-1. Further, the size of the central hole 105-0 of the substrate side wall 101-0 is made smaller than the size of the central hole 105-1 of the first substrate side wall electrode 106-1 so that the charged particles G are the first substrate side wall electrode 106-1. You can also make it easier to draw. It is desirable that the central holes 105 (105-1,...) Of the substrate side wall electrodes 106 (106-1,...) Have the same size because uniform acceleration can be achieved. The size of the central hole 105-5 of the substrate side wall 101-5, which is a partition from the adjacent chamber 104-3, is larger than the size of the central hole 105 (105-4 in the diagram) of the last substrate side wall electrode 106 (101-4 in the diagram). It is desirable to increase the size so that charged particles do not collide with the side wall 101-5 of the substrate.

FIG. 4 is a diagram showing an example of a charged particle accelerating tube using a high frequency waveguide, which is a kind of a disk-loaded traveling wave accelerating tube. 4A is a sectional view perpendicular to the substrate surface (schematic diagram thereof) parallel to the traveling direction of the charged particle beam G, and FIG. 4B is (schematic diagram) parallel to the substrate surface. 4(c) is a cross-sectional view (schematic diagram) perpendicular to the substrate surface as seen from the left and right directions of FIGS. 4(a) and 4(b), and is a cross-sectional view of the central hole. The charged particle accelerating tube 200 shown in FIG. 4 is formed on the main substrate 201 and is attached to the through-hole cavity 204 that serves as a passage for charged particles, the upper surface and the lower surface of the main substrate 201, and has the through-hole cavity 204 as an airtight space. It is composed of a substrate 202 and a lower substrate 203. In the charged particle acceleration tube 200, in the traveling direction (longitudinal direction of the penetrating cavity) G of charged particles, both sides of the charged particle acceleration tube 200 are partitioned by substrate partition walls 201S-A and 201S-B having holes (center holes) in the center. Further, a plurality of spaces partitioned by the substrate partition walls 201S-i (i=1, 2, 3,...) With a hole (central hole) in the center are formed between them, and on both sides of these spaces. , A space in which a high-frequency introduction port 208 for microwaves or the like is provided in the upper substrate 202 (may be provided in the lower substrate 203) (this may be referred to as a high-frequency introduction chamber) 204C-A, microwaves, etc. There is a space (which may be referred to as a high-frequency outlet chamber) 204C-B in which the high-frequency outlet 209 of the high-frequency outlet 209 is open in the upper substrate 202 (may be in the lower substrate 203), and the space between them is charged. There are multiple spaces (sometimes referred to as acceleration cavities) 204C-i (i=1, 2, 3,...) That accelerate the particles. In addition, a vacuum exhaust port 210 is appropriately provided in the upper substrate 202 or the lower substrate 203 in these spaces, and the vacuum exhaust port 210 is connected to a vacuum pump 213 to make the space through which the charged particles pass close to a vacuum. ing. In FIG. 4, the vacuum exhaust port 213 is opened to the high frequency introducing chamber or the high frequency introducing chamber, but it is not limited to these and may be provided in another space or cavity.

When a semiconductor substrate such as a silicon substrate is used as the main substrate used in the present invention, since the main substrate has a high electric resistance, a conductor film 206 is formed in a large number of through-hole cavities 204 in the charged particle acceleration tube 200. That is, in the cavity 204 formed in the main substrate 201, the conductor films 206S1 and 206S2 are formed on the cavity side surface of the main substrate 201, the conductor film 206U is formed on the lower surface of the upper substrate 202, and the conductor film 206B is formed on the upper surface of the lower substrate 203. Is formed. Since FIG. 4C is a cross-sectional view of the central hole 205, the conductor films 206S1, S2, U, and B are not visible, but the conductor films 206S, S2, U, and B are illustrated as being transparent. The central hole 205 is arranged at the center of the substrate side wall 201S-i (i=1, 2,...) And the conductor film 206 is formed in an annular shape on the inner surface of the central hole 205. Although the cross section of the central hole 205 is described as a rectangular shape, since the central hole 205 is formed by an etching method (wet or dry) in a state where the main substrate 201 is divided, a shape in which a trapezoid is vertically matched or an elliptical shape, Alternatively, it can be formed into various shapes such as a circular shape.

Since a high-frequency current flows through the inner wall of the acceleration cavity 204C-i (i=1, 2, 3,... ), the conductive film 206 preferably has good conductivity, such as copper, gold, silver, aluminum, or the like. Tungsten, cobalt, etc. are better. When the temperature may rise, a metal film having a high melting point is preferable. Since the charged particle accelerating tube of the present invention can be made small, it is possible to cool the entire apparatus to a low temperature by using a superconductor film. Examples of the superconductor film include niobium (Nb), niobium-titanium (Nb-Ti), niobium-tin (Nb-Sb), magnesium diboride, and high-temperature oxide superconductors (yttrium-based, bismuth-based, etc.). These can be formed as a sputter film or a coating film. If the thickness of the main substrate 201 is h2, the lateral width (planar width) is a2, and the thickness of the conductor film 206 is t2, the depth d5 of the through hole cavity 204 is h2-2t2, and the lateral width b2 of the through hole cavity 204 is It becomes a2-2t1. When an insulating film (for example, a silicon oxide film) or an adhesion improving film (for example, Ti or TiN film) is formed between the main substrate 201 and the conductor film 206, an excellent film (protection film) is formed on the conductor film 206. When forming a film, it is necessary to consider the thickness of the film.

The charged particles G are emitted from a charge generator or the like, pass through the inside of the cavity 204-1 and enter the charged particle accelerator tube 200 through the central hole 205 of the substrate partition wall 201S-A which is the entrance of the charged particle accelerator tube 200. To do. The charged particles G enter the high frequency introduction space 204C-A, then enter the acceleration space 204-1 through the central hole 205 of the substrate partition wall (side wall) 201S-1, and successively enter the substrate partition 201S-i (i=1). , 2, 3,...) into the acceleration space 204C-i (i=1, 2, 3,...) Through the central hole 205, and finally into the high frequency derivation space 204C-B, It passes through the central hole 205 of the substrate partition 201S-B, which is the exit of the charged particle acceleration tube 200, and exits into the cavity 204-2 outside the charged particle acceleration tube 200. The high frequency wave 211 enters the high frequency wave introducing space 204C-A from the high frequency wave introducing port 208, passes through the central hole 205 of each substrate partition wall, and is charged in each acceleration space 204C-i (i=1, 2, 3,...). A high-frequency electric field for accelerating is generated, goes out to the high-frequency derivation space 204C-B, and goes out as a high-frequency 212 from the high-frequency derivation port 209. Therefore, the charged particles are sequentially accelerated by the accelerating electric field generated in each accelerating space 204C-i (i=1, 2, 3,...) And pass through the central hole 205 of the substrate partition 201S-B. Exit the accelerator tube 200.

The accelerating tube 200 may be provided with a focusing electromagnet 207 that converges the divergence of the accelerated charged particles. The focusing electromagnet 207 is installed in the portion of the cavity 204 after the charged particles G have left the central hole 205 of the substrate partition wall 201S-B. For example, as shown in FIG. 4, a quadrupole electromagnet 207 (207-1, 2, 3, 4) is arranged around the cavity 204. FIG. 4D is a view showing a sectional structure perpendicular to the longitudinal direction of the cavity 204 in the portion where the quadrupole electromagnet is arranged. A coil 207-2 and a coil 207-4 are formed on both lateral sides of the cavity 204 with the substrate side walls 201S-S1 and 201S-S2 sandwiched therebetween. The closer the coil 207 is to the center of the cavity 204, the stronger the magnetic flux density (or magnetic field) becomes, and the easier it is to control the charged particles (the charged particles G pass through the center of the cavity 204). 201S-S2 should be thin. Since the LSI process can be used, a very thin substrate side wall of, for example, 10 μm to 1000 μm can be formed.

Although the upper substrate 202 exists above the cavity 204, the coil 207-1 is arranged above the upper substrate 202, embedded in the upper substrate 202, or above or inside the upper substrate 202. The closer the coil 207 is to the center of the cavity 204, the stronger the magnetic flux density (or magnetic field) becomes, which facilitates control of charged particles. Therefore, when the coil 207-1 is arranged above the upper substrate 202, the coil 207-1 is placed as close to the upper surface of the upper substrate 202 as possible. Optimally, the coil 207-1 may be in contact with the upper surface of the upper substrate 202. When the coil 207-1 is embedded in the upper substrate 202 or formed inside the upper substrate 202, the upper substrate 202 existing between the cavity 204 and the bottom surface of the coil 207-1 and the cavity is the upper substrate 202- U, the thickness of this portion is thinner than the thickness of the upper substrate 202. The thinner the upper substrate 202-U, the better. However, the upper substrate 202-U can be made extremely thin, for example, 10 μm to 1000 μm.

The lower substrate 203 exists below the cavity 204, and the coil 207-3 is arranged below the lower substrate 203, embedded in the lower substrate 203, or inside the lower substrate 203. The closer the coil 207 is to the center of the cavity 204, the stronger the magnetic flux density (or magnetic field) becomes, which facilitates control of charged particles. Therefore, when the coil 207-3 is arranged below the lower substrate 203, the coil 207-3 should be as close to the lower surface of the lower substrate 203 as possible. Optimally, the coil 207-3 may be in contact with the lower surface of the lower substrate 203. When the coil 207-3 is embedded in the lower substrate 203 or formed inside the lower substrate 203, the lower substrate 203 existing between the cavity 204 and the upper surface of the coil 207-3 is the lower substrate 203- However, the thickness of this portion is thinner than the thickness of the lower substrate 203. The lower substrate 203-B is preferably as thin as possible, but it can be made extremely thin, for example, 10 μm to 1000 μm.

As shown in FIG. 4D, when the horizontal centerline of the main substrate 201 is C1, the center O1 of the cavity 204 is on the horizontal centerline C1 and the axes of the coils 207-2 and 207-4 are located. The coil 207-2 and the coil 207-4 are arranged in the main substrate 201 so that the lines are aligned with the lateral centerline C1. The coils 207-1 and 207-3 are arranged so that the axes of the coils 207-1 and 207-3 are aligned with the vertical centerline C2 that passes through the center O1 of the cavity 204 and is orthogonal to the horizontal centerline C1. To do. By arranging the quadrupole electromagnets (coils) in this way, the magnetic field distribution in the cavity 204 can be brought into a state close to a symmetrical shape, so that the charged particles can be converged in the vicinity of the center O1 of the cavity 204. In particular, the substrate sidewalls 201S-S1 and 201S-S2 have substantially the same thickness, the coils 207-2 and 207-4 have the same characteristics, and they are arranged at positions symmetrical with respect to the center O1 of the cavity 204. The thicknesses of 202-U and 202-B are made substantially equal, the characteristics of the coil 207-1 and the coil 207-3 are made the same, and they are arranged symmetrically with respect to the center O1 of the cavity 204. By making the characteristics of the coil 1, the coil 207-2, the coil 207-3, and the coil 207-4 the same, the magnetic field distribution in the cavity 204 can be made to be in a nearly symmetrical state. However, in the quadrupole electromagnet of the present invention, the voltage applied to each coil can be freely set and the internal magnetic field of the cavity 204 can be freely set even if the characteristics and arrangement of the constituent coils, the side wall of the substrate and the thickness of the substrate are slightly different. Since it can be changed to, it is easy to converge the beam of charged particles in the vicinity of the center O1 of the cavity. The center O1 of the cavity 204 is the traveling direction G of the charged particles, and therefore, the center of the central hole 205 is preferably aligned with the center O1 of the cavity 204.

Assuming that the width of the substrate side wall 201S-i, that is, the length of the central hole 205 is m1 and the length of the acceleration cavity 204C-i (the size of the charged particle accelerator 200 in the longitudinal direction) is p1, the high frequency introduction chamber 204C-A and The distance of the high frequency extraction chamber 204C-B is (n+1)×m1+n×p1. (When the charged particle accelerator 200 has n accelerating cavities) The accelerating electric field distribution may be changed by changing the length p1 of each accelerating cavity or the length of the central hole 205 by m1. .. In addition, the size (a2, h2) of the cavity 204 and the size of the central hole 205 (for example, if the central hole 205 is rectangular, the length or width, and if the central hole 205 is circular, the diameter) are changed. Then, the acceleration electric field distribution may be changed. Since the charged particle accelerator of the present invention can be manufactured by using an LSI process, these sizes can be easily and inexpensively changed. Further, the size and number of quadrupole electromagnets can be freely changed according to the size of the cavity 204.

Next, a method of manufacturing the electromagnet (coil) will be described. FIG. 11 is an embodiment showing a method for producing an electromagnet (coil). The coil production substrate 115-1 is attached to the support substrate 114-1. Since the support substrate 114-1 is separated from the coil forming substrate 115-1 later, the support substrate 114-1 can be attached by a softening adhesive (softening temperature T1). The support substrate 114-1 is an insulating substrate such as a glass substrate, a stone substrate, an alumina substrate, a plastic, an epoxy substrate, a polymer substrate, a semiconductor substrate such as Si, or a conductor substrate such as Cu or Al. The coil production substrate 115-1 is a non-magnetic substrate, and is an insulating substrate such as a glass substrate, a stone substrate, an alumina substrate, a ceramic substrate, a plastic, an epoxy substrate, or a polymer substrate, or a semiconductor substrate such as Si. As shown in FIG. 11A, a photosensitive film pattern for a coil conducting wire pattern is formed on the coil production substrate 115-1 and the coil production substrate 115-1 is etched. It is desirable that this etching be vertical etching faithful to the photosensitive film pattern. Alternatively, the coil production board 115-1 having a coil conductor wire pattern punched by a die may be attached to the support board 114-1. Alternatively, a plastic or polymer resin film having a coil conductor pattern formed thereon may be attached to the support substrate 114-1. When the coil production substrate 115-1 is a semiconductor substrate made of Si or the like, a conductor film is laminated on the side surface of the recess so that the coil wirings are not short-circuited.

Next, the coil conductor pattern in the recess is filled with a conductor film. The conductor film is, for example, Cu, Ni, Cr, Au, Al, W, Mo, Ti, Zr, various solders, alloys or composite metals thereof, various silicide films, and superconductors. As the filling method, a method of laminating by CVD or PVD method and polishing (for example, CMP) to fill only the concave portion with the conductive film, a method of filling the concave portion with the conductive film by selective CVD method, or a plating method There is a method of filling the recess with a conductor film or a method of applying a conductive paste. It is also possible to polish these to make them flat. By these methods, the first layer (116-1) of the coil wiring pattern having the width a and the depth c1 is completed. The plane pattern of the first layer is a wiring pattern having a length d (width a) and a distance b as shown in FIG. 11(g), for example.

Next, a pattern for the second layer is produced in the same manner. Also for the second layer, the coil production substrate 115-2 is attached to the support substrate 114-2, and the coil wiring pattern 116-2 for the second layer is formed with a photosensitive film or the like. The cross-sectional pattern of the pattern of the second layer is the same as that of FIG. 11A, but the plane pattern is a rectangular pattern of (horizontal) width a, distance b, and (vertical) width e, as shown in FIG. 11H. So, when they are stacked, they match the pattern of the first layer. Since the coil wire width is (horizontal) width a×(longitudinal) width e, it is preferable to take e substantially equal to a. Next, as shown in FIG. 11B, the coil wiring pattern of the second layer is attached to the coil wiring pattern of the first layer while pattern matching. That is, the coil manufacturing substrate 115-1 having the coil conductive wire pattern of the first layer attached to the support substrate 114-1 and the coil manufacturing substrate 115 having the coil conductive wire pattern of the second layer attached to the support substrate 114-2 have been formed. -2 is attached. As this attachment method, a room temperature bonding method, a diffusion bonding method, a high temperature bonding method, the coil production substrate 115-1 or 2 is an insulating substrate such as a glass substrate or a quartz substrate, and the coil production substrate 115-2 or 1 is made of Si or the like. When it is a semiconductor substrate, the electrostatic anodic bonding method can also be used. It is also possible to use an adhesive to attach the conductive films. A conductive adhesive is used for the joint between the conductor films, and an insulating adhesive is used for the other portions. With other joining methods, a conductive adhesive can be used for the joint between the conductor films. If the distance b between the wirings is 10 μm or more (at the present time), the conductive adhesive can be applied to the joint pattern using a metal mask, or the photosensitive film conductive adhesive or the photosensitive film pattern+etching method can be used. For example, the conductive adhesive can be applied to the joint pattern even when the distance b between the wirings is 1 μm. Further, solder may be applied or plated on the joint to be attached. If the depth of the recess of the second layer is also c1, C2 is 2c1. The adhesive used to bond the coil-forming substrates 115 to each other is preferably a thermosetting adhesive so as not to separate in the subsequent heat treatment. When a solder metal or a thermoplastic adhesive is used, the coil-making substrates 115 are not moved by the subsequent heat treatment to cause pattern shift or separation.

Next, the support substrate 114-2 is removed. The adhesive to which the support substrate 114-2 and the coil production substrate 115-2 are attached is a thermoplastic adhesive, and when the softening temperature is T2, an adhesive that satisfies T1>T2 is selected. As a result, only the support substrate 114-2 can be separated at a temperature between T1 and T2. FIG. 11C is a diagram showing a state in which the support substrate 114-2 is separated. The patterns of the third and subsequent layers are also the same as those of the second layer, and by sequentially adhering the patterns, wiring in the height direction of the coil can be manufactured. However, since it takes time to stack one sheet at a time, as shown in FIG. 11(d), two sheets are stacked next to each other into four sheets (state of FIG. 11(d)). Next, by stacking four sheets, the number of sheets becomes eight. If c1=0.1 mm, the thickness of 0.8 mm will be obtained after five depositions.

Since the last coil wiring pattern needs to be spirally connected as a coil, the wiring pattern is as shown in FIG. 11(i). The first layer is the wiring pattern shown in FIG. 11(g), and the uppermost layer is the wiring pattern shown in FIG. 11(i). (The reverse is also possible.) The wiring pattern between them is the pattern shown in FIG. When the predetermined height c4 is reached, the support substrate on the uppermost layer side is separated, and then the photosensitive film 117 is attached (coated) to form the photosensitive film pattern 117. Using this as a mask, the coil production substrate 115 is removed by etching. Since the support substrate 114-1 is not yet separated, it is desirable to perform etching with a high selection ratio between the coil production substrate 115 and the support substrate 114-1. If the materials of the support substrate 114-1 and the coil production substrate 115 are different, the etching selection ratio can be easily increased. For example, the case where the support substrate 114-1 is Si or glass and the coil production substrate 115 is glass or Si. Alternatively, it may be cut by a dicing method to separate unnecessary portions. For example, when the support substrate 114-1 and the coil production substrate 115-1 are attached, an adhesive that can be separated by light irradiation is used at a place where it is separated as an unnecessary portion, and an ordinary thermoplastic adhesive is used at other places. By using, it is possible to perform dicing, cut only a part (a little in the depth direction) of the coil production substrate 115 and the support substrate 114-1, and then irradiate light to separate unnecessary portions. In order to separately attach the adhesive, for example, a mask may be used for application. As a result, the coil 118 having the shape shown in FIG. 11F is attached to the support substrate 114-1.

Next, the support substrate is attached to the main substrate 201 which is attached to the lower substrate 203 and has the coil insertion cavity 120 (120-1, 2) and the cavity 204-2 (see FIG. 4) through which the charged particle beam G passes. Electromagnets (coils) 118-1 and 118-2 formed on 114-1 are inserted. Since a conductor electrode/wiring 119 for connecting the terminal of the coil 118 is formed on the lower substrate 203, the lower substrate 203 is inserted so as to match the pattern. The size of the coil 118 is adjusted so that the central axis of the coil 118 comes to the center of the main substrate 201. It is desirable to attach a conductive adhesive or solder metal to the connecting portion in advance. If these are softened and attached while applying heat, the height can be adjusted in the vertical direction. If an insulating film is laminated on the wiring pattern of the coil 118 or an insulating sheet is attached and a window is opened only at the connection portion, a conductive adhesive or the like can be widely applied, so that the connection can be made surely, and the height can be adjusted or leveled. Adjustment becomes easy.

Further, if all the terminals on the coil side are provided on the opposite side (like the coil 118-1 shown in FIGS. 11(j) to 11(m)), the conductor film electrode/wiring pattern 109 is provided on the lower substrate 203. Since it is not necessary, the insulating adhesive can be applied to the lower substrate 203 and/or the lower side of the coil 118, so that the coil 18 can be surely attached, and the height and the level can be easily adjusted. Can be done. For example, it is possible to easily adjust the levelness and pressing of the lift press of the support substrate 114. Since the size of the coil insertion cavity 120 (120-1, 2) is not so limited, it can be opened considerably larger than the coil 118, so that there is no particular problem in coil insertion. In addition, if the conductor film electrode/wiring is also formed large, there is no particular problem in connection with the coil side. The distance between the end surface of the coil 118 (the right side for the coil 118-1 and the left side for the coil 118-1) and the center of the cavity 204-2 affects the magnetic field exerted on the charged particles, but the current alignment error is 1 μm. Since it is between 10 μm, there is not much influence.

Furthermore, since the distance between the two coils 118-1 and 118-2 is not deviated at all, the combined magnetic field exerted on the center of the cavity 204-2 is hardly changed. In order to make the magnetic field uniform throughout the cavity 204-2, it is desirable to make the size of the coil (on the end face) larger than the size of the cavity 204-2 (in the depth direction). The lower substrate 203 in the coil insertion cavity 120 (120-1, 2) may be thinned so that the coil insertion cavity 120 (120-1, 2) is deeper than the cavity 204-2. In that case, naturally, the size of the coil 118 is correspondingly increased.

After fixing the coil 118 to the lower substrate 203 in the coil insertion cavity 120 (120-1, 2), the support substrate 114-1 is separated. In this method, the coil 118 is fixed to the lower substrate 203 by using, for example, a thermosetting adhesive having a curing temperature T3 lower than T1 such as an adhesive used for bonding the coil 118 and the lower substrate 203. After that, the temperature is raised to T1 or higher to separate the support substrate 114-1. (FIG. 11(k)) Next, as shown in FIG. 11(l), the upper substrate 121 on which the conductor film electrode wiring 121 connected to the coil terminal is formed is aligned with the terminal of the coil 118 and is attached to the main substrate 201. Adhere to. When the wiring pattern is formed on the coil 118, it is applied after applying or forming a conductive adhesive or solder metal in a state where the insulating film is laminated or an insulating film is attached to open the connection part window. You can do it.

Next, contact hole conductor film wirings 122 connected to the conductor film electrode wirings 121 are formed on the upper substrate 202, and outer electrode wirings 123 (123-1, 2, 3) connected to the contact hole conductor film wirings 122 are formed. Contact hole conductor film wirings 124 connected to the conductor film electrode wirings 119 are also formed on the lower substrate 203, and outer electrode wirings 125 connected to the contact hole conductor film wirings 125 are formed. As a result, the coils 118 (118-1, 2) are arranged in the coil insertion cavities 120 (120-1, 2) sandwiching the main substrate side walls 201S-S2 and 201S-S1 on both sides of the cavity 204-2. To be done. Moreover, since they are arranged very accurately (the current alignment error is 10 μm or less), the magnetic field in the cavity is also uniform. Current can be passed from the outer electrodes 123-1 and 123-2 to the coil 118-1, and current can be passed from the outer electrodes 123-3 and 125 to the coil 118-2. (Fig. 11(m))

In the process of FIG. 11, the method of adhering to the support substrate from the first layer pattern is adopted. However, the coil pattern of the first layer is prepared on the lower substrate, and the second layer is attached to the support substrate. It can also be formed. If this method is adopted, the first process of the first layer can be omitted. Similarly, the pattern of the last uppermost layer can be formed on (the lower surface of) the upper substrate. This also allows the top layer process to be omitted. Further, in this case, since the coil wiring patterns from the second layer to the n−1th layer (nth layer is the uppermost layer) are the same, they may be simply stacked, or stacked layers may be desired. It can also be manufactured by stacking so as to have the size of. Finally, they may be attached to the first layer pattern of the lower substrate and the (n-1)th layer may be attached to the uppermost layer pattern of the upper substrate.

In the process of FIG. 11(j), the substrate side wall 201S-S1 and the substrate side wall 201S-S2 are provided as partitions between the cavity 204-2 through which the charged particle beam G passes and the coil insertion cavity 120 (120-1, 2). Although present, the substrate side walls 201S-S1 and the substrate side walls 201S-S2 act as a partition in the direction of weakening the magnetic field or disturbing the magnetic field, and thus can be removed. However, since charged particles pass through the cavity 204-2, it is necessary to set the pressure to the same level as that of the cavity 204-2. Therefore, the coil insertion cavities 120 (120-1, 2) can also be provided with openings for vacuuming the upper and lower substrates 202 and 203. If the substrate side wall 201S-S1 and the substrate side wall 201S-S2 are not provided, the cavity 204-2 and the coil inserting cavity 120 (120-1, 2) become the same cavity, so when the coils 118-1 and 2 are inserted. In addition, since there is no concern that the coils 118-1 and 2 collide with the substrate side wall 201S-S1 and the substrate side wall 201S-S2, the insertion becomes easy.

Furthermore, regarding the distances between the board sidewalls 201S-S1 and 201S-S2 and the coils 118-1 and 118, it is not necessary to consider the margin (margin distance) at the time of insertion. Therefore, the distance between the coil 118-1 and the coil 118-2 can be shortened, and the current for creating the magnetic field in the cavity can be reduced. Alternatively, the magnetic field can be further strengthened. Alternatively, by forming a central hole in the substrate sidewall 201S-S1 and the substrate sidewall 201S-S2, the magnetic field at that portion is not affected by the material (material) of the substrate sidewall 201S-S1 and the substrate sidewall 201S-S2. The pressure in the cavity 204-2 does not have to be much affected by the coil insertion cavity 120 (120-1, 2).

Further, although the supporting substrate 114-1 is used, if the upper substrate 202 or the lower substrate 203 is used instead of this, the supporting substrate can be used as it is without removing the supporting substrate in the process shown in FIG. Further, as in the case of FIG. 12D, if the supporting substrate 114-1 is provided with a convex portion to form the coil 118, the supporting substrate 114-1 and the main substrate can be inserted when the coil is inserted (process shown in FIG. 11J). Since the support substrate 114-1 can be removed without bringing the main substrate 201 into contact with the main substrate 201, damaging the main substrate 201 is not necessary. As shown in FIG. 11(m), the electrode connected to the wiring end of the coil can be freely formed on the upper substrate 202 or the lower substrate 203. In FIG. 11J, since the electrode wiring pattern is formed on the lower substrate 203, it is necessary to match the terminals of the coil 118 to the electrode wiring pattern, but it is not necessary to form the electrode wiring pattern on the lower substrate 203. Since it is also possible to do so, there is no need to adjust it at the time of inserting the coil, so that the process can be performed at high speed. Furthermore, it is not necessary to use a conductive adhesive, and it is also possible to attach it to the lower substrate 203 using one ordinary type of adhesive (for example, an insulating adhesive). Further, at that time, if the upper substrate 202 or the lower substrate 203 is used instead of the supporting substrate 114-1, it is not necessary to bring the coil 118 into contact with the lower substrate 203, and the upper substrate 204 to which the coil 118 is attached is attached to the main substrate 201. Since you only have to do it, there is no need for precise alignment.

In the process of FIG. 11, if the coil size is a=e=30 μm, b=20 μm, d=1 mm (=5×10 ³ μm), height=1 mm, length=5 mm, a coil with 100 turns is formed, If the coil conductor is made of Cu, and if a current of 10 ⁶ A/cm ² can be passed (this level is possible due to electromigration resistance), a current of I=9 A can be passed through the coil. Therefore, the magnetic field Hc formed at the center of the end face of the coil is 8×10 ⁵ A/m.

Furthermore, the magnetic field generated can be increased by inserting a core having a high relative permeability μ into this coil. Therefore, a method of inserting a core having a high relative permeability μ into the coil used in the accelerator of the present invention will be described. Since a method similar to this method has already been described in JP 2012-134329 A, they are also applicable to the present invention. FIG. 12 is a diagram showing a method for producing a high-performance coil in which a core having a high relative permeability μ is inserted. In the embodiment shown in FIG. 12, four types of coil manufacturing patterns are used. 12G to 12J are plan views showing the patterns. FIG. 12(g) is the same as FIG. 11(g), but the region corresponding to the core insertion hole is indicated by a broken line A. Further, a portion corresponding to the outer shape of the coil is shown by a dotted line B. In FIG. 11 and FIG. 12, the same substrate (layer) exists in each layer outside the coil, and in the process of FIG. 11E, the outer substrate layer 115 is etched at once by using the photosensitive film pattern 117 as a mask. Although it has been removed, after adhering to the support substrate 114, a photosensitive film pattern or the like is formed in the portion indicated by the dotted line B, and the substrate 115 outside the region indicated by the dotted line B is removed by etching using this as a mask. Then, it is also possible to attach only the coil forming region and stack them. Alternatively, it is possible to fabricate the state shown in FIG. 11F by not adhering to the supporting substrate but adhering only this coil portion and stacking it, and finally adhering the coil to a predetermined portion of the supporting substrate 114. it can.

FIG. 12A is the same diagram as FIG. 11C. That is, the coil production board 130-1 is the coil production board 115 having the coil wiring pattern 116 shown in FIG. The coil insertion area has a rectangular (rectangular) shape indicated by a broken line A, and enters the inside of the coil wiring pattern 116 shown in FIG. 12G on the vertical side (width side of the coil) and the lateral side (axial direction of the coil). ) Is protruding from both sides of the coil wiring. The dotted line B is the portion that becomes the outer shape of the coil. The coil production board 130-2 is the coil production board 115 having the coil wiring pattern 116 shown in FIG. The coil wiring patterns 116 are stacked in the coil height direction to form a coil wiring pattern. In the patterns of FIGS. 12G and 12H, the coil insertion area A is the same as that of the coil-fabricated substrate 115 and is flat in plan view. The pattern deposited on this is a coil production substrate 115 having the pattern shown in FIG. That is, the coil production substrate 130-3 is the coil production substrate 115 having the pattern shown in FIG. In FIG. 12(i), the coil insertion area A is hollowed out to form a cavity. This cavity can be produced by attaching the coil production substrate 115 shown in FIG. 12(h) to a support substrate and opening a window, etching the coil production substrate 115, or punching it with a die. Further, it is also possible to manufacture by coiling or punching the coil manufacturing substrate 115 shown in FIG. Also on this coil production substrate 130-3. The coil insertion area A shown in FIG. 12(i) is hollowed to form a hollow coil-making substrate 115, and a predetermined number of this is prepared. (FIG. 12B) Here, the coil production substrates 130-4, 5 and 6 are the coil production substrates 115 having the pattern shown in FIG. 12(i). A large number of the coil-fabricated substrates 115 having the pattern shown in FIG. 12(i) attached (all of which are hollowed out by hollowing out the coil insertion area A) are collectively shown in FIG. 12(a). Alternatively, the coil insertion area A shown in FIG. 12(h) may be attached onto the coil production substrate 130-2 which is the coil production substrate 115 which is not hollowed out. In this case, the portion indicated by the broken line A in FIG. 12B has a hollow inside. This cavity also has a vertical shape when superposed if it has a side surface perpendicular to the substrate surface, but since this region A is a portion that is lost because it is larger than the coil region B in the axial direction, it does not necessarily have a vertical shape. You don't have to.

Alternatively, the coil-fabricated substrate 115 shown in FIG. 12(h) in which the coil insertion area A is not hollowed out may be additionally attached to the one shown in FIG. 12(a). That is, the coil-producing substrates 130-2 to 130-6 are all flat without the coil insertion region A being hollowed out. In that case, as shown in FIG. 12C, the photosensitive film 131 is patterned, a portion of the coil insertion area A is opened, and the coil production substrate 115 in that portion is etched to form the coil insertion area. A concave portion (opening) 134 of A is formed. In FIG. 12C, the recessed portion (opening) 134 that is the etched coil insertion area A reaches the portion of the coil production substrate 130-3, but the portion of the coil production substrate 130-2 may also be etched. .. When reaching the area of the coil manufacturing substrate 130-1, the coil wiring 116 is exposed, which is not preferable (the coil wiring 116 is not etched or damaging is prevented). Therefore, etching is performed to the extent that the coil wiring 116 is not exposed. Stop. Then, the photosensitive film pattern 131 is removed.

Next, an adhesive (coating liquid) is put into the recess 134, or an adhesive is attached to the core member 133 shown in FIG. 12D, and the core member 133 is inserted into the recess 134. The core member 133 is previously attached to the support substrate 132 with an adhesive or the like. For example, a core member sheet or a film or a thin plate to be a core member may be attached to the supporting member 133, and then a predetermined pattern may be formed by photolithography+etching, or may be punched by a die. Alternatively, the core member sheet or the like may be diced and unnecessary portions may be picked up and removed. In that case, if the adhesive is divided into a part to be removed and a part to be directly attached, only the unnecessary part can be easily removed by using different peeling methods. (For example, an adhesive having a different softening temperature is used.) A non-magnetic insulating adhesive can be used as the adhesive, but a paste-like or liquid adhesive containing ferromagnetic particles such as ferrite particles is used. Is also good. Since these ferromagnetic particles are also a kind of core, the effect of the core can be enhanced.

The core member 133 attached to the support substrate 132 is inserted into the recess (opening) 134 which is the coil insertion area A. At this time, if the convex portion 135 is provided on the support substrate 132, the upper portion of the core member 133 does not extend outside the upper surface of the uppermost coil-making substrate 130-6, that is, the entire core member 133 is a concave portion ( (Opening) 134. (The sum of the height h1 of the core member 133 and the thickness h2 of the adhesive is set to be smaller than the depth h3 of the concave portion 134 (that is, when h1+h2<h3 and the height of the convex portion 135 are h4, h1+h2+h4>). If designed to be h3, the support substrate 132 does not hit the upper surface of the coil production substrate 130-6, and the core member 133 can be smoothly inserted into the recess (opening) 134.) For example, when the adhesive is a thermosetting adhesive (curing temperature T1) and the adhesive between the core member 133 and the supporting member 132 is a thermoplastic adhesive (softening temperature T2), T1<T2. By using, the core member 133 may be first fixed in the recess 134 between T1 and T2, and then the core member 133 may be separated from the support member 132 at a temperature of T2 or higher.

After the core member 133 is inserted into the recess 134, if foreign matter such as adhesive is prevented from adhering to the surface of the uppermost coil manufacturing substrate 130-6, the step shown in FIG. The coil production substrate 130-7 can be attached to the coil production substrate 130-6. When a foreign substance such as an adhesive adheres to the surface of the uppermost coil-making substrate 130-6, or when the core member 133 is completely embedded in the recess, after the core member 133 is put in the recess 134 and fixed. The same adhesive is put into the recess 134 from above the core member 133 to fill the gap space of the recess 134 with the adhesive. Alternatively, insulating films may be laminated or applied. At this time, since the adhesive or the insulating film is also adhered or laminated on the surface of the highest coil production substrate 130-6, the adhesive or the insulating film adhered or laminated by CMP, BG (grinder) or etch back is removed. , And planarize to expose the coil wiring pattern 116. This flattening is performed, for example, by applying an organic film such as a resist solution and flattening, and then polishing by CMP, BG (grinder) or the like, or etching by an etch back method to flatten the coil-making substrate 130. -6 Display the surface. (Fig. 12(e))

Then, the coil production substrate 130-7, which is the coil production substrate 115 in which the coil insertion area A shown in FIG. 12(h) is not hollowed out, is changed to the coil production substrate 130-6 (slightly etched or polished). Attach it. After that, the coil manufacturing substrate 130-8, which is the coil manufacturing substrate 130-5 having the coil wiring pattern shown in FIG. 12(j), which is the uppermost coil manufacturing substrate, is attached to the coil manufacturing substrate 130-7. In this way, a coil containing the core member 133 can be manufactured. A coil in which a required number of core members 133 are incorporated is produced at a required location on the support substrate 114-1. Thereafter, the coil having the core member 133 built therein is inserted into the coil insertion cavity 120 in the process shown in FIG. A coil containing the core member 133 can be arranged at the same time in a portion requiring a large number of accelerators and electromagnets. It should be noted that if an insulating film is interposed by applying or laminating an insulating film on the coil manufacturing substrate 130-1 which is the coil manufacturing substrate 115 having the coil wiring pattern shown in FIG. The coil insertion area A shown in FIG. 12( i) is not cut out, and the coil insertion area A shown in FIG. The coil production substrate 130-3, which is the removed coil production substrate 115, may be attached. (Because the coil wiring pattern and the core member 133 are not electrically connected to each other.) Similarly, if an insulating film is interposed on the upper surface of the core member 133, the coil insertion area A shown in FIG. The coil production substrate 115, which is the coil production substrate 115 which has not been hollowed out, is the coil production substrate 115 which has the coil wiring pattern shown in FIG. 12(j) without attaching the coil production substrate 130-7 to the coil production substrate 130-6. It is also possible to attach a certain coil making substrate 130-8. The intervening insulating film can be realized by an insulating adhesive, an insulating sheet, or a stack of insulating films (CVD, PVD, coating method, etc.). As a result, the layer shown in FIG. 12(h) is unnecessary. As the core member, iron (μ=about 5000), pure iron (μ=about 10000), silicon iron (μ=about 7000), permalloy (μ=about 100000), supermalloy (μ=about 1000000), Examples of soft magnetic materials include amorphous iron (μ=about 3000), ferrite (μ=about 2000), sendust (μ=about 30,000), and vermendur (μ=about 5000).

Next, a method of manufacturing the coils arranged on the upper and lower substrates will be described. FIG. 13 is a diagram showing a method of manufacturing the coils arranged on the upper and lower substrates. The coil wiring substrate 142-1 of the first layer is attached to the support substrate 141-1. This coil wiring board 142-1 is a board without coil wiring, for example, without the conductor film wiring pattern 144 of FIG. 13(i). When the coil wiring substrate 142-1 is a semiconductor substrate such as Si or a conductor substrate, an insulating film is formed on the substrate surface so that the wiring and the coil wiring substrate 142-1 are not connected. When the coil wiring board 142-1 is an insulator such as glass, quartz, sapphire, alumina, plastic, or polymer resin, it is not usually necessary to form an insulating film, but in order to improve the adhesion with the conductor film, In some cases, the insulating film of is required. The coil wiring board 142-1 of the first layer protects the wiring pattern of the wiring board adhered on the coil wiring board 142-1. However, an insulating film can be formed on the lower surface of the coil wiring of the second layer for protection. The coil wiring board 142-1 of the first layer may not be provided. However, in order to make the coil strong, it is better to provide the coil wiring substrate 142-1 of the first layer.

Next, the second-layer coil wiring board 142-2 is attached. Since there is no pattern for the first layer, pattern matching is unnecessary. The second-layer coil wiring board 142-2 is a wiring board having a wiring pattern shown in FIG. In this attachment method, the coil wiring board 142-2 of the second layer is attached to another support board 141-2 (not shown) as described above, and the coil wiring board 142 attached to the support board 141-1. -1 and the coil wiring substrate 142-2 attached to the supporting substrate 141-2 are faced to each other and attached, and then the supporting substrate 141-2 may be separated from the coil wiring substrate 142-2. Alternatively, if the coil wiring substrate 142 can be supported by itself, the coil wiring substrate 142-1 and the supporting substrate 141-2 can be directly attached while being aligned. Alternatively, the coil wiring substrate 143 having no wiring pattern is attached to the support substrate 141-2, the coil wiring substrate 143 having no wiring pattern is patterned, and the photosensitive film pattern having the wiring pattern as an opening is formed by a photolithography method. Then, the coil wiring board 143 is etched to form a through groove pattern. It is desirable that the through groove pattern has a vertical shape. Alternatively, the through groove pattern can be formed by punching out the coil wiring board 143 having no wiring pattern with a die having a wiring pattern. Alternatively, the through hole pattern is formed by applying a photosensitive resin to the support substrate 141, opening the through groove pattern, and curing the area other than the opening. Alternatively, an insulating film paste is applied, the through-groove pattern is opened with a mold or the like, and the paste is cured to form the through-groove pattern. Alternatively, the paste is applied by a screen printing method to open the through groove pattern, and then the paste is cured to form the through groove pattern.

If necessary, an insulating film is formed on the coil wiring board 143 in which the through-grooves are formed in this manner, then a conductor film is formed, and the through-groove pattern is filled with the conductor film. After the conductor film is thickly formed by the CVD method, the PVD method or the plating method to fill the through groove, the surface is etched (etch back method) or polished (BG method or CMP method) to remove the surface. The conductor film is removed and only the through groove is filled with the conductor film. Alternatively, a conductive film (seed layer) is thinly laminated on the inner wall of the through groove and the surface of the coil wiring substrate 143 by the CVD method or the PVD method, and then a photosensitive film is applied or a photosensitive sheet is attached and the photolithography method is used. The conductor except for the through-groove pattern is covered with a photosensitive film, the through-groove pattern is then filled with a plating film by a plating method, and then the conductor is laminated on the surface of the coil wiring board 143 by an etch-back method or a polishing method. The film is removed, and a coil wiring board 143 having a pattern in which only the through groove pattern is filled with a conductor film (for example, the one shown in FIGS. 13I to 13K) is formed. Alternatively, a conductor paste is applied to fill the through-groove pattern, the paste in the portion excluding the through-groove pattern is removed, and the conductor paste in the through-groove is hardened by heat treatment or the like. Alternatively, the molten metal is poured into the through groove pattern, cooled, solidified, and the inside of the through groove is filled with metal (conductor). The coil wiring pattern 144-2 of the coil wiring substrate 142-2 of the second layer is the first spiral pattern as shown in FIG. 13(i). Although it is formed in a rectangular pattern, it may be a circular pattern or an elliptical pattern. Next, when the coil wiring board 142-2 is attached to the supporting board 141-2, the supporting board 141-2 is separated from the coil wiring board 142-2. (FIG. 13(a)) The wiring pattern 144 on the right side of FIG. 13(i) is a pattern for forming the coil terminal on the upper side, but this is shown for the sake of easy understanding in the drawing. However, this pattern may extend the wiring toward the left side of the figure.

Next, the coil wiring board 142-3 of the third layer is attached onto the coil wiring board 142-2 of the second layer. The wiring pattern of the coil wiring substrate 142-3 of the third layer is such that the upper and lower annular wiring patterns as shown in FIG. The wiring pattern 144-2 on the right side is a contact wiring for providing the terminal electrode of the coil on the upper portion. The coil wiring board 142-3 is attached to the support board 141-3, and the coil wiring board 142-3 of the third layer is further attached onto the coil wiring board 142-2 of the second layer. (FIG.13(b)) The figure which separated the support substrate 141-3 is FIG.13(c). In such upper and lower contact wirings, a current does not flow in the horizontal direction but a current flows in the vertical direction. Therefore, the coil wiring board 143 may be thin. Therefore, an insulating film is directly formed on the second-layer coil wiring board 142-2 by a CVD method, a PVD method, or a coating method (SOG, paste), and if necessary, an appropriate heat treatment or the like is performed, and then a photolithography method is performed. The contact hole is opened by using the CVD method, the PVD method, the plating method, or the coating method (paste), and the conductive film is laminated, and the contact hole is filled with the conductive film (it is not always necessary to fill depending on the current flowing through the coil). No.), a photolithography method or an etching method is used to form a conductor film pattern around the contact hole and a contact conductor film pattern with the upper wiring. According to this manufacturing method, the thickness between the coil wirings, that is, the depth of the contact hole can be about 1 μm to 10 μm.
(This figure is also FIG. 13C.)

The contact hole size (vertical a μm, horizontal b μm in the case of a rectangular shape) is selected according to the current passed through the coil. (Of course, the width d and the thickness h of the upper and lower coil wirings) The current flowing through the coil determines the magnetic field generated by the coil. For example, when the contact holes (144-1 and 144-2 in FIG. 13(j)) and the coil wiring 144 are formed by plating, a current of about 106 A/cm 2 is taken into consideration in consideration of electromigration and stress migration. Since the density can be passed, a current of about 10 A can be passed when a=b=30 μm, or d=30 μm and h=30 μm. The coil size is a rectangle of x=1 mm and y=1 mm, the coil is 100 turns, and the central magnetic field of the coil end face generated at this time is considerably large. If the contact depth is 2 μm, the pitch per turn is 32 μm, and the coil length is 3200 μm=3.2 mm after 100 turns. If the contact depth is 20 μm, the pitch per winding is 50 μm, and the coil length is 5000 μm=5.0 mm after 100 turns. It should be noted that the coil wiring board having the coil wiring pattern of the annular winding can be manufactured by the lamination method instead of the adhesion method. The method is the same as the method of forming the contact wiring pattern described above.

Next, a coil wiring board having a contact hole pattern or a coil wiring board 143 having a ring-shaped coil wiring pattern 144 as shown in FIG. 13K is formed on the insulating layer 142-3 having the contact hole pattern. A coil wiring board 142-4 is attached. The coil wiring substrate 142-4 is also attached to the support substrate 141-4 (not shown) and then attached to the coil wiring substrate 142-3, and then the support substrate 141-4 is separated. When the coil wiring board 142-4 can be treated alone, the coil wiring board 142-4 can be directly attached onto the coil wiring board 142-3. Next, a coil wiring board 142-5, which is a coil wiring board 143 having a contact pattern as shown in FIG. 13J, is attached to the support substrate 141-5 and then to the coil wiring board 142-4. As described above, the contacts 144-5-1 can be formed without using the coil wiring board 142-5. Further, the contacts 144-3-2, 144-4-2, and 144-5-2 that connect the lower coil terminal to the upper electrode are sequentially stacked and connected. (Fig. 13(d))

By repeating these processes, the coil wiring pattern as shown in FIG. 13(k) and the contact pattern as shown in FIG. 13(i) are alternately attached or laminated to form a coil having a predetermined number of turns. To form. In FIG. 13E, a coil wiring board having an annular coil wiring pattern has four layers 142-2, 4, 6, and 8, and a coil wiring board having a contact wiring pattern has 142-3, 5, 7,. It is 4 layers of 9. Although the number of turns of the coil wiring has been reduced for simplicity, it is possible to stack more and more. Alternatively, several layers can be stacked on top of each other. When the core is inserted into the coil, the portion after which the coil is to be inserted, that is, the inner portion of the annular coil wiring 144, the inner portion of the portion indicated by the broken line 147 in FIG. A photosensitive film pattern 145 for hollowing out the pattern shown in FIGS. 13(i) to 13(k) inside the portion indicated by the broken line 147 is formed. Since a considerable thickness is etched, a film or thin plate for an etching stopper may be interposed. Using the photosensitive film pattern 145 as a mask, etching is performed from the opening 146 to remove the coil wiring substrate inside the coil wiring. The innermost coil wiring board in the coil wiring board 142-2 having the wiring pattern in the lowermost layer is completely removed, and further the coil wiring board 142-1 having no wiring pattern thereunder is partially (or entirely) etched away. To do. As a result, the coil insertion hole 148 (the side surface becomes 147) is formed. Since a considerable amount of the coil substrate is etched in this etching, it is necessary to make the etching selection ratio of the photosensitive film pattern 145 (and also the etching stopper when the etching stopper is present) and the coil substrate considerably large. Alternatively, the photosensitive film needs to be 145 considerably thicker. Therefore, it is advisable to hollow out the portion 148 to be the coil insertion hole in advance at the stage of manufacturing each coil wiring board. For example, as shown in FIGS. 13(i) to 13(k), the inner portion 148 of the region indicated by the broken line 147 is also removed. Since this removing method can be performed simultaneously with the formation of the wiring groove (through hole) at the time of forming the wiring pattern 144, the number of processes does not increase and the cost does not increase. When forming the wiring pattern 144, the conductor film formed in the cut-out portion 148 may be removed at the same time, or may be masked so that the conductor film is not formed. This also does not increase the number of processes. As a result, when a predetermined number of coil wiring boards are laminated, the coil insertion hole 148 is formed at the same time, and the process of attaching the photosensitive film pattern 145 and the etching stopper is unnecessary.

Next, as shown in FIG. 13F, the core 151 attached to the support substrate 149 is inserted into the coil insertion hole 148. In order to prevent the support substrate 149 from colliding with the uppermost coil wiring substrate 142-9, the protrusion 150 may be provided, the core 151 may be attached to the protrusion 150, and the core 151 may be inserted into the coil insertion hole 148. As a result, the core 151 can be completely inserted into the coil insertion hole 148. The core 151 may be inserted into the coil insertion hole 148 after the adhesive is put into the coil insertion hole 148 by a dispenser or coating, or the core 151 may be attached to the lower surface or the side surface of the core 151 before the core is attached. You may insert it. When the adhesive is in the form of paste, liquid, or gel, it also serves as a buffering agent, so that damage to the coil wiring board 142 can be reduced. Alternatively, an adhesive sheet may be attached to the core 151, and the adhesive sheet also functions as a cushioning material by providing cushioning properties. As described above, the effect as a core can be further enhanced by using a paste containing a powdery soft magnetic material or a liquid or gel material as an adhesive. Even when the core 151 is not used, the magnetic flux density of the coil can be increased to some extent by filling the coil insertion hole with a paste containing a powdery soft magnetic material or a liquid or gel material. In addition, a paste containing a powdery soft magnetic material, or a liquid or gel material is injected to the extent that the coil insertion hole 148 is filled, or the above-mentioned material is filled to the extent that the coil insertion hole 148 is filled when the core 151 is inserted. By injecting the core 151, the core 151 is covered with these materials, and thereafter, it is not necessary to use a material such as an adhesive for filling the coil insertion hole 148.
When the core 151 is inserted and the core 151 is covered with the adhesive or the like in the coil insertion hole 148, the wiring layer exposed on the upper surface of the uppermost coil wiring board 142-9 may be covered with the adhesive or the like. Therefore, the adhesive or the like attached to the upper surface of the uppermost coil wiring board 142-9 is removed by a polishing method (BG method, CMP method, etc.) or an etching method. Further, it is desirable to flatten the upper surface of the uppermost coil wiring board 142-9.

Next, as shown in FIG. 13G, patterning 152 of the photosensitive film for determining the outer shape of the coil is performed. The coil wiring substrate 142 is etched by using the pattern 152 of the photosensitive film as a mask to remove unnecessary portions up to the coil wiring substrate 142-1 in the lowermost layer. Since the coil wiring board 142 is also thick, the coil wiring boards 142 can be stacked in a state where the outer shapes of the coils are determined. The outer shape of each coil wiring board 142 (142-1, 2,...) is wired on a board having a fixed outer shape from the beginning (for example, a board 143 having only the outer shape shown in FIGS. 13( i) to 13 (k )). It is also possible to use a through hole having a pattern and a pattern for filling the conductor film in the through hole. Alternatively, a large number of coil wiring boards 142 (142-1, 2,...) Having a large area on which external portions and through holes for wiring and a pattern for filling a conductor film in the through holes are formed (or It is also possible to stack the manufactured products. Thus, as shown in FIG. 13H, the coil 140 attached to the support substrate 141-1 is formed.

Next, the fourth substrate 153 is attached to the upper surface of the coil 140 (the coil wiring substrate 142-9 in FIG. 13G). (FIG. 13(l)) The fourth substrate 153 is an insulating substrate such as a glass substrate, a quartz substrate, a sapphire substrate, an alumina substrate, an AlN substrate, a ceramic substrate, various polymer substrates such as epoxy and polyimide, and a plastic substrate. In the case of a semiconductor substrate such as a conductor substrate or a Si substrate, it is necessary to cover the surface and contact hole portions with an insulating film. After the fourth substrate is attached, contact holes are formed in the fourth substrate 153 and the conductivity inside the conductor film wiring patterns 144-9-1 and 144-9-2 of the uppermost coil wiring substrate 142-9. The body film wiring 154 is formed, and further electrode/wiring patterns 155-1 and 155-2 connected to at least the contact 154 thereof are manufactured. The conductor film wiring pattern 144-9-2 is a wiring connected to the coil wiring terminal of the coil wiring substrate 142-2 at the bottom, and the electrode/wiring pattern 155-2 is connected to this. The other coil wiring terminal is the coil wiring terminal 144-9-1 of the uppermost coil wiring board 142-9, and the one connected to this is the electrode/wiring pattern 155-1. Therefore, a current can be passed through the coil 140 between the conductor film wiring patterns 144-9-1 and 144-9-2 to generate a magnetic field. When the fourth substrate 153 is an insulating substrate (or a conductor film substrate or a semiconductor substrate whose surface is covered with an insulating film), the coil wiring substrate 142-9, which is only the contact wiring pattern, can be omitted, and the coil wiring substrate 142-9 can be omitted. The coil wiring board 142-8 having the coil wiring pattern can be directly attached. In that case, an insulating adhesive is used as the adhesive. The fourth substrate 153 on which the contact 154 and the conductor film/wiring electrode 155 are formed in advance can be attached to the coil 140, but the conductor film wiring patterns 144-9-1 and 144-9-2 and the contact 154 are connected. For this, a conductive adhesive is used, and for other parts, an insulating adhesive is used. Alternatively, the conductor film wiring patterns 144-9-1 and 144-9-2 and the contacts 154 and other portions can be joined by direct joining (normal temperature, high temperature, fusion bonding, etc.).

After that, the support substrate 141-1 is separated. As a result, the coil 140 attached to the fourth substrate 153 can be manufactured. The coil 140 has a core 151 inside the coil wiring. When the core is not used, it is not necessary to form the coil insertion hole 148, so that the process is simplified. By using the fourth substrate as the supporting substrate 141-1, the same coil 140 can be manufactured, it is not necessary to separate the last supporting substrate 141-1, and the coil without the first wiring pattern is used. There are merits such as not having to use the wiring board 142-1. However, since the fourth substrate 153 is used as a product, it is necessary to construct materials and processes in consideration of reliability such as durability. At this time, contact holes and electrodes/wirings are formed on the side of the fourth substrate 153 which is also a supporting substrate.

The coil 140 attached to the fourth substrate 153 is attached to the second substrate (upper substrate) 202 and the third substrate (lower substrate) 203 attached above and below the cavity 204-2 through which the charged particles shown in FIG. 11 pass. .. FIG. 14 is a diagram showing this state. That is, FIG. 14 shows a quadrupole electromagnet manufactured by the coil (electromagnet) of the present invention. Coils 118-1 and 118-2 are respectively arranged in cavities (coil insertion cavities) 120-1 and 120-2 provided on the left and right (Y direction) of the charged particle passage cavity 204-2, and the coils 118-1 and 118-2 are arranged above them. The second substrate (upper substrate) 202 is attached, and the third substrate (lower substrate) 203 is attached to the lower portion. The lower surface of the coil 140 (140-1) attached to the fourth substrate 153 (153-1) on the second substrate (upper substrate) 202 above the charged particle passage cavity 204-2 in such an accelerator. Attach. The coil 140 (140-1) is attached by applying an adhesive or an adhesive sheet to the attachment surface of the second substrate (upper substrate) 202. Alternatively, an adhesive is applied to the lower surface of the coil 140 (140-1) or an adhesive sheet is applied to attach the coil 140 (140-1). A recess is formed in a portion of the second substrate (upper substrate) 202 where the coil 140 (140-1) is arranged, the second substrate (upper substrate) 202 in that portion is thinned, and the coil 140 (140- 1) may be inserted. Since the thickness of the second substrate (upper substrate) 202 on the charged particle passage cavity 204-2 is thin, the end surface of the coil 140 (140-1) is closer to the charged particle passage cavity 204-2, so that the charged particle passage cavity 204-2 is charged. The magnetic field strength of the particle passage cavity 204-2 can be increased. Since the second substrate (upper substrate) 202 weakens the magnetic field or disturbs the magnetic field, a part of the second substrate (upper substrate) on the charged particle passage cavity 204-2 (the opening portion 159-1 indicated by the dotted line) is removed. May be removed. In that case, in order to prevent the pressure in the charged particle passage cavity 204-2 from rising, the coil 140-1 is sealed with an adhesive or the like so as to completely close the opening 159-1. If a semiconductor substrate such as a conductor film (conductor thin plate) or a Si film (Si substrate) is adhered to the seal portion on the lower end face of the coil 140-1, the second substrate (upper substrate) becomes a glass substrate or the like. If so, it can be firmly attached by anodic electrostatic coupling. Alternatively, if these films, layers or substrates are used for the coil wiring substrate 142-1, they can be strongly adhered similarly by anodic electrostatic coupling.

Alternatively, as shown in FIG. 14, the column 156-1 is attached to the second substrate (upper substrate), and the fourth substrate 153-1 is attached to the column 156-1 to form the cavity 157-1. If the coil 140-1 is arranged therein and the opening 158-1 is provided in the fourth substrate 153-1 so that the vacuum can be drawn, the pressure in the charged particle passage cavity 204-2 rises. Can be prevented. In this case, when the fourth substrate 153-1 is attached to the support 156-1, if the distance between the second substrate (upper substrate) 202 and the end face of the coil 140-1 is set to almost zero, the attachment is performed at the same time. Alternatively, the distance between the charged particle passage cavity 204-2 and the end surface of the coil 140-1 is fixed even if the second substrate (upper substrate) 202 and the end surface of the coil 140-1 are not attached. .. If the pillar 156-1 is formed by using the coil wiring board 142, the number of processes does not increase. Alternatively, the cavity 157-1 is formed in a substrate having a thickness equal to or slightly longer than that of the coil 140-1 (this can be a semiconductor substrate such as an insulating substrate, a conductor substrate, or a Si substrate). The second substrate (upper substrate) 202 or the fourth substrate 153-1 and the coil 140-1 is placed, the second substrate (upper substrate) 202 or the fourth substrate 153 is attached. -1 can be attached. If the second substrate (upper substrate) 202 and the fourth substrate 153-1 are glass substrates or the like and the columns 156-1 are semiconductor substrates such as conductor substrates or Si substrates, they are firmly bonded by electrostatic anodic bonding. You can also Although the direction perpendicular to the paper surface (the traveling direction of the charged particles) is not described, since it can be surrounded by the pillars 156-1 wider than the charged particle passage cavity 204-2, the upper portion of the charged particle passage cavity 204-2 is completely covered. It may be included in cavity 157-1. Therefore, since the outside of the charged particle passage cavity 204-2 is also surrounded by the pressure-controlled cavity 157-1, the pressure of the charged particle passage cavity 204-2 can be controlled to a lower pressure. The electrodes of the coils 118 (118-1, 2) are inside the cavity 157-1, but since they can be routed as wiring, they can be extended to the outside of the cavity.

The coil 140-2 can be arranged exactly under the charged particle passage cavity 204-2. The support 156-2, the opening 159-2 of the third substrate (lower substrate) 203 facing the end surface of the coil, the formation of a recess, the formation of the cavity 157-2, and the formation of the opening 158-2 for evacuation are also formed. It is the same. Further, a plurality of coils 118 (118-1, 2) and a plurality of coils 140 (140-1, 2) can be arranged in the direction perpendicular to the paper surface, that is, along the charged particle passage cavity 204-2, and a plurality of quadrupole magnet spaces can be arranged. Can be manufactured simultaneously and easily. This quadrupole electromagnet can control the convergence and divergence of the charged particles passing through the charged particle passage cavity 204-2.

Although the substrate coil is arranged in FIG. 4, a normal electromagnet may be arranged. For example, a portion for arranging various electromagnets to converge the charged particles (for example, a portion such as 15, 17, 19, 21, 22, 23, 26, 28, 29, 31, 32, 35, 36 in FIG. 1). A quadrupole magnet can be placed in the. One of the magnetic poles of the electromagnet can be easily arranged in the vertical direction, and the magnetic pole may be brought into contact with or brought close to the upper and lower substrates. The closer to the upper and lower substrates, the closer to the charged particle trajectory (near the center of the through chamber), so that the charged particles can be converged even with a smaller magnetic field. On the lateral side, the electromagnet cannot be placed as it is, so in the part where the charged particles are converged, the outer regions (both sides) of the part where the charged particles are converged are cut substantially parallel to the charged particle trajectories and the opening region (both sides) is formed in the substrate. ) Is provided, and the electromagnet is arranged so that the magnetic field is applied to the opening region perpendicularly to the charged particle trajectories. Since the area is limited in space, it is desirable that the area be small and generate a strong magnetic field. The superconducting magnet can be arranged if the magnetic field strength can obtain a desired magnitude considering the container space. Since the accelerator of the present invention has a small size, the size of the container in which the electromagnet is placed is not too large even if the accelerator is placed in a container at a temperature capable of maintaining superconductivity. Laser dicing, high-pressure water dicing, or the like can be used as a method for forming the opening in the substrate. It is possible to accurately open a desired portion in the substrate. The closer the electromagnet disposed on the lateral side is brought into contact with or closer to the substrate, and the closer it is to the substrate, the closer it is to the charged particle trajectory (near the center of the through chamber), so that the charged particles can be converged even with a smaller magnetic field.

In the case of a synchrotron, acceleration of the cavity between the deflection magnets 25, 30, 34, and 37 can generate faster charged particles. For example, the acceleration electrode used in the mass spectrometer described later can be used. That is, a large number of accelerating electrodes (which can also be used for focusing and decelerating) in which conductor film electrodes are laminated on a substrate side wall plate having a central hole are formed in parallel in the penetration chamber. If gradually increasing voltage is applied to the accelerating electrodes arranged in large numbers in the traveling direction of the charged particles, the charged particles passing through the central hole of the accelerating electrode are accelerated. For example, if 100 side wall boards are arranged at a pitch of 1 mm, the length is 100 mm, but if the voltage is divided between them and 100 V is applied as a whole, 1/2 mv2=qV (m: mass of charged particles) , V: speed, q: charge, V: applied voltage), m=10 ⁻²⁵ kg and q=e, and v=14 km/sec. Accelerating at 4 places will result in 56 km/sec. After 1000 laps, the speed becomes 56000 km/sec, which is 1/5 of the speed of light.
Alternatively, the charged particles are also accelerated by applying a high frequency voltage to a large number of accelerating electrodes arranged, and the speed can be increased by increasing the frequency. Since a large number of circular orbits of the synchrotron can be arranged (see FIG. 16), the velocity of the charged particles can be reasonably increased by gradually increasing the frequency of the high frequency voltage in each orbit. In the case of a linear accelerator, it is only necessary to cut the substrate on the lateral side of the penetration chamber, so it is easy to arrange the electromagnets from the lateral side (left and right direction).

FIG. 5 is a diagram showing an accelerator in which a plurality of charged particle accelerators of the present invention are connected. A large number of (200-1, 2, 3,...) Accelerators 200 shown in FIG. 4 are connected, and a high-frequency generator 225 is passed through a high-frequency introduction pipe (waveguide) 223 for inputting a high frequency to each accelerator. A high frequency is input and an accelerating device 200 creates an accelerating electric field to accelerate the velocity of the charged particles incident on the accelerating device 200 (200-1) from the charged particle generating device 221 to obtain the final stage accelerating device 200 (200-3). The charged particles 227 are emitted at high speed. Further, the high frequency wave that has passed through the accelerator 200 exits from the high frequency discharge tube 224. The control unit 226 controls the frequency, power, timing (pulses, etc.) of each of the high-frequency generator 200 and the charged particle generator 221. Since the accelerator of the present invention can be manufactured by freely changing the size, it can be selected according to the application. For example, if the cavity depth (h1, that is, the thickness of the main substrate) is 1 mm, the width of the accelerator can be set to about 3 mm, so that a 300 mm×300 mm wafer (rectangle in this case) and an accelerator with a length of 300 mm can be used. 100 can be produced. Therefore, one wafer can be used to fabricate an accelerator having a length of 30 m. If the accelerator has such a small width, the whole can be covered with a vacuum (ultra-low pressure) box. Therefore, if the inside of the accelerator is also evacuated, an ultra-low pressure cavity can be realized. Further, since the whole can be immersed in liquid He, liquid nitrogen or the like, it is possible to suppress heat generation due to high frequency application, and since a superconductor can be used for the focusing electromagnet, it is possible to enhance the magnetic field of the electromagnet.

FIG. 6 is a diagram showing an example of a method of manufacturing the charged particle accelerator of the present invention. The charged particle accelerator of the present invention uses the through hole formed in the main substrate 201 as the charged particle accelerating cavity. The main substrate 201 is attached to the lower substrate 203. For the main substrate 201, various materials such as a conductor substrate, an insulator substrate, and a semiconductor substrate can be used. As the conductor substrate, a metal substrate such as copper or aluminum, a semiconductor substrate highly doped with carriers (for example, a low resistance semiconductor substrate), a conductive plastic, a conductive ceramic, a conductive carbon substrate, or the like can be used. However, it is desirable not to use a ferromagnetic material or a paramagnetic material because it affects the magnetic field generated by the introduction of high frequency. Therefore, non-magnetic stainless steel such as austenitic stainless steel can be used. As the insulating substrate, a glass substrate, a quartz substrate, a sapphire substrate, an alumina substrate, an AlN substrate, a plastic substrate, a ceramic substrate, or the like can be used. A silicon substrate, a SiC substrate, a carbon substrate, a compound semiconductor substrate, or the like can be used as the semiconductor substrate. In this specification, unless otherwise specified, the main substrate will be described as a silicon substrate which is a semiconductor substrate.

For the lower substrate 203, various materials such as a conductor substrate, an insulator substrate, and a semiconductor substrate can be used, and the specific material is the same as that of the main substrate 201. In this specification, unless otherwise specified, the lower substrate will be described as a glass substrate which is an insulator substrate. As a method of attaching the main substrate 201 and the lower substrate 203, there are a method of attaching using an adhesive, a fusion method of melting and attaching the attaching surfaces, a room temperature joining method, a high temperature joining method, a diffusion joining method, and the like. In the case of a semiconductor substrate such as a silicon substrate or a conductor substrate and a glass substrate, an electrostatic bonding (anodic bonding) method can also be used. It is also possible to form an insulating film, a metal film, or the like on the lower surface of the main substrate 201 by a CVD (chemical vapor deposition) method or a PVD (physical growth) method, and then adhere the lower substrate 203. Next, as shown in FIG. 6A, a photosensitive film 233 such as a photoresist is formed on the upper surface of the main substrate 201 by a coating method or a sheet attachment method, and a window is opened by a photolithography method to form a photosensitive film pattern 233. Form. The photosensitive film pattern 233 is for forming a through hole (may be considered as a through chamber) in the main substrate 201. An insulating film or a metal film may be formed between the main substrate 201 and the photosensitive film. These insulating films and metal films serve as a protective film for the main substrate 201, and the photosensitive film 233 is also etched during the etching of the main substrate 201. At that time, when the photosensitive film 233 is also completely etched. Also has a role as an etching stopper.

Next, using the patterned photosensitive film 233 as a mask, the portion of the main substrate 201 having the window opened is etched. When the main substrate 201 is silicon, CF-based, SF-based, CCl-based, SiCl-based, Cl-based, Br-based, or the like can be used as an etching gas, and the through holes (cavities) are desirably patterns that are as perpendicular to the main substrate surface as possible. It is desirable to perform etching in a shape that is faithful to the photosensitive film pattern 233 (shown by the dotted line 234 in FIG. 6A). As such a vertical etching method, there are an RIE (reactive ion etching) method, a Bosch method, and a cryo method.

When the lower substrate 203 is a glass substrate, a large etching selection ratio can be obtained by the above-mentioned etching gas or etching method. However, the etching amount of the lower substrate 203 is small. For example, when the thickness of the main substrate 201 is 500 μm and the etching selection ratio is 50, even if overetching is performed by 25%, the through hole can be completely formed in the entire main substrate 201 by this degree of overetching of the lower substrate 203. The etching amount is at most 5 μm. Therefore, it is sufficient for the lower substrate to have a thickness of 10 μm, but it is desirable to set the thickness to about 100 μm or more in order to maintain a certain level of strength. Another substrate may be attached to the lower substrate 203 for reinforcement later. There is also a method in which a thick lower substrate 203 (for example, 300 μm or more) is adhered and then thinned to a thickness of 100 μm or less by a polishing method (CMP method or BG method) or an etch back method.

FIG. 6B is a sectional view after the main substrate 201 is etched to form the through holes and the photosensitive film 233 is removed. This cross section is a view as seen in the longitudinal direction (left and right) of the cavity, and corresponds to FIG. 5A, and substrate side walls 201S-(A), 201S-(1), 201S-(i) {i= 1, 2,...}, 201S-(B), etc. are cavities (may be called a through hole, a through groove, a through chamber) 204C-(A), 204C-(i), 204C-(B), etc. Is formed. The parentheses () here mean that a cavity or a half of the side wall of the substrate is formed, as described later. Therefore, here, the substrate thickness of the main substrate 201 is h2/2. In FIG. 6A, H indicating half of the main substrate 201 (201H) is attached. The substrate side wall 201S is formed as a main substrate side wall substantially perpendicular to the front surface or the back surface of the main substrate 201. However, even if it cannot be formed almost vertically, it is possible to obtain predetermined characteristics as an accelerator by suppressing the angle to within 90°±10°. Even in the case of more than this, the speed and direction of the charged particles can be controlled by adjusting the high frequency input voltage, the conditions of the charged particle generator, the input voltage of the focusing electromagnet, and the like.

6C and 6D, the substrate side wall 201S is perpendicular to the longitudinal direction of the cavity 204 (the traveling direction of charged particles, the horizontal direction in FIGS. 6A and 6B). It is the figure seen from. That is, it is a diagram showing a method of forming the central hole 205. In order to form the central hole 205 after forming the substrate side wall 201S shown in FIG. 6B, forming the photosensitive film 235 (using a photolithography method for the photosensitive sheet attachment method or the photosensitive film coating method). Open the window 236 of. The photosensitive film 235 may be formed after forming the insulating film on the surface of the main substrate 201. Using the patterned photosensitive film 235 as a mask, the main substrate 201 is etched from the window opening portion 236 to form the central hole 205. When the shape of the central hole is rectangular and the vertical length is e1 and the horizontal length is e2, the state after removing the photosensitive film 235 is shown in FIG. 6(d). In addition, the depth (vertical length) of the central hole at this stage is ½×e1. Although the cavity is not visible in FIGS. 6C and 6D, the cavity is present before or behind this substrate side wall 201 (for example, 201S-(i)) {i=1, 2, 3,...}, The boundary is indicated by a dotted line 237. As can be easily understood, the process of forming the central hole 205 in FIGS. 6C and 6D is performed before forming the substrate sidewall 201S and the cavity 204 shown in FIG. 6B, that is, before FIG. 6A. It can also be formed. In that case, since there is no unevenness such as cavities, there is an advantage that a photosensitive film pattern can be easily formed.

Next, as shown in FIG. 6E, an insulating film 238 is formed on the main substrate 201 and inside the through holes 204. The insulating film 238 is formed in the case where the main substrate 201 is a semiconductor or a conductor and the conductive film 206 to be formed later becomes conductive and causes a problem. Alternatively, it is formed as an adhesion improving film with the conductor film. When the main substrate 201 is an insulator, it is not necessary because it does not conduct, but an insulating film can be formed to improve the adhesion. The insulating film 238 is formed by a CVD method, a PVD method, or the like. For example, a silicon oxide film (SiOx), a silicon nitride film (SiNx), a silicon oxynitride film (SiNxOy). When the main substrate 201 is silicon, it can also be formed by oxidation or nitridation. After that, the conductor film 206 is formed. Since the conductor film 206 is for forming an acceleration electric field by high frequency, it is preferable that the conductor film 206 has high conductivity. Further, a non-magnetic material (including a diamagnetic material) that does not affect the magnetic field generation is preferable. For example, copper, gold, silver, Ti, Zr, Ta, tungsten, aluminum, carbon (for example, conductive nanotube), various silicides, alloys thereof, conductive PolySi, and composite films of these are preferable. These conductor films can be formed by the CVD method, PVD method, or plating method. The conductor film 206 may be formed after the conductor film 206, the insulating film 238, the main substrate 201, and the lower (upper) substrates 202 and 203 are formed with the adhesiveness improving film for improving the adhesiveness. Examples of the adhesion improving film include titanium (Ti) and titanium nitride (TiN).

Since it is necessary to remove or pattern the conductor film in the cavities other than the charged particle accelerator portion, a photosensitive film is formed and patterned, and the unnecessary conductor film 206 is etched. A conductor film 206 is formed inside the cavity (acceleration cavity) 204C-(i) in the charged particle accelerator and the high-frequency introduction chamber 204C-(A) and the high-frequency extraction chamber 204C-(B). After patterning the conductor film 206, an insulating film for a protective film can be formed, but if the protective film is unnecessary, it may not be formed.

FIG. 7 shows the details of the process. FIG. 7 is a diagram showing a process from the formation of the side wall of the substrate to the patterning of the conductor film, and for simplicity, only a part of the structure shown in FIG. 6 is shown. As shown in FIG. 7A, after forming the substrate sidewall 201S (201S-(A), 201S-(1), etc.) and the cavity 204 (204C-(A), 204C-(1), etc.), the insulating film is formed. 238 is formed, then the conductor film 206 is formed, and then the photosensitive film 241 is formed. The photosensitive film 241 is formed by a coating method or by attaching a photosensitive sheet and softening the sheet. Next, as shown in FIG. 7B, a desired pattern 241 is formed by an exposure method (including development and baking), the photosensitive film in a portion where the conductor film 206 is to be removed is removed, and a window is opened. .. The exposed conductor film 206 in the window-opened portion is removed by dry etching or wet etching. When a protective film or the like is present on the conductor film 206, the conductor film 206 is etched after the protective film or the like is removed by etching. After the conductor film 206 is etched, the insulating film 238 exists below it, and when it is also removed, the insulating film 238 is also removed by dry etching or wet etching. Then, if the photosensitive film 241 is removed, the conductor film 206 is formed at a desired portion as shown in FIG. 7C. When the conductor film 206 in the accelerator is connected, the conductor film 206 on the convex portion of the substrate side wall 201S can be left. When the conductor film is formed in the central hole, the photosensitive film may be formed (remained) in the central hole portion.

A method of thickly laminating the conductor film at a portion where the conductor film 206 is desired to be left will be described. Since the conductor film 206 only needs to be a seed (seed) for plating, it need only be thinly laminated. For example, when the conductor film 206 is copper, it may have a thickness of about 100 nm. After FIG. 7A, a window is opened in a portion where the conductor film 206 is to be laminated. That is, as shown in FIG. 7D, the photosensitive film 242 is patterned, and a window is opened in the acceleration cavity portion or the like where the conductor film 206 is to be laminated. Therefore, the patterning is the reverse of that of FIG. In this state, it is immersed in a plating solution (for example, copper sulfate solution in the case of copper plating) and a thick plating film 243 of copper or the like is plated on the portion of the conductor film 206 exposed by the electric field application. If the electroless plating method is used, the conductor film 206 to be laminated first may be unnecessary. After that, the photosensitive film 242 is removed, and then the thin conductor film 206 is etched. However, since the conductor film 206 is thinner than the plated film 243 (+206), an etching solution or etching gas for the conductor film 206 is used. The entire surface is etched. In this way, a new mask (photosensitive film or the like) is unnecessary, and the conductor films 206 and 243 can be formed only in desired regions.

The same structure is formed on the upper substrate 202 by the process shown in FIGS. The charged particle accelerator of the present invention has a (substantially) symmetrical shape vertically and horizontally with respect to the center of the cavity 204. Therefore, as shown in FIG. 6(f), the structure shown in FIG. 6(e) formed on the lower substrate 203 and the structure shown in FIG. 6(e) formed on the upper substrate 202 are attached to each other on the upper surfaces of the main substrate 201. Let Since the upper substrate 202 and the lower substrate 203 are, for example, glass substrates, visible light passes through the hollow portion 204 without the conductor film 206. Therefore, the upper substrate (the upper substrate 202 and the main substrate 201) and the lower substrate (the lower substrate) are directly connected. Since 203 and the main substrate 201) can be aligned, the alignment can be performed extremely accurately. Since the accelerating device of the present invention can be manufactured by the LSI process, the pattern accuracy is 1 μm or less. Therefore, if the alignment accuracy is 3 μm, the upper substrate and the lower substrate can be attached with an accuracy of 5 μm or less. This accuracy is sufficient for controlling the accelerator.

The main substrates can be firmly attached to each other by a room temperature bonding method, a diffusion bonding method, a high temperature bonding method, or an adhesive. If the insulating film is present in the adhered portion 239 and the adhesion is insufficient, the insulating film in this portion is removed, and the main substrates (for example, silicon) are bonded to each other at room temperature, surface activation method, high temperature bonding method or diffusion. It can be attached by a joining method. Alternatively, a metal film or an adhesive may be attached to this portion, and the upper substrate and the lower substrate may be firmly attached by room temperature bonding or by applying heat or pressure. Further, a thin glass substrate may be sandwiched in this portion and firmly adhered to the upper and lower main substrates (for example, silicon) by electrostatic coupling (anodic bonding). Further, if a conductive adhesive is used, it is possible to electrically connect the conductor film 206 formed on the upper substrate and the conductor film 206 formed on the lower substrate. Even without using a conductive adhesive, it is possible to bond at room temperature or electrically connect the conductive film 206 by applying an appropriate temperature or pressure. Here, S1 is a joint surface, and the center of the accelerating cavity substantially overlaps with S1. The center of the central hole also overlaps with S1.

FIG. 6G is a view of the cross section of the substrate side wall 201S in FIG. 6F as seen from a direction perpendicular to the longitudinal direction of the cavity. In the figure in which the upper substrate (upper substrate 202 and main substrate 201) and the lower substrate (lower substrate 203 and main substrate 201) are attached at the bonding surface S2, the boundary of the cavity is indicated by the broken line 237. When the upper substrate 202 and the lower substrate 203 are substantially the same substrate, the upper and lower sides are substantially symmetrical with respect to the bonding surface S2. A central hole 205 is formed in the center thereof. When the central hole 205 has a rectangular shape, the vertical is e1 and the horizontal is e2, as can be seen from FIG. In the central hole 205, an insulating film 239 such as a silicon oxide film may be laminated on the surface of the substrate side wall 201S to further form a conductor film 206. In FIG. 6G, the conductor film 206 between the upper substrate and the lower substrate 203 is removed. In this removal, the portion where the conductor film 206 is to be left is masked with a photosensitive film. The window of the photosensitive film is opened in the portion to be removed, and the conductive film 206 is removed by etching with an etchant or etching gas. The insulating film 239 may be removed at the bonding surface (adhesion surface) S2. In this case, the main substrate 201 and the main substrate 201 are joined together. Further, a thin glass substrate is sandwiched between the main substrate 201 (201 (U) because it is on the upper side) and the main substrate 201 (201 (B) because it is on the lower side), and they are firmly attached by electrostatic (anodic) coupling. You can also

As described above, the charged particle accelerator can be manufactured using the flat substrate (including the main substrate, the lower substrate, and the upper substrate). Conventionally, the disks to be placed in the accelerating tube are manufactured one by one, and the accelerating cavities are also manufactured one by one to assemble them, so that the device becomes large, and the assembling time and the assembling cost become enormous. Although it was difficult to improve the accuracy, in the case of the present invention, since the LSI process is used or applied, a large amount, inexpensively and accurately (the alignment error is at most 1 to 5 μm or less). ) Can be made.

FIG. 8 shows a charged particle accelerator in which a glass substrate 251 is sandwiched between an upper substrate (main substrate 201U, upper substrate 202) and a lower substrate (main substrate 201B, lower substrate 203) to be attached by electrostatic coupling. It is a figure which shows the manufacturing method. 6 and 7 are omitted in some places. A silicon substrate 201 (which is referred to as 201B because it is a substrate on the lower side) and a glass substrate or a quartz glass substrate which is the lower substrate 203 are bonded by anodic bonding. Next, the glass substrate or the quartz glass substrate 251 is also bonded to the other surface of the silicon substrate 201 by anodic bonding. At this time, since it is necessary to apply a plus (+) voltage to the silicon substrate 201, a plus (+) voltage is applied from the side surface of the silicon substrate 201, or the periphery of the lower substrate 203 is removed by photolithography. The silicon substrate 201 is exposed by applying a positive (+) voltage from the exposed portion. (Note that the silicon substrate 201 can also be anodically bonded to a conductive substrate such as a metal plate. Further, if a metal film such as aluminum is thinly laminated on the silicon substrate 201 and then bonded to a glass substrate, the metal film is formed. Low temperature bonding is possible as compared with anodic bonding in the case of no glass substrate.) Since the thickness of the glass substrate 251 and the like is preferably thin, 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less. It may be 10 μm or less. As a thinning method, a thick glass substrate or the like may be first attached and then thinning can be performed by a polishing method (CMP, BG, etc.) or an etching method (wet, dry, etc.).

Next, a pattern of the photosensitive film 233 for forming the substrate sidewall 201S is formed by photolithography. Next, using the pattern of the photosensitive film 233, the glass substrate 251 in the region where the window is opened is removed by etching. Anisotropic dry etching (vertical etching) is desirable in order to etch the pattern of the photosensitive film 233 as faithfully as possible, but wet etching or isotropic dry etching may be used in consideration of the side etching amount. After the glass substrate 251 is removed by etching, the silicon substrate 201 is removed by etching. Anisotropic dry etching (vertical etching) is desirable in order to etch the pattern of the photosensitive film 233 as faithfully as possible, but wet etching or isotropic dry etching may be used in consideration of the side etching amount. In FIG. 8A, the vertical etching line 234 is indicated by a broken line.

The central hole 205 is also formed by patterning the photosensitive film on the glass substrate 251 and partially etching the glass substrate 251 and the main substrate 201. When the size of the central hole is equal to or less than the thickness of the glass substrate 251, only the glass substrate 251 may be etched. On the contrary, the thickness of the glass substrate 251 can be matched with the size of the central hole. In that case, by increasing the etching selection ratio between the glass substrate 251 and the main substrate 201, the size of the central hole becomes equal to the thickness of the glass substrate. , Very accurately control the size of the central hole. The patterning of the central hole is performed by patterning the substrate side walls 201S-(A), 201S-(i) {i=1, 2,...}, 201S-(B) and the through holes 204C-(A), 204C-(i). , 204C-(B) may be formed. Next, the insulating film 238 is formed and then the conductor film 206 is formed. (FIG. 8B) Next, required patterning of the conductor film is performed by photolithography and etching. (FIG. 8C) The conductor film 206 is formed on the inner surface of the through holes 204C-(A), 204C-(i) {i=1, 2,...}, 204C-(B) to be the acceleration cavities. Is formed. Further, the conductor film 206 is left in the necessary portion on the inner surface of the central hole 205 connecting them.
The other side (the upper substrate 202 side on the upper side in FIG. 8) is similarly prepared and they are attached. (FIG. 8D) Since the conductor film 206 is also attached to the side surface of the glass substrate 251, they can be attached and connected by performing pressure or heat treatment. Further, if necessary, a conductive adhesive or a solder metal may be attached to the connection portion and then attached together to ensure sufficient connection. The conductive adhesive or the solder metal can be applied by tracing with a dispenser or the like. Alternatively, a dispenser or the like having the same inlet as the connecting portion can be manufactured, and the conductive adhesive or the solder metal (melted or paste) can be attached to the connecting portion all at once from the inlet. Alternatively, a required portion of the conductor film is patterned and exposed by a photosensitive film, and a solder metal is deposited on the exposed portion by a plating method. These may be adhered and heat treated. Further, after that, openings for vacuuming or purging/cleaning are opened in the upper substrate 202 or the lower substrate 203. It is also possible to use this opening to inject a plating solution to plate the connecting portion and the like. Alternatively, a selective CVD gas (for example, WF6) may be introduced through the opening, and a metal film (for example, W) may be selectively laminated on the exposed portion of the conductor film 206 such as the connection portion. Alternatively, even if the connection is insufficient, the electrodes can be formed above and below, so that the same high-frequency voltage may be applied from both. An adhesive surface when the same objects as those in FIG. 8C are attached to each other is 244 indicated by a chain line, and has a shape that is substantially symmetrical vertically with respect to the adhesive surface 244. Since this bonding is a bonding of glass surfaces to each other, electrostatic anodic bonding cannot be performed. Therefore, if the glass substrate 251 is not used on one side, electrostatic anodic bonding can be used when bonding the upper and lower sides. Therefore, strong joining can be realized.

Next, as shown in FIG. 8E, contact holes are formed in the lower substrate 203 and the insulating film 238, a conductor film is formed therein, and a contact 245 for connecting to the conductor film 206 is formed. Further, a conductor film/electrode/wiring 246 connected to the contact 245 is formed. Similarly, a contact hole is formed in the upper substrate 202 and the insulating film 238, a conductor film is formed therein, and a contact 248 connecting to the conductor film 206 is formed. Further, a conductor film/electrode/wiring 249 connected to the contact 248 is formed. As shown in FIG. 8E, the contacts 245, 248 and the electrodes/wirings 245, 249 are formed of the conductor film 206 formed on the inner surfaces of the respective cavity chambers 204C-A, B, 204C-i. Each can be made so that it can be connected to, and no increase in process occurs. As a result, it is possible to individually apply a voltage from the outside to the conductor film 206 formed on the inner surface of each cavity. Further, the upper and lower conductor films 206 are joined to each other at the joint surface 244 and bonded, but even if the bonding is insufficient, since the (high frequency) voltage can be applied from the upper and lower electrodes 246 and 249, respectively, the same potential can be obtained. .. Further, an opening 247 for evacuation is formed in the lower substrate 203, and an opening 250 for evacuation is formed in the upper substrate 202. The openings 247 and 250 can also be formed in the respective cavities at the same time, the pressure in each of the cavities can be individually controlled, and a very small space can be individually evacuated, so that an ultra-low pressure cavity can be realized. it can. As described above, by using this opening, the plating solution can be introduced into the cavity to plate the connection portion of the inner conductor film, or the selective CVD gas can be introduced into the cavity to remove the inner conductor film. A selective conductor film may be laminated on the connection portion. As described above, a very small accelerating cavity can be produced extremely easily.
Next, the bending electromagnet will be described. A bending electromagnet can be manufactured by using the coils arranged above and below among the quadrupole magnets shown in FIGS. 4 and 11 to 14. FIG. 15 is a diagram showing charged particle passage cavities such as the deflection electromagnets 25, 30, 34, 37 in FIG. 1 and electromagnets arranged therein. FIG. 15A is a diagram showing the arrangement state of the charged particle passage cavity 257 and the coil in the deflection electromagnet portion. The charged particle passage cavity 257 is a cavity along which the central orbit has a curvature of radius R. A large number of minute coils 258, which are electromagnets, are arranged above and below this cavity. The micro coils 258 are densely arranged so as to cover the entire charged particle passage cavity 257. The charged particles G enter through the entrance of the charged particle passage cavity 257, undergo Lorentz force by the vertical magnetic field in the charged particle passage cavity 257, make circular motion with the orbital radius R, and exit from the exit of the charged particle passage cavity 257. ..

A cross-sectional view of the charged particle passage cavity 257 along a cross section A1-A2 perpendicular to the center of curvature is shown in FIG. An upper substrate 262 and a lower substrate 263 close the upper and lower sides of the through chamber 264 formed in the main substrate 261. The penetrating chamber 264 is a charged particle passage cavity 257, and the central orbit is a cavity having a circular orbit of radius R. A plurality of coils 260 (260-1, 2, 3) are arranged on the upper surface of the upper substrate 262. The coils 260 (260-1, 2, 3) are attached to the fourth substrate 266, the fourth substrate 266 is attached to the columns 265 (265-1, 2), and the columns 265 are attached to the upper substrate 262. The smaller the coil size (size in the direction perpendicular to the coil axis), the larger the number of turns, the larger the flowing current, and the larger the magnetic field at the end surface of the coil. The magnetic field exerted on the cavity 257 is large. In the coil of the present invention, it is easy to reduce the coil size as shown in FIG. 13, but the current that can be passed is also reduced when the wiring size is reduced. Therefore, although the coil size cannot be determined unconditionally, when the size of the coil 260 is smaller than that of the charged particle passage cavity 257, a plurality of charged particle passage cavities 257 are arranged so that the entire coil 260 is completely covered. For example, when the coil size is 0.5 mm×0.5 mm and the width of the charged particle passage cavity 257 is 1 mm, at least three coils have a width of the charged particle passage cavity 257 as shown in FIG. Arrange in the direction. At that time, since the central orbit of the charged particles G is substantially the center in the width direction of the charged particle passage cavity 257, it is desirable to arrange the coils so that the axes of one coil substantially coincide with each other. This is because the center of the coil end face has the largest magnetic field. (However, there is not much difference.) The coils are arranged closely in the width direction. The distance between the coils (for example, the distance between the coils 260-1 and 260-2) is determined when the coils are manufactured (when the coil wiring boards are stacked and attached), and it is not necessary to separate the coils from each other. Can be quite small. For example, it is possible to set the inter-wiring distance to about the coil wiring width. When the coil size is larger than the charged particle passage cavity 257, one coil may be used in the width direction. Also at this time, it is desirable to arrange the coil so that the axis of the coil is located on the center of the charged particle passage cavity 257.

Further, regarding the traveling direction of the charged particles in the charged particle passage cavity 257, the coils may be arranged without gaps by using the coil pattern of the coil wiring board that matches the trajectory. For example, the coils 258 are arranged as shown in FIG. Then, the coil array groups are collectively separated (or may be separated) and attached to the fourth substrate, and the pillars 265 (265-1, 2) are used as the base (or together) on the upper substrate 262. Adhere to. This is similar to that described with reference to FIG. The axis of the coil 260 is made perpendicular to the surface of the upper substrate 262 and the main substrate. Further, since the end surface of the coil 260 should be as close to the charged particle passage cavity 257 as possible, the end surface of the coil 260 should be brought into contact with and attached to the upper substrate 262, or as close as possible. The portion 273-1 of the upper substrate 262 in the portion where the coil 260 is arranged is made thin (in practice, the coil 260 (260-1, 2, 3) is wider than the width of the charged particle passage cavity 257, It is also desirable to insert a recess into which the coil 260 wider than the width of the charged particle passage cavity 257 can all enter) and insert the coil 260 (260-1, 2, 3) into the recess. Further, it is also possible to open the portion 273-1 of the upper substrate 262 in the portion where the coil 260 is arranged in the charged particle passage cavity 257 so that the magnetic field of the coil 260 is not weakened or disturbed by the upper substrate 262. desirable. In this case, since the airtight space of the charged particle passage cavity 257 is broken, it is desirable to reliably adhere the outer peripheral portion of the lower end surface of the coil 260 (in this case, the outer peripheral portions of the plurality of coils) and the upper substrate 262. For example, an adhesive (solder metal) is attached to the outer peripheral portion of the coil, or room temperature bonding, high temperature bonding, diffusion bonding, or electrostatic anodic bonding is performed reliably. Further, a space 269 in which the coil is arranged is used as an airtight space, and an opening 270 for evacuation is provided in the fourth substrate 266, and the airtight space 269 is made to have an extremely low pressure through the evacuation opening 270. Of course, the charged particle passage cavity 257 is also provided with an opening for vacuuming the upper substrate 262 and the lower substrate 263 so that vacuum can be drawn through the opening. As a result, the charged particle passage cavity 257 can be an ultra-ultra-low pressure space.

Similarly, on the lower substrate 263, the coils 259 (259-1, 2, 3) are arranged. A recess 273-2 or an opening 273-2 can be provided to bring the end surface of the coil 259 (259-1, 2, 3) closer to the charged particle passage cavity 257. The coil 259 is attached to the fourth substrate 268, the columns 267 (267-1, 2) are attached to the lower substrate 263, and the fourth substrate 268 is attached to the columns 267. The space 271 in which the coil 259 is arranged may be an airtight space, and the fourth substrate 268 may be provided with the vacuuming opening 272. It is desirable that the same number of coils 259 on the lower substrate 263 side as those on the upper substrate 262 side are arranged symmetrically with respect to the charged particle passage cavities 257. If the characteristics are the same, it is easy to control the magnetic field in the charged particle passage cavity 257. However, even with coils of different sizes, the magnetic field in the charged particle passage cavity 257 can be controlled in the same manner by adjusting the magnitude of the current to be passed. According to the present invention, the shape of the coil can be set according to the shape of the cavity in which the coil is arranged. For example, the coil wiring can have an arbitrary curved shape. Further, the coil size can be freely set, and the number of coil arrangement items and the arrangement shape can be freely changed. The deflection magnet portions 25, 30, 34, 37, etc. of the synchrotron shown in FIG. 1 are fan-shaped cavities having a radius of curvature of R, but coils corresponding thereto can be freely arranged. Of course, the arrangement shape and the number of arrangement of the quadrupole electromagnets and the focusing electromagnets in the linear cavity can be freely set.

As described above, the accelerator of the present invention can collectively manufacture devices having various functions, so that the substrate can be enlarged and further devices can be connected. The micro-accelerator as the synchrotron shown in FIG. 1 can be connected to a synchrotron that is one size larger, and they can be simultaneously manufactured. FIG. 16 is a diagram in which the micro-accelerator 10-1 having the circular accelerator (synchrotron) 8-1 shown in FIG. 1 is connected to the circular accelerator 8-2 which is one size larger, and is a double synchrotron (or 2). It is a figure which shows a cycle synchrotron. A second synchrotron 8-2 surrounds the first small micro-accelerator 10-1. These are collectively referred to as a micro device 10-2. The outlet 41-1 of the first small micro-accelerator 10-1 (which may be considered to be the same as that shown in FIG. 1) (41 in FIG. 1, but the outlet 41 of the second large synchrotron) (This is attached with "-1" to distinguish it from 41-2.) is connected to the inflector 21-2 of the second synchrotron 8-2. That is, the charged particles that have exited the outlet 41-1 of the first small synchrotron 8-1 pass through the inflector 21-2 and enter the storage ring 24-2 that is a cavity through which the charged particles pass in the circular accelerator 8. Incident. A linear accelerator 39-1 may be provided in the middle of the cavity exiting the circular accelerator 8 to adjust the velocity of charged particles entering the inflector 21-2. In addition, another deflection electromagnet, an acceleration electrode, a deceleration electrode, a linear acceleration device, a focusing electromagnet, etc. may be provided on the way.

The charged particles that have entered the storage ring 24-2 of the circular accelerator 8-2 from the inflector 21-2 may be converged by providing a (horizontal direction) focusing electromagnet or a (vertical direction) focusing electromagnet. It is deflected and accelerated by the electromagnet 25-2, enters the next storage ring 27-2, is further accelerated by the high-frequency acceleration cavity 29-2, and is converged (for vertical direction) electromagnet 26-2 and converged (for horizontal direction). It is converged by the electromagnet 28-2, deflected/accelerated by the deflection electromagnet 30-2, and enters the next storage ring 33-2. Here again, the convergence electromagnet 31-2 (for vertical direction) and the convergence electromagnet 32 (for horizontal direction) are used. -2, the deflection electromagnet 34-2 deflects/accelerates, enters the next storage ring 38-2, and again (vertical direction) focusing electromagnet 35-2 and (horizontal direction) focusing electromagnet 36-2. Then, the beam is converged by, is deflected and accelerated by the next deflection electromagnet 37-2, and enters the next storage ring 24-2. In this way, the charged particles continue to rotate while accelerating in the storage rings 24-2, 27-2, 33-2, 38-2, and when the desired velocity and the desired number of charged particles are obtained, the charged particles are charged. The particles enter the cavity 40-2 that guides the particles to the outside (this may be referred to as a charged particle discharge cavity) 40-2, and the charged particles are extracted from the outlet 41-2 of the charged particle discharge cavity 40-2 to the outside. A linear accelerator 39-2 may be provided in the middle of the charged particle discharge cavity 40-2 to further accelerate the charged particles. In addition, another deflection electromagnet, an acceleration electrode, a deceleration electrode, a linear acceleration device, a focusing electromagnet, etc. may be provided on the way.

In this way, any number of circular accelerators can be connected. This can be used to increase the velocity of charged particles. Moreover, since charged particles can be stored in each storage ring, a required amount of charged particles can be prepared in a short time. For example, if the cavity diameter of the storage ring through which charged particles pass is 1 mm, the innermost micro accelerator size is 50 mm radius, the ring pitch is 3 mm, and the substrate radius is 270 mm, then 70 circular Accelerators can be placed.

FIG. 17 is a diagram showing a schematic diagram in the case where the circular accelerator 8 is divided and manufactured on a substrate. That is, a method for producing an accelerator will be shown when the size of the substrate cannot be increased and the circular accelerator or the like is larger than the substrate size. The circular accelerator 8 as shown in FIG. 1 is considerably large, for example, a substrate of 2 m×2 m is required, but when only a 1 m×1 m substrate can be prepared, four 1 m×1 m substrates 44-1 to 44 -4 (indicated by a broken line) is prepared, and quarter patterns 43-1 to 43-4 of the circular accelerator 8 are prepared for each. The substrates 44-1 to 44-4 are cut at a position of 45-1, 2, 3, and 4 which is a pattern of the connecting portion by, for example, a dicing device. Since the parts to be connected here are the storage rings 24, 27, 33, 38, they are connected so that the central axes of the storage rings in these parts are aligned. In order to ensure this connection, the cut surface is polished or etched to smooth the connection surface. The attachment of the connecting portion can be performed by various joining methods. Another material may be interposed between the connecting portions. For example, a glass substrate, a plastic substrate, a metal substrate, or the like can be used to perform fusion bonding of these and a connecting member, or electrostatic anodic bonding. If the inside of the storage rings 24, 27, 33, 38 can be made to have an ultra-low pressure, the connection portion does not necessarily need to be securely attached. For example, a member or a box covering this portion may be prepared, and the substrates 44-1 to 44-4 and the member may be attached. A somewhat flexible or flexible member capable of adjusting the axial alignment of the storage rings 24, 27, 33, 38 is desirable. It is even better if a vacuuming line is provided on the member or the like so that the inside of the member can be vacuumed. By repeating this, an extremely large circular accelerator can be manufactured. This method can also be applied to the fabrication of ionization sources and long linear accelerators, as described above. That is, a large number of linear accelerators may be produced in the substrate, they may be cut by dicing or the like, and the cavities may be connected to each other.

FIG. 18 is a diagram showing a microwave ion source of the present invention. The microwave ion source of the present invention has an upper substrate 162 attached to an upper surface of a main substrate 161, and a lower substrate 163 attached to a lower surface thereof, and includes penetration chambers 164-1, 164-2, 164-3 formed in the main substrate, The penetration chamber 164-1 is a waveguide into which a high frequency wave 160 from a microwave or a high frequency (hereinafter, high frequency) oscillator is introduced through an opening 166-1 opened in the upper substrate 162 or the lower substrate 163. (Hereinafter, also referred to as a waveguide chamber 164-1.) The through chamber 164-2 is a chamber adjacent to the waveguide chamber 164-1 and is a discharge chamber separated by a substrate side wall 161-2 having a central hole 165-1. (Hereinafter, also referred to as the discharge chamber 164-2), the high frequency wave is incident from the waveguide chamber 164-1 through the central hole 165-1 of the substrate side wall 161-2. A coil 169 surrounded by a coil wiring is arranged around the discharge chamber 164-2, and a magnetic field B1 is generated in the coil axis direction in the discharge chamber 164-2 by the coil 169. Electrons in the discharge chamber 164-2 are accelerated by the high frequency electric field and collide and ionize the gas to cause discharge, thereby generating plasma. A high-frequency oscillator (not shown) is connected to the opening 166-1, but a high-frequency oscillator leaks from the connection between the high-frequency oscillator and the waveguide chamber 164-1 by providing a seal 168-1 at the connection. It is desirable not to let the vacuum leak. The seal portion 168-1 can be formed by attaching an insulating material substrate such as glass or plastic with an adhesive or the like. The waveguide chamber 164-1 can be omitted by providing it outside the main substrate 161. In that case, the high frequency wave 160 can be directly introduced into the discharge chamber 164-2. An opening 166-2 for introducing a gas (gas) is opened in the upper substrate 162 and/or the lower substrate 163 of the waveguide chamber 164-1, and various gases (gases) that are a source of ions (gas) are opened from the opening 166-2. ) Is introduced and sent to the discharge chamber 164-2 together with the high frequency. Further, the upper substrate 162 and/or the lower substrate 163 of the waveguide chamber 164-1 are provided with an opening 167-1 for vacuuming, so that the waveguide chamber 164-1 can be set to a predetermined pressure. Further, an opening may be provided in the upper substrate 162 and/or the lower substrate 163 of each penetration chamber to perform pressure measurement and temperature measurement. Further, the temperature of each penetration chamber can be controlled by irradiating infrared rays from the outside. Alternatively, it can be heated from the outside with a heater or hot water or hot air, and can be cooled with a Peltier element or the like, or with cold water or cold air, cold gas, liquid He, liquid nitrogen or other cold liquid. Its small volume makes it easy to control.

The through chamber 164-3 adjacent to the discharge chamber 164-2 is an ion extraction electrode chamber, and is separated from the discharge chamber 164-2 by a substrate side wall 161-3 having a central hole 165-2. In the discharge chamber 164-2, a substrate side wall 161-4 having a central hole 165-3 serving as an extraction electrode, a substrate side wall 161-5 having a central hole 165-4 serving as a deceleration electrode/focusing electrode, and a central region serving as an acceleration electrode. There is a substrate sidewall 161-6 with holes 165-5. Ions (charged particles) generated in the discharge chamber 164-2 are attracted to the electric field of the extraction electrode 161-4, pass through the central hole 165-2 of the partitioning substrate side wall 161-3, and are further extracted. Through the central hole 165-3 of the adjacent decelerating electrode/focusing electrode 161-5 and further through the central hole 165-5 of the adjacent accelerating electrode 161-6. Accelerate through. By repeating these, acceleration/deceleration/convergence, emission to the deflection magnet chamber, focusing in the quadrupole magnet chamber, emission to various penetration chambers for ion implantation and other applications such as mass spectrometry chambers, etc. .. In the ion extraction electrode chamber, an ion beam having a desired velocity and current density is obtained by combining an acceleration electrode and a deceleration/focusing electrode.

Since the conductor film is usually not laminated on the side wall of the substrate having a central hole for partitioning the through chambers from each other, acceleration or deceleration is not performed here. A substrate side wall 161-4, which is an extraction electrode and has a central hole 165-3, has conductor films 170-1 (front side surface) and 170-2 (rear side surface) laminated on its side surface. If the main substrate 161 is an insulator, the conductor film 170 can be directly formed. If the main substrate 161 is not an insulator, an insulating film may be interposed between the main substrate 161 and the conductor film 170. The conductor film 170 is connected to the conductor film 176 formed on the lower surface of the upper substrate 162 and/or the conductor film 175 formed on the upper surface of the lower substrate 163, and further connected to the upper substrate 162 and the lower substrate 163. It is connected to the formed contact 173 and further connected to the conductor film electrode wiring 172 formed on the upper surface of the upper substrate 162 and/or the conductor film electrode wiring 174 formed on the lower surface of the lower substrate 163. Therefore, a voltage can be applied to the conductor film 170 from the conductor film electrode wirings 172 and/or 174. When the ions have negative charges, a positive voltage is applied to the extraction electrode 161-4 to attract the ions and accelerate them. When the ions have a positive charge, a negative voltage is applied to the extraction electrode 161-4 to attract the ions and accelerate them. A deceleration/focusing electrode 161-5 is provided to prevent the ions from diverging or to prevent the ions from accelerating too much. Its structure is similar to that of the extraction electrode 161-4. When the ions have negative charges, a negative voltage is applied to the deceleration/focusing electrodes 161-5 to focus the ions and decelerate them. When the ions are positively charged, a positive voltage is applied to the deceleration/focusing electrodes 161-5 to focus the ions and decelerate them. The acceleration electrode 161-6 has the same structure and voltage application method as the extraction electrode 161-4. In the present invention, since a plurality of these substrate side wall electrodes can be freely arranged, it is possible to control the ion beam G by freely selecting the positive/negative of the voltage applied to each substrate side wall electrode and the magnitude of the applied voltage.

The upper substrate 162 and/or the lower substrate 163 of the discharge chamber 164-2 may be provided with an opening 166-3 for introducing gas, and the gas may be introduced into the discharge chamber 164-2 from there to be ionized. Further, the upper substrate 162 and/or the lower substrate 163 of the discharge chamber 164-2 may be provided with an opening 167-2 for evacuation. The wiring of the coil 169 spirally surrounds the outside of the discharge chamber 164-2, and this generates a magnetic field in the discharge chamber 164-2 (first magnetic field generation). Inside the discharge chamber 164-2, a plurality of magnets 178, which are second magnetic field generating means, are arranged. The magnet 178 may be a permanent magnet and has the same polarity in the longitudinal direction of the discharge chamber 164-2 (which is also the ion traveling direction), and as shown in FIG. 18A) is a cross-sectional view taken along line A1-A2 of FIG. 18A), and a plurality of them are arranged at regular intervals around the discharge chamber 164-2. (The 16-pole magnet in FIG. 18) The magnets 178 on the surface facing the discharge chamber 164-2 have the same polarity, and the adjacent magnets are arranged so that their polarities are opposite. As a result, the magnetic field generated between the magnets becomes a multi-pole magnetic field (indicated by a broken line) B2 that is localized on the inner surface of the discharge chamber 164-2. This multipole magnetic field B2 becomes smaller as it approaches the inside from the inner surface of the discharge chamber 164-2. As a result, the magnetic field B2 is considerably weakened near the center of the discharge chamber 164-2, and uniform plasma is generated near the center of the discharge chamber 164-2. At the same time, on the inner surface side of the discharge chamber 164-2, the penetration of plasma is suppressed by the magnetic field B2, and the plasma loss is reduced. Further, by these magnets 178, the characteristics of the plasma are further stabilized by the high frequency, and the fluctuation of the ion current due to the main magnetic field B1 can be reduced. Even if the main magnetic field B1 is precisely controlled, the plasma in the discharge chamber 164-2 can be stabilized and the amount of the ion beam G can be stably generated, but by arranging the magnet 178, more precise control is possible. Becomes

When the magnet 178 is a permanent magnet, for example, a ferrite magnet, a neodymium magnet, a samarium cobalt magnet, an Fe-Cr-Co magnet, an Fe-Pt magnet, an Fe-Al-Ni-Co magnet, a Co-Pt magnet can be used. The magnet 178 may be one in which a plurality of minute coils of the present invention are arranged in addition to the permanent magnet. That is, in the case of a 16-pole magnet, a plurality of minute coils are arranged on the same side of each pole so as to have the same polarity. Alternatively, each pole may be a single coil. In that case, the coil is elongated in the ion traveling direction. When a minute coil is used, the magnetic field of each coil can be controlled by the applied current, so that a more precise magnetic field B2 can be generated and controlled. When the magnets 178 are arranged, the recesses 181 and 182 may be formed in the upper substrate 162 and the lower substrate 163 in the region where the magnets 178 of the discharge chamber 164-2 are arranged, and the substrate thickness in those portions may be reduced. Magnetic field generation in the discharge chamber 164-2 can be enhanced. Further, when the magnet 178 is arranged, the fourth substrate 168 and the fifth substrate 177 are attached to the upper substrate 162 and the lower substrate 163 outside the discharge chamber 164-2, and as shown in FIG. Can be left open. In particular, when arranging the minute coil, if this portion is left open, it is easy to apply a current to the minute coil terminal. For example, it can be wire-bonded to the micro coil terminal. The fourth substrate 168 (168-2, 3) can also serve as the sealing substrate 168-1. That is, the same substrate can be attached to the upper substrate 162.

A space is provided above the magnet 178 to attach the sixth substrate 179 to the fourth substrate 168 and the seventh substrate 180 to the fifth substrate 177, as shown in FIG. At this time, the coil wiring 169 is formed on the sixth substrate 179 and the seventh substrate 180 in advance, and the contacts 183-1 connected to the coil wiring 169 are formed on the sixth substrate 179 and the seventh substrate 180. It is connected to the contact 183-2 formed on the fourth substrate 168. Further, the contact 183-2 formed on the fourth substrate 168 is connected to the contact 183-3 formed on the upper substrate 162. Further, the contact 183-3 formed on the upper substrate 162 is connected to the contact 183-4 formed on the main substrate 161. Further, the contact 183-4 formed on the main substrate 161 is connected to the contact 183-5 formed on the lower substrate 163. Further, the contact 183-5 formed on the lower substrate 163 is connected to the contact 183-6 formed on the fifth substrate 177. Then, the contact 183-7 formed on the seventh substrate connected to the coil wiring 169 formed on the seventh substrate 180 is connected to the contact 183-6 formed on the fifth substrate 177. As a result, the coil wiring 169 is connected in a spiral shape, surrounds the discharge chamber 164-2, and the coil 169 is manufactured. When the magnet 178 is not arranged, the fourth to seventh substrates are unnecessary, and the coil wiring pattern may be formed on the upper substrate 162 and the lower substrate 163.

For the contacts 183 (183-1 to 183-1) of the coil wiring 169, a contact hole is formed in each substrate, and when the substrate is not an insulator, an insulating film is formed on the inner surface of the contact hole. Next, if necessary, an adhesion or seed conductive film is laminated on the inner surface of the contact hole, and then a plating method, a squeeze method, a molten metal pouring method, a dispensing method, an electroforming method, a CVD method, a selective CVD method or the like is used. The inside of the contact hole is filled or semi-filled with a conductor film. It is sufficient to sequentially attach these. As shown in FIG. 18B, the magnet group 184 (184-1, 2) arranged between the upper substrate 162 and the lower substrate 163, that is, on the side surface side of the discharge chamber 164-2 is the discharge chamber 164-. 2 and the substrate side walls 161-4 and 161-5 are inserted into the magnet group insertion through chambers 164-4 and 164-5. This insertion method is the same as the coil insertion method already described. The magnet group 184 (184-1, 2) may be manufactured by sequentially stacking the magnet 178 with the non-magnetic body 183 interposed. This manufacturing method is also the same as the coil manufacturing method.

Alternatively, the side surface of the discharge chamber 164-2 can be obtained by dividing the main substrate 161 into several pieces and mounting the magnet groups 184 (184-1, 2) and the non-magnetic body 183 on the divided main substrate and sequentially adhering them. The magnet group 184 (184-1, 2) can be arranged on the side. In that case, the thickness of the magnet 178 in the magnet group 184 (184-1, 2) and the non-magnetic body 183 interposed therebetween.
It is desirable to match the thickness of the main substrate 161 with the thickness of the divided main substrate 161.
Further, in FIG. 18, the upper magnet 178 can be attached to the lower surface of the sixth substrate 179 to dispose the magnet 178 above the discharge chamber 164-2. At this time, naturally, it is desirable that the thickness of the fourth substrate 168, the depth of the concave portion 181, and the thickness of the magnet 178 be made uniform so as to be as close to the discharge chamber 164-2 as possible. Similarly, the lower magnet 178 can be attached to the upper surface of the seventh substrate 180 to dispose the magnet 178 below the discharge chamber 164-2. At this time, it is desirable that the thickness of the fifth substrate 177, the depth of the recessed portion 182, and the thickness of the magnet 178 be made uniform so that they are as close to the discharge chamber 164-2 as possible.

The space 185 formed by the upper substrate 162, the fourth substrate 168, and the sixth substrate 179 may be an airtight space, and the space 186 formed by the lower substrate 163, the fifth substrate 177, and the seventh substrate 180 may be an airtight space. it can. In this case, if a part of the upper substrate 162 and a part of the lower substrate 163 in the discharge chamber 164-2, especially a region where the magnet 178 is arranged, is removed, the magnetic field of the magnet is directly applied to the discharge chamber 164-2. Therefore, the efficient magnetic field B2 can be generated. In this case, when the magnet 178 is attached to the upper substrate 162 and the lower substrate 163, the upper substrate 162 and the lower substrate 163 that can support the magnet 178 as much as possible are left. When the magnet 178 is attached to the sixth substrate 179 and the seventh substrate 180, the substrates 162 and 163 directly below or above the magnet can be removed. Similarly, the substrate side walls 161-4 and 161-5 on the side surface side of the discharge chamber 164-2 can also be removed. Alternatively, only a part may be left. In this case, openings for vacuuming the spaces 185 and 186 and introducing gas can be provided in the sixth substrate 179 and the seventh substrate 180. Similarly, openings for vacuuming the magnet group insertion through chambers 164-4 and 164-5 and for introducing gas can be provided in the upper substrate 162 and the lower substrate 163.

The size of the high frequency ion source using the substrate of the present invention is estimated. The penetration chamber of the present invention has a height and a width of 0.1 mm to 100 mm, and a penetration chamber having a height or more can be used. A substrate ingot method using a mold is also possible. It can also be made with a 3D printer. The length is determined by the substrate size, but it is 10 mm to 1000 mm, and more than this is possible with the connection method. As an example, if the thickness of the main substrate is 1 mm, the thickness of the upper/lower substrate/the fourth to seventh substrates is 0.2 mm, and the substrate size is 600 mm×600 mm, the height of the discharge chamber is 1 mm for one main substrate, 10-ply is 10 mm, 50-ply is 50 mm, 100-ply is 100 mm, width can be adjusted to 1-100 mm, height can be made up to about 500 mm. Further, if the length of the discharge chamber 164-2 is 200 mm, the width and thickness of the coil 169 are 1.5 mm×1.5 mm, and the pitch is 2 mm, a coil (electromagnet) of 100 turns can be manufactured. The coil 169 is manufactured by embedding a conductor film in the substrate in FIG. 18, but after the substrate is cut and an accelerator or the like including the discharge chamber 164-2 is individually cut, the discharge chamber 164-2 is formed. The coil 169 can be produced by winding the coil wiring 169 around the coil manually or automatically. As described above, the ion generation source of the present invention using the substrate can be manufactured in various sizes.

Mass spectrometry is widely used for analysis of substances such as composition analysis of solid surface and composition analysis of reaction solution. The conventional mass spectrometry has a complicated structure, and it is not easy to fabricate the individual parts because it requires accurate assembly. The size of the mass spectrometry is at least about 1 m ³ , which makes it expensive and difficult to carry. Met. Therefore, by applying the present invention in which the main substrate (the first substrate) and the upper substrate (the second substrate) and the lower substrate (the third substrate) are attached to the upper and lower sides of the main substrate to form the microchannels, it is possible to realize a very small size and a very low cost. A mass spectrometer can be realized.

FIG. 19 is a diagram showing an embodiment of the mass spectrometry of the present invention. Through-grooves (penetration chambers) 305, 306, 307, 308, 309 penetrating from the upper surface to the lower surface of the main substrate 301 are formed, the upper substrate 302 is on the upper surface of the main substrate 301, and the lower substrate 303 is on the lower surface of the main substrate 301. It is attached. This attachment may be performed by using an adhesive, or the main substrate 301 may be a semiconductor substrate such as Si, carbon-based, SiC-based, or compound-based semiconductor or a conductive substrate such as a metal plate, and the upper substrate 302 or the lower substrate. In the case where the substrate 303 is a glass substrate or the like, electrostatic anodic bonding may be used, or another bonding method described in this specification or a bonding method described in other documents may be used. The through groove 305 is a sample chamber, and is a space sandwiched between a main substrate side wall 301-1 and a substrate side wall (also referred to as a partition) 301-2 separating the sample chamber 305 and the ionization chamber 306 adjacent thereto. (The side surface is the side wall of the main substrate 301.) The sample 311 is placed in the sample chamber 305. The sample 311 is easy to analyze, for example, if it is inserted from the sample opening portion 312 opened in a part of the upper substrate 302 and attached to the substrate side wall 301-1. The accelerated ion beam hits a part of the surface of the sample 311 and a part of the sample is sputtered. However, since there is a sample (analysis sample) to be analyzed only in the part where the ion beam hits, the sample 311 is used. A sample holder may be used. It is also possible to evacuate from the vacuum line 313 provided on the back surface side of the sample 311 to attach the sample 311 to the substrate side wall 301-1 and fix it. When the sample chamber 205 is to have a low pressure, the vacuum line 313 may further reduce the pressure to pull the sample 311. If it is difficult to support the sample 311 under the same low pressure, the sample 311 may be supported by cutting a groove in a part of the upper and lower substrates and inserting the sample 311 therein.

An ion beam inlet 314 is opened in the upper substrate 302 of the sample chamber 305, and an ion beam 316 emitted from an ion gun 315 arranged outside the mass spectrometer 300 is passed through the ion beam inlet 314 to the sample 311. Then, the constituent material of the sample 311 is sputtered. The ion gun 315 can also be arranged in the main substrate 301, but in this case, the ion gun 315 formed on the side surface side of the sample chamber 305 (the direction perpendicular to the paper surface of FIG. 19) is used to remove the main substrate 301. An ion beam is applied to the sample 311 through the through groove. The ion beam 316 is, for example, nitrogen (N) ions, argon (Ar) ions, xenon (Xe) ions, or the like. The sputtered sample material is neutral particles 317 and ions (secondary ions) 318, and these particles enter the ionization chamber 306 through the central hole 310-2 of the partition 301-2. The inside of the sample chamber 305 may be at a pressure near the atmospheric pressure, but the inside of the sample chamber 305 may be depressurized by opening the vacuuming line 319 in the lower substrate 303 or the like and connecting a vacuum pump.

In the sample chamber 305, an insulating film such as a silicon oxide film, a silicon nitride film, or a silicon oxynitride film may be stacked on the inner surface of the main substrate 301. These insulating films are formed by a CVD method, a PVD method, or an oxidation method. It can be formed by the nitriding method. As described above, the central hole 310-2 is formed by forming (through half) the through groove of the sample chamber or the like and the partition wall such as the partition wall 301-2 in the state where the main substrate 301 is vertically separated, and then the partition wall 301-2. The central part such as -2 is partially removed (these may be reversed; that is, the central hole is formed and then the substrate side wall is formed.) After that, the separated upper and lower main substrates 301 are attached and formed. The insulating film is formed before the main substrate 301 is attached or after the main substrate 301 is attached.

The ionization chamber 306 formed adjacent to the sample chamber 305 is a space for ionizing neutral particles incident from the sample chamber 305 and focusing the ionized ions and the ions incident from the sample chamber 305 near the center. .. Next to the ionization chamber 306 is a charged particle acceleration chamber 307 that draws out and accelerates the ions existing in the ionization chamber 306, and a partition having a central hole 310-3 between the ionization chamber 306 and the charged particle acceleration chamber 307. Separated by 301-3. That is, the ionization chamber 306 is a space sandwiched between the partition walls 301-2 and 301-3. (The side surface is the side wall of the main substrate 301.)

In the ionization chamber 306, the ionization beam 320 is applied to the neutral particles 317 existing in the ionization chamber 306 through the upper substrate 302 or the lower substrate 303 to be ionized. As the ionization beam 320, various beams introduced in the literatures so far can be used, and examples thereof include laser light, electron beam, synchrotron radiation light, X-ray, and the like. In addition to laser light, laser light can be used. May be applied to a solid target, and the X-rays generated at that time may be further used to ionize the neutral particles. (Patent 3079585) In order to facilitate passage of the ionization beam 320 into the ionization chamber, a portion of the upper substrate 302 or the lower substrate 303 which serves as a path for the ionization beam 320 may be removed (an opening is provided).

A conductive film 321 is stacked on the inner surface of the ionization chamber 306, a contact hole 323 is formed in the upper substrate 302 or the lower substrate 303, a conductive film is stacked in the contact hole 323, and the upper substrate 302 or the lower substrate is further stacked. A conductor film electrode/wiring 324 is formed over 303 so that a voltage can be applied to the conductor film 321 from the electrode/wiring 324. When the conductor film 321 covers the inner surface of the ionization chamber except for the portion passing through the ionization beam 320, the inner surface of the ionization chamber can be in the same potential state. When the ions are positive ions, a positive voltage is applied to the conductor film 321 to focus the positive ions on the center. When the ions are negative ions, a negative voltage is applied to the conductor film 321 to focus the negative ions on the center. By dividing the upper, lower, left, and right conductor films and forming contact holes and electrodes/wirings in the respective conductor films, the voltages of the respective conductor film regions can be individually controlled, so that the charged particle beam 325 in the ionization chamber 306 can be controlled. You can adjust the position. When the main substrate 301 is a semiconductor substrate such as Si or a conductor substrate such as Cu or Al, the conductor film 321 is laminated after forming the insulating film. Further, an insulating film may be stacked on the conductor film 321 as a protective film for the conductor film 321. The formation and patterning of the ionization chamber 306, the partition wall 301, the central hole 310, the insulating film, the conductor film 321, the protective film, and the like are performed by dividing the main substrate 301 into individual portions as described in this specification. It can be realized by a method of attaching a substrate. If the ions 318 generated in the sample chamber 305 enter the ionization chamber 306, they are naturally converged by the voltage applied to the inner surface of the ionization chamber 306 and become part of the ionization beam 325.

The charged particle beam 325 converged in the ionization chamber 306 enters the charged particle acceleration chamber 307 through the central hole 310-3. A partition 301-11 having a central hole 327-1 is arranged at a position closest to the entrance side of the acceleration chamber 307, and a conductor film 326 is laminated and patterned around the partition 301-11. The conductor film 326 is connected to the conductor film laminated in the contact hole 323 and the conductor film electrode/wiring 324, and a voltage having an electric charge opposite to that of the ion of the charged particle beam 325 is applied to 325 is withdrawn from the ionization chamber 306 and accelerated. Therefore, the partition wall 301-11 may be called a lead electrode. By dividing the upper, lower, left, and right conductor films and forming contact holes and electrodes/wirings in the respective conductor films, the voltage of each conductor film region can be controlled individually. The position of 325 can be adjusted.

A partition 301-12 (also having a central hole 327-2) is arranged adjacent to the partition 301-11 in the traveling direction of the charged particle beam 325, and a conductor film 326 is stacked around the partition 301-12 and patterned. To be done. The conductor film 326 is connected to the conductor film laminated in the contact hole 323 and the conductor film electrode/wiring 324, and a voltage having the same charge as or the opposite charge of the ions of the charged particle beam 325 is applied. It When a voltage having the same charge as that of the ions of the charged particle beam 325 is applied, the charged particle beam 325 is focused, and when a voltage having an opposite charge to the charge of the ions of the charged particle beam 325 is applied, the charged particles are charged. Beam 325 is accelerated. In the traveling direction of the charged particle beam 325, a necessary number of partition walls (also having a central hole) in which the same conductive film as the partition wall 301-12 is stacked are formed after the partition wall 301-12, and these conductive film are charged. A voltage having the same charge as or an opposite charge to the ion of the particle beam 325 is applied to accelerate the required number of charged particle beams 325 and focus the required number of charged particle beams 325 to generate the central hole 310. The charged particle beam 325 is guided to the adjacent mass analysis chamber 308 separated by the partition wall 301-4 having -4. By dividing the conductor film of each partition after the partition 301-12 into upper, lower, left, and right and individually forming a contact hole and a conductor film and an electrode/wiring therein, the conductor film is divided into separate conductor films. Since different voltages can be applied to the beam, it is possible to control the traveling direction and the focusing position of the charged particle beam 325. As a result, it becomes possible to freely control the beam radius, position, and traveling direction of the charged particle beam that enters the mass analysis chamber.

The size of the central holes 310-2, 3, 4, 5 and the central holes 301-11, 12,... Which the partition walls 327-1, 2,... Can be changed. For example, 310-2 is made large in order to guide most of the sputtered neutral particles 317 and ions 318 to the ionization chamber. Further, the central hole 327-11 in the acceleration chamber 307 is made smaller than the central hole 310-3 at the boundary with the ionization chamber 306 in order to facilitate extraction of ions. Further, the central holes 327-2,... In the acceleration chamber 307 are made smaller than the central holes 310-3 and 327-11 for acceleration. In the method of changing the size of the central hole in this manner, the main substrate is divided into upper and lower parts, the partition walls are formed, and then patterning is performed according to the size of the central hole formed in each partition wall (for example, photolithography). The partition wall may be removed by etching in accordance with the resist pattern) and the size of each central hole. Alternatively, the main substrate is divided into upper and lower parts, and patterning is performed at a position where each partition wall is to be formed in accordance with the size of the central hole formed therein (for example, a photoresist pattern). Each partition is formed after the main substrate is removed by etching in accordance with this. After that, an insulating film, a conductor film, a protective film, and their patterning are performed. As the acceleration chamber 307, the acceleration chamber used in the accelerator described with reference to FIGS. 1 to 17 can be used.

The mass spectrometric chamber 308 is, for example, a quadrupole type. The mass spectrometry chamber 308 is adjacent to the acceleration chamber 307 and is separated by a partition wall 301-4 having a central hole 310-4. When the charged particle beam 325 accelerated and focused in the acceleration chamber 307 enters the mass analysis chamber 308, the electric field or magnetic field of the mass analysis chamber 308 causes the ratio m/q (mass) of the charge q and the mass m of the charged particles. The orbits are sorted by the charge ratio), and only specific charged particles enter the ion detection chamber 309. The ion detection chamber 309 is separated from the acceleration chamber 307 by a partition wall 301-5 having a central hole 310-5.

The mass spectrometric chamber 308 is, for example, a quadrupole type. FIG. 19 is shown as a quadrupole mass spectrometric type. Here, the mass analysis chamber 308 has no partition walls other than the partition walls 301-4 and 301-5 that are the partition walls thereof, and the main substrate 301 has a through groove (or a through chamber) penetrating from the upper substrate 302 to the lower substrate 303. Has become. (The side surface is the main substrate 301.) Four quadrupole electrodes 329 (329-1 and 329 are shown in FIG. 19) that are long in the traveling direction of the charged particle beam 325 are arranged in the mass analysis chamber. It One or a plurality of conductor films/electrodes/wirings 324 are connected to each quadrupole electrode 329 through the conductor film in the contact hole 323, and a voltage can be applied. Further, the upper and lower substrates 302 and 303 are provided with a vacuuming opening portion 330, which can evacuate the inside of the mass analysis chamber 308 to a predetermined pressure (for example, 10 ⁻⁹ to 10 ⁻² torr). Similarly, another opening may be formed so that a gas for purging or cleaning can be made to flow therethrough. Further, an opening for introducing or exiting a selective CVD gas (for example, WF6) or a plating solution (for example, copper sulfate solution for Cu plating) for connecting the conductor film in the mass spectrometry chamber 308. Can be provided.

FIG. 20 is a diagram showing an example of a method for manufacturing a quadrupole mass spectrometer. A conductor film 355 serving as a quadrupole electrode is stacked on the third substrate 353 and patterned to form a quadrupole electrode 355. The conductor film 355 is, for example, a metal such as molybdenum (Mo), tungsten (W), chromium (Cr), titanium (Ti), copper (Cu), iron (Fe), nickel (Ni), aluminum (Al). , Or an alloy thereof, or a silicide or the like which is a compound of these and Si, which is stacked by a PVD method or a CVD method and then patterned by a photolithography+etching method. Alternatively, a quadrupole electrode rod of this size is attached by an attachment method. When the third substrate 353 is an insulator such as glass, quartz, ceramics, or plastic, it can be directly laminated or attached, but when the third substrate 353 is a conductor or a semiconductor, an insulating film is laminated and then the conductor is laminated. The film 355 is laminated. Alternatively, the conductor film 355 can be formed by a coating method. A desired quadrupole electrode 355 can be formed by applying a conductor paste on the third substrate 353 using a metal mask and then performing heat treatment. The conductor paste contains the above metal and the like. Alternatively, the conductor film 355 can also be formed by attaching a foil of the above metal or the like on the third substrate 353 and patterning it. Further, the main substrate 351 has a recess 354 formed by cutting out a portion 354 in which the quadrupole electrode 355 is arranged. When the main substrate 351 is a semiconductor substrate such as a Si substrate, an insulating substrate such as a glass substrate or a quartz substrate, or a metal substrate, it can be formed by a simple process. (Fig. 20(a))

Next, as shown in FIG. 20B, the main substrate 351 and the third substrate 353 are attached. These attachments can be done by the methods described herein. At this time, the depth of the recess 354 is set larger than the height of the quadrupole electrode 355 so that the main substrate 351 and the quadrupole electrode 355 do not come into contact with each other. Next, the upper surface of the main substrate 351 is patterned with a photoresist or the like to form a through groove which becomes the mass analysis chamber 356. At this time, since the patterns are aligned with each other, precise alignment is performed. When the main substrate 351 is etched to form the through groove 356, it is etched with a dry etching gas or a wet etching solution having a high etching selection ratio with the conductor film 355 and the third substrate 353, and the conductor film 355 and the third substrate 356 are used as much as possible. Do not etch 353. (FIG. 20C) At the stage of FIG. 20A, a protective film which is an insulating film (eg, SiO 2 film, SiN film, etc.) can be formed on the conductor film 355. The etching selection ratio in this case is the main substrate 351 and the protective film.

The same process is performed on the second substrate side 352, the main substrate 351 (351-1) is attached to the second substrate side 352, the through groove 356, and the conductor film 355 which is the quadrupole electrode 355 therein. To form. The thus formed main substrate 351 (351-1) attached to the second substrate side 352 and the main substrate 351 (351-2) attached to the third substrate side 353 are aligned so that the through grooves 356 are aligned with each other. And then stack and attach. Adhesive methods include adhesives, diffusion bonding, room temperature bonding, and high temperature bonding. Further, when the main substrate 351 is a semiconductor substrate such as Si or a conductor substrate such as metal, a glass substrate or a quartz substrate 357 can be used to firmly attach them by electrostatic coupling (anodic bonding). In this case, the substrate 357 which is sandwiched between the substrates 357 and 356 is removed by removing the portion to be the mass spectrometric chamber 356, and the second substrate side 352 and/or the third substrate side 353 is attached to the substrate 357. As a result, a closed mass spectrometric chamber 358 (356 is combined to form 358) can be formed. (FIGS. 20(d) and 20(e)) Incidentally, in the process shown in FIG. 20(a), the main substrate 351 in which the through groove is formed instead of the recess may be attached. At this time, the through groove and the conductor film pattern are accurately aligned. In the case where the depth of the through groove is only one groove, in FIG. 20D, the conductor film 355 is formed in which one of the main substrates is absent (for example, 351 (351-1) is absent). The formed second substrate 352) may be attached to the main substrate 351 (351-2).

Next, a contact hole 371 is formed in the second substrate 352 and the third substrate 353, a conductor film is laminated in the contact hole 371, and then an electrode/wiring 372 is formed. A CVD method, a PVD method, a plating method, a coating method, or the like can be used to stack the conductor film in the contact hole 371. The electrode/wiring 372 can also be formed by the CVD method, PVD method, plating method, coating method, or the like. The conductor film in the contact hole 371 can also be used as the electrode/wiring 372. The electrodes/wirings 372 can be routed over the second substrate 352 and the third substrate 353, and pad electrodes (electrode connection portions with the outside) can be provided at appropriate places. A protective film can be formed if necessary. Note that FIG. 20 is a view seen from the traveling direction of the ion beam 325 in FIG. 19, that is, a cross-sectional view in the direction perpendicular to the paper surface of FIG.

As a result, an alternating current (high frequency voltage) and a direct current voltage can be applied from the external electrode 372 to the four quadrupole electrodes 355 (355-1, 2, 3, 4). Since the mass spectrometry chamber can be formed by using the semiconductor process as described above, a mass spectrometry chamber having an extremely accurate size can be produced, and highly accurate mass spectrometry can be performed. As is clear from this process, the depth of the mass spectrometric chamber can be increased by stacking and adhering the main substrates (a glass substrate or the like may be interposed therebetween). For example, the thickness of a normal Si substrate is about 1 mm at the maximum, but it becomes 10 mm by stacking 10 sheets. Of course, since a thicker Si substrate can be manufactured, a predetermined thickness can be realized by bonding a small number of substrates. Further, by forming a vacuuming line opening 359 and connecting a vacuum pump, the mass spectrometry chamber 358 can be vacuumed and the pressure can be lowered. The present invention is a mass spectrometric chamber of a desired size (even if the height of the mass spectrometric chamber is 1 mm or less or 100 μm or less), and the number of joints is small. The pressure and the desired pressure can be easily realized. Since the process is simple and the vacuum pump is small, a low cost mass spectrometer can be realized.

In the case of quadrupole mass spectrometry, only ions having a predetermined m/q pass through the quadrupole electrode 355 (329 in FIG. 19) and reach the detection chamber (309 in FIG. 19). Ions having m/q of 6 may collide with and damage the quadrupole electrode 355 and the main substrate 351, the second substrate 352, and the third substrate 353 outside thereof. Therefore, if the mass analysis chamber 358 is enlarged, the kinetic energy of the ions is also reduced and damage can be reduced. FIG. 20(f) shows the structure and method for enlarging the mass spectrometry chamber. That is, the second main substrate 361 (361-1, 2), the fourth substrate 362, and the fifth substrate 363 are attached to the upper and lower sides of the second substrate 352 and the third substrate 353, and are attached to the upper and lower portions of the mass spectrometry chamber 358. A mass analysis upper chamber 365 and a lower chamber 368 are provided, the width (w21) of the mass analysis chamber 358 is increased, and the left and right walls of the main substrate 351 are separated from the quadrupole electrode 355 (d21 is increased). Further, the planar area of the mass analysis upper chamber 365 and the lower chamber 368 is made larger than the area of the mass analysis chamber 358 (that is, the left and right width w22 of the mass analysis upper chamber 365 and the left and right width w23 of the mass analysis lower chamber 368). At this time, w22, w23>w21), and the regions of the second substrate 352 and the third substrate 353 are set to such an extent that the quadrupole electrode 355 is strongly supported, and the mass analysis chamber 367, the mass analysis upper chamber 365, and the lower chamber 368. The partition (the second substrate 352 and the third substrate 353) between and is removed to make the openings 364 and 367 as wide as possible (may be divided into a plurality of openings). Further, vacuum evacuation line openings 366 and 369 are provided on both the fourth substrate 362 and the fifth substrate 363. Further, the vacuum evacuation line openings 366 and 369 are made large to the extent that there is no problem (may be divided into a plurality of openings). The heights (h22, h23) of the mass analysis upper chamber 365 and the lower chamber 368 are also increased.

For example, the size of the mass spectrometric chamber 358 is w21=6 mm, h21=2 mm, d21=1.8 mm, the main substrate 351 (351-1, 2) is 0.8 mm thick, and the glass substrate 357 is 0.1 mm thick. 4 mm, the thickness of the second substrate 352 is 0.3 mm, the thickness of the third substrate 353 is 0.3 mm, the thickness of the fourth substrate 362 is 0.5 mm, the thickness of the fifth substrate 363 is 0.5 mm, and the quadrupole electrode 355 is Width 0.2 mm, height 50 μm, length of quadrupole electrode (horizontal length in FIG. 19 or length perpendicular to paper surface of FIG. 20) 1 mm to 100 mm, w22=8 mm, h22=2 mm, w23= 8 mm and h23=2 mm. Alternatively, in the case of enlarging the mass analysis chamber, the size of the mass analysis chamber 358 is w21=30 mm, h21=10 mm, d21=9 mm, and the thickness of the main substrate 351 (351-1, 2) is 5 mm each. Glass substrate thickness 0.5 mm, second substrate 352 thickness 1 mm, third substrate 353 thickness 1 mm, fourth substrate 362 thickness 1 mm, fifth substrate 363 thickness 1 mm, quadrupole electrode 355 width 1 mm , Height 0.4 mm, quadrupole electrode length 20 mm to 200 mm, w22=40 mm, h22=10 mm, w23=40 mm, h23=10 mm.

As a result, the ions moving through the gap between the quadrupole electrodes 355 without reaching the ion detection chamber 309 have a low ion moving speed toward the wall (side surface) of the main substrate 351, The damage to the wall (side surface) of the main substrate 351 is small. In particular, by providing a large number or wide areas of vacuum drawing openings 364 and 367 around the wall (side surface) of the main substrate 351, ions that have deviated from the inside of the quadrupole electrode can be subjected to mass analysis from those openings 364 and 367. It goes out to the upper chamber 365 and the mass analysis lower chamber 368. Further, the damage can be reduced by covering the inner surface of the mass spectrometric chamber 358 with a film that is not easily attacked by ions. For example, a silicon oxide film, a silicon nitride film, alumina, etc. have high ion resistance. These films can be laminated by a CVD method or a PVD method. Further, the ions moving toward the upper mass analysis upper chamber 365 and the lower mass analysis lower chamber 368 also have a low ion moving speed, and move to the walls (side surfaces) of the fourth substrate 362, the fifth substrate 363, and the second main substrate 361. Damage is small. Further, since the gas is discharged from the vacuum drawing openings 366 and 369 to the vacuum pump side, the influence on the mass spectrometer is small. Furthermore, an opening for purging or cleaning is provided in the fourth substrate 362 or the fifth substrate 363, and the mass spectrometric chamber can be maintained in a clean state by occasionally purging or cleaning with nitrogen, Ar, He, or the like. It is effective for longevity and longevity.

Alternatively, by forming a conductor film on the inner surface of the ion detection chamber 309 so that a voltage can be applied from the outside and applying a weak voltage having the same charge as the ions, collision of ions can be reduced. The quadrupole electrode 355 is connected to the conductor film 372 formed on the second substrate 352 and the third substrate 353 through the conductor film laminated in the contact hole 371 formed on the second substrate 352 and the third substrate 353. Then, it is connected to the conductor film 373 formed on the inner surface of the second main substrate 352 or the third substrate 353, and further connected to the conductor film 374 formed on the upper and lower surfaces of the fourth substrate 362 or the fifth substrate 363. Connecting. The conductor film 374 is a conductor film electrode/wiring formed on the upper surface of the fourth substrate 362 or the fifth substrate 363 through the conductor film laminated in the contact hole 375 formed on the fourth substrate 362 or the fifth substrate 363. Connect to 376. As a result, DC voltage and AC (high frequency) voltage can be applied to the four quadrupole electrodes 355 from the external electrodes/wirings 376. Further, if a plurality of outer electrodes and wirings are provided on one quadrupole electrode as shown in FIG. 19, DC voltage and AC (high frequency) can be applied from these plurality of electrodes, and the trajectory of the ions 325 can be changed. Can be precisely controlled.

An example of a method for manufacturing FIG. 20F from the state of FIG. 20E will be described. A through hole 368 penetrating the fifth substrate 363 is formed in the second main substrate 361 (361-2) attached to the fifth substrate 363. In addition, in order to widen the overlapping region of the conductor film 373 formed on the second main substrate 361 (361-2) side and the conductor film 372 formed on the lower surface of the third substrate (lower substrate) 353, the concave portion is formed. Also forms 377. The depth of the recess 377 is about the sum of the thickness of the conductor film 372 and the thickness of the conductor film 373 (when an insulating film is formed as a base, the thickness is taken into consideration. When a conductive adhesive is used, its thickness is also taken into consideration.) so that the conductor film 372 and the conductor film 373 can be sufficiently connected. After forming the through hole 368 and the recess 377, the conductor films 373 and 374 are stacked, and the conductor film 373 and the conductor film 373 are formed on a necessary portion of the side surface of the recess 377 and the through hole 368 and a necessary portion of the upper surface of the fifth substrate 363. 374 is formed. The conductor films 373 and 374 are Cu, Al, conductive Si, Cr, Ni, W, Mo, Ti, Au, Ag, alloys thereof, conductive polycrystalline silicon, various silicides, conductive graphene, and conductive nanotubes. If the electrical connection between the conductor films 373 and 372 is insufficient, a conductive adhesive or solder alloy (for example, Pb-Sn system, Ag-Cu-Sn) is formed on the conductor films 372, 373, and 374. System, Sn-Zn-Bi system, Cu-Sn system, Sn-Ag-In-Bi system, Sn-Zn-Al system, etc.) are attached.

The conductor film 372 formed on the lower surface of the third substrate 353 is laid out as a wiring as shown in FIG. 20F and is also formed on the side connected to the recess 377 so that it can be connected to the conductor film 373. Further, vacuum drawing openings 364 and 367 are also formed in the second substrate (upper substrate) and the third substrate (lower substrate). These openings 364 and 367 may be formed before the conductor film 372 is formed, or the second substrate (upper substrate) and the third substrate (lower substrate) may be removed by etching after the conductor film 372 is patterned. Can be formed. Alternatively, it can be formed in the same manner as the quadrupole electrode 355 before the main substrate 351 is attached to the second substrate (upper substrate) or the third substrate. Next, the second main substrate 361 to which the fifth substrate 363 has been attached is attached to the third substrate 353 while aligning the mass analysis lower chamber 368 to the mass analysis chamber 358. After that, a contact hole 375 and a vacuum drawing opening 369 are formed in the fifth substrate 363, a conductor film is laminated on the contact hole 375, and a conductor film electrode/wiring 376 connected to the contact hole 375 is formed. When a conductor film enters the mass analysis lower chamber 368 through the vacuum drawing opening 369, the vacuum drawing opening 369 may be formed after the conductor film electrode/wiring 376 is formed.

The same applies to the fourth substrate 362, the second main substrate 361 (361-1) and the second substrate (upper substrate) side. Further, as described in other parts of the specification, when the base is not an insulator, an insulating film such as a silicon oxide film is laminated before laminating the conductor film to protect the conductor film. For this purpose, an insulating film such as a silicon oxide film is laminated on the conductor film. Further, after attaching the main substrate 361 to the upper substrate 362 and the lower substrate 363 and forming the openings 369 and 366, in order to surely connect the conductor films 372 and 373, through the openings 369 and 366, It is also possible to flow a selective CVD gas or introduce a plating solution to selectively stack the conductor film on the connection portion.

FIG. 21 is a diagram illustrating an example of a structure and method for attaching a quadrupole electrode to a substrate. 21A is a sectional view and FIG. 21B is a plan view. A quadrupole electrode 386 is attached on the second substrate 382 and the third substrate 383. Although the quadrupole electrode 386 has a circular cross section, it may have a commonly used right-angled hyperbolic shape or any other shape, and an optimum shape for the quadrupole electrode can be selected. Further, as shown in FIG. 21B, the longitudinal direction is linear and the whole is rod-shaped. Further, it is also possible to form a waveform in the longitudinal direction, and it is also possible to select a shape in which the electric field in the quadrupole electrode is optimum for mass spectrometry. As the material of the quadrupole electrode 386, various materials such as Mo-based alloy, SUS, and copper-based alloy can be used. The quadrupole electrode 386 can be manufactured using a mold, or can be manufactured as a wire rod, or can be manufactured by a patterning method or a plating method or an electroforming method.

By forming an adhesive pattern on the second substrate 382 and the third substrate 383 and attaching the quadrupole electrode rod 386 to the pattern, the adhesive pattern can be accurately arranged on the second substrate 382 and the third substrate. A groove pattern 385 is formed on the second substrate 382 and the third substrate 383 by a photolithography+etching method, and an adhesive is formed on the groove pattern 385 if necessary, and a quadrupole electrode rod 386 is formed on the groove pattern 385. By putting in and adhering them, it is possible to more accurately arrange them on the second substrate 382 and the third substrate. When the length of the quadrupole electrode rod 386 is long, the length of the quadrupole electrode rod 386 can be accurately aligned by the photolithography+etching method. The adhesive may be a normal adhesive, a conductive adhesive, or a metal such as solder. It is desirable that the surface shape of the quadrupole electrode is arranged so that the electric field in the quadrupole electrode is optimized. Then, heat treatment or ultraviolet irradiation is performed to fix the quadrupole electrode rod 386 on the second substrate 382 and the third substrate 383.

Next, the main substrate 381 obtained by hollowing out the mass spectrometry chamber 384 is attached to the second substrate 382 and the third substrate 383. This attachment may be performed separately or at the same time. The second substrate 382 and the third substrate 383 are aligned and attached to the main substrate 381 so that the quadrupole electrode rod 386 is arranged at a predetermined position in the mass spectrometry chamber 384. When the main substrate 381 is divided, the main substrate 381 having the mass analysis chamber 384 is attached to the second substrate 382, and the main substrate 381 having the mass analysis chamber 384 is attached to the third substrate 383. Attach. At this time, a glass substrate or a quartz substrate may be interposed between the main substrates 381 to attach them by using an electrostatic bonding method. Furthermore, if the main substrate 381 is divided into a large number and they are stacked and attached, the height of the mass spectrometry chamber can be freely adjusted. In the embodiment shown in FIG. 21, quadrupole electrodes 386 of various thicknesses (eg, 50 μm to 5 mmφ) can be used. The length of the quadrupole electrode 386 can also be selected according to the size of the substrate, but if the size of the substrate is a wafer having a diameter of 300 mm, it can be formed in 1 mm to 200 mm. The contact hole and the extraction electrode can be easily manufactured by the method shown in FIG. Further, the mass analysis chamber can be expanded, part of the partition walls of the second substrate and the third substrate can be removed, and the mass analysis upper chamber and the mass analysis lower chamber can be provided by the method shown in FIG. 20.

FIG. 22 is a diagram illustrating another example of the structure and method for attaching the quadrupole electrode to the substrate. In the embodiment shown in FIG. 22, the quadrupole electrode 394 (394-1, 2, 3, 4) is arranged at a position separated from the mass spectrometry chamber 396 (396-1) by a boundary wall (substrate side wall or substrate partition wall). However, in this embodiment, no electrodes or the like are arranged in the mass spectrometric chamber 396 (396-1). The main substrate 391 has a mass spectrometric chamber 396 (396-1), which is partitioned on the left and right sides by substrate partition walls 391 (391-1, 2) to provide a through chamber 396 (396-2) and a through chamber 396 (396-). 3) is arranged. Quadrupole electrodes 394 (394-2, 4) are arranged in the through chambers 396 (396-1, 2), respectively. A part (called a pedestal) 397 of the main substrate 391 is left to adjust the height, or the pedestal 397 is attached to the third substrate 393. Alternatively, the main substrate 391 having the same height as the pedestal 397 is attached to the third substrate, and the portion to be the mass spectrometric chamber 396 (396-1) is removed. If a quadrupole electrode of a size that does not require height adjustment is used, the pedestal is unnecessary.

Then, the quadrupole electrodes 396 (396-2, 4) are attached to the pedestal 397. If the groove pattern 398 is formed on the pedestal, the quadrupole electrode can be fixed and arranged with high accuracy. On the other hand, the main substrate 391 is attached to the side of the second substrate 392 as well, and the portion of the main substrate 391 that becomes the mass spectrometry chamber 396 (396-1) and the portion where the quadrupole electrodes 396 (396-2, 4) are arranged. 396 (396-2, 3) is hollowed out to form a through hole reaching the second substrate 392. At this time, the main substrate outside the quadrupole electrode 396 (396-2, 4), the partition wall 391 (391-1) between the through hole 396-2 and the mass spectrometry chamber 396-1, the through hole 396-. The partition 391 (391-2) between the No. 3 and the mass spectrometric chamber 396-1 is left.

Next, the main substrate 391 attached to the third substrate 393 and the main substrate 391 attached to the second substrate are aligned and attached so that their mass spectrometry chambers 396-1 are aligned. The quadrupole electrodes 394 (394-2, 4) arranged on the pedestal 397 enter into the through holes 396 (396-2, 3) formed in the main substrate on the second substrate side. The main substrates 391 can be bonded to each other using an adhesive, room temperature bonding, diffusion bonding, or high temperature bonding. Further, by interposing a glass substrate or the like therebetween, when the main substrate 391 is a semiconductor substrate such as a Si substrate or a conductor substrate, it can be firmly attached by anodic electrostatic bonding.

Then, the quadrupole electrodes 394 (394-1, 3) are attached to the predetermined positions of the second substrate 392 and the third substrate 393, or the quadrupole electrodes are attached to the predetermined positions of the second substrate 392 and the third substrate 393 in advance. By attaching the electrodes 394 (394-1, 3) in advance, the partition wall, the second substrate, and the second substrate, the second substrate, and the second substrate, can be surrounded by the mass analysis chamber 396 (396-1). The quadrupole electrode 394 (394-1, 2, 3, 4) can be arranged at a position separated from the three substrates.

22(b) is a perspective perspective view of the mass spectrometry chamber having the quadrupole electrode shown in FIG. 22(a). Quadrupole electrodes 394 (394-1, 2, 3, 4) are arranged in a rod shape in the longitudinal direction of the mass spectrometric chamber 396-1. In FIG. 22B, the quadrupole electrode 394 is shown as a cylindrical rod having a circular cross-sectional shape, but the cross-sectional shape may be another shape such as a right-angled hyperbolic shape, an elliptical shape, or a hyperbolic shape. Generally, the shape of a right-angled hyperbola is considered to be good. A DC voltage and a high frequency voltage of voltage ±(U+Vcosωt) are applied to the electrodes facing each other. That is, +(U+Vcosωt) is applied to the quadrupole electrodes 394-1 and 39, and −(U+Vcosωt) is applied to the quadrupole electrodes 394-2 and 4 at the same time. As a result, among the charged particle (ion) beams passing through the mass analysis chamber 396-1, only ions having a specific m/e can pass through the mass analysis chamber 396-1. In the mass spectrometry chamber having the quadrupole electrode shown in FIGS. Since it is separated from the charged particle (ion) beam passing through the chamber 396-1, the damage of the quadrupole electrode 394 is very small. Although charged particles (ions) may collide with the substrate 393, the charged particle (ion) beam colliding with the wall can be discharged to the outside by widening the vacuuming opening 399 of the mass analysis chamber 396-1. Further, it is preferable to protect the inner surface of the mass spectrometric chamber 396-1 by laminating a film having a high resistance to charged particles (ions) (for example, silicon nitride film, alumina).

FIG. 22C shows the case where the quadrupole electrode is formed of a conductor film, although it has the same structure as FIG. 22A. In the central mass analysis chamber 425 (425-1), the left and right side surfaces are formed by the partition walls (substrate side walls) 421-1 and 421-2 of the main substrate 421, and the upper and lower surfaces are formed by the second substrate (upper substrate) 422 and the third substrate ( Lower substrate). A through hole 425-2 is arranged on the left side of the mass spectrometry chamber 425 (425-1) separated by a partition wall 421-1, and the inner surface and the lower surface (the side of the third substrate 423) of the through hole 425-2 are insulating films. A conductor film 426 (426-1) is formed on the inner side thereof by being surrounded by 427. The insulating film 428 is formed on the conductor film 426 (426-1), but it may be omitted. This conductor film 426 (426-1) becomes one of the quadrupole electrodes. The right side 425 (425-3) of the mass spectrometry chamber 425 (425-1) has the same structure, and the conductor film 426 (426-2) is also one of the quadrupole electrodes. For the conductor film 426, after forming the through chamber 425 (425-2, 3), the insulating film 427 is formed on the inner surface of the through chamber 425 (425-2, 3), and the conductor film is formed on the insulating film 427 by the CVD method. And PVD method. In this state, the through chamber 425 (425-2, 3) is not filled with the conductor film and has a space. It is possible to form a quadrupole electrode only with this conductor film, but in order to make it a stronger quadrupole electrode, the space in the penetration chamber 425 (425-2, 3) is made into a conductor by a plating method. Fill with membrane. Alternatively, the space in the through chamber 425 (425-2, 3) is filled with a conductor film by the selective CVD method. Alternatively, after the space in the penetration chamber 425 (425-2, 3) is filled with a conductive film by the CVD method or the PVD method, a portion other than the space in the penetration chamber 425 (425-2, 3) is etched back. The conductor film of is removed. It is also possible to leave the upper part of the space in the penetration chamber 425 (425-2, 3) slightly open and cover the rest with the insulating film 428. The insulating film 428 is also formed by a CVD method, a PVD method, a coating method, a screen printing method, or a combination thereof, and then the upper surface of the through chamber 425 (425-2, 3) is flattened by an etch back method. After that, the upper substrate 422 is attached.

Conductor film patterns 429 (429-1, 2) are formed in the upper and lower regions of the mass analysis chamber on the upper surface of the second substrate (upper substrate) 422 and the lower surface of the third substrate (lower substrate). This conductor film pattern 429 (429-1, 2) can also be formed by a CVD method, a PVD method, a plating method, a screen printing method, or a combination thereof. This conductor film pattern 429 (429-1, 2) becomes the remaining quadrupole electrode. A contact hole 430 is formed in the left and right quadrupole electrodes 425 (425-1, 2) to form a conductor film. An electrode 431 is formed by connecting to the conductor film in the contact hole. A voltage is applied to the quadrupole electrode 425 (425-1, 2). A voltage is also applied to the upper and lower quadrupole electrodes 429 (429-1, 229). By applying these voltages, an electric field is formed in the mass analysis chamber, and the trajectory of the charged particle (ion) beam moving in the mass analysis chamber 425-1 changes depending on the value of m/q. In this embodiment, since the quadrupole electrode is formed of a conductor film and is manufactured by a normal semiconductor process, the mass spectrometry chamber can be manufactured with extremely high accuracy.

FIG. 22D shows an embodiment in which all the quadrupole electrodes are housed in the mass spectrometry chamber and the mass spectrometry chamber is wide. The main substrate 401 attached to the third substrate 403 is provided with a through chamber 413 serving as a mass analysis chamber, and two quadrupole electrodes 407 (407-2, 4) are arranged on the left and right in the through chamber 413 so as to be separated from each other. To be done. One quadrupole on the upper side on a straight line that intersects with the straight line (substantially) at a (substantially) middle (M1) of the straight line connecting the two quadrupole electrodes 407 (407-2, 4). The electrode 407-1 is arranged, one quadrupole electrode 407-3 is arranged on the lower side, and the substantially middle (M2) of the quadrupole electrodes 407-1 and 407-3 substantially coincides with M1. The distance between the two quadrupole electrodes 407 (407-2, 4) and the distance between the two quadrupole electrodes 407 (407-1, 3) are substantially equal. However, even if there is some deviation, it is possible to select ions with a specific m/e value by changing the voltage or frequency applied to the quadrupole electrode. The two quadrupole electrodes 407 (407-2, 4) are attached to the third substrate 403 or a part of the main substrate 401 attached to the third substrate 403 (the pedestal portion 401 (401-1, 2)). doing. Even if the third substrate 403 on which the two quadrupole electrodes 407 (407-2, 4) are arranged or the pedestal portion 401 (401-1, 2) is fixed at a predetermined position by applying an adhesive agent or solder. good. Alternatively, a groove 408 or the like is provided at a predetermined position and the quadrupole electrode 407 (407-2, 4) is arranged and fixed therein. When the pedestal portion 401 (401-1, 2) is present, the contact hole 410 is opened and a conductor film is stacked in the contact hole 410. The conductor film is, for example, a metal such as Cu, Al, Mo, W, Ti, Ni, Cr, Au, or Ag, conductive carbon (for example, nanotube, graphene), a laminated body thereof, an alloy thereof, or a metal alloy thereof. Silicide or low resistance (poly) silicon. On the upper surface of the third substrate 403, the conductive film 411 is patterned in advance at the portion where the contact hole 410 is formed, and the pedestals 401 (401-1, 2) are arranged on it.

A second main substrate 404 (404-2) is attached to the lower portion of the third substrate 403, and a through hole space 414 that serves as a mass analysis lower chamber is formed. The mass spectrometric lower chamber 414 may be formed to have the same size (in plan size) as the mass spectrometric chamber 413 or to have a larger size. The portion of the third substrate 403 that enters the region connecting the upper and lower quadrupole electrodes 407-1 and 3 is removed as wide as possible, and the opening 412 is made wide. One of the merits of this is to minimize the disturbance of the electric field due to the quadrupole electrode. As a result of widening the opening 412, a load may be applied to the third substrate 403 in a portion where the quadrupole electrode 407 (407-2, 4) is arranged, so that the quadrupole electrode 407 (407-). The second main board 404 (404-3, 4) may be arranged as a pillar on the portion of the third board 403 on which the 2, 4) are arranged. The columns 404 (404-3, 4) do not necessarily have to be continuous in the traveling direction of the charged particles (the direction perpendicular to the paper surface and the longitudinal direction of the mass analysis chamber), and the quadrupole electrode 407 ( 407-2 and 4) may be discontinuously arranged as long as they can be supported. Then, the pressure becomes the same as that of the through-hole spaces 414-2 and 41-2 outside the column 404 (404-3, 4) and the central mass analysis lower chamber space 414-1. The fifth substrate 406 is attached to the lower surface of the second main substrate 404. A quadrupole electrode 407-3 is attached to a predetermined position on the fifth substrate 406. An adhesive pattern, a solder alloy pattern, or the like is formed at a predetermined position on the fifth substrate 406, and the quadrupole electrode 407-3 is aligned with the pattern, and heat treatment or the like is performed to fix the quadrupole electrode 407-3 on the fifth substrate 406. .. If the groove pattern 409 is formed at a predetermined position on the fifth substrate 406, and a part of the quadrupole electrode 407-3 is put into the groove pattern 409 and fixed, the groove pattern 409 can be more accurately fixed. The quadrupole electrode 407 (407-1, 2, 3, 4) has, for example, a cross-section having a cylindrical shape, an elliptical shape, a curved shape such as a hyperbolic shape, or a triangular, quadrangular, or polygonal shape. , Or a combination of these, is a rod-shaped electrode. This rod-shaped electrode is attached to a predetermined portion by, for example, a mounting machine (for example, a flip chip bonder). When the adhesive or the like is liquid, it is arranged in a predetermined portion in a self-aligned manner. When a light vibration such as ultrasonic waves is applied, the parts are easily arranged in a predetermined portion in a self-aligning manner. Alternatively, a rod-shaped electrode is mounted on another substrate, the another substrate and the substrate to be mounted are aligned, the rod-shaped electrode is attached to a predetermined position of the substrate to be mounted, and after fixing, the another substrate is separated.

A contact hole 416 is formed in the fifth substrate 406 at the position of the quadrupole electrode 407-3, a conductor film is laminated there, and further an external electrode wiring (conductor film) 417 is formed. (Although not shown on the fifth substrate 406 side, it is shown on the fourth substrate 405 side.) External to the conductor film wiring pattern 411 formed on the third substrate 403 connected to the quadrupole electrode 407-2. Conductor film wiring patterns 443, 419, 440, 441, 442 connected to the electrodes 418 are formed. First, a contact hole 443 is formed in the third substrate 403, a conductor film is stacked in the contact hole 443, and connected to the conductor film wiring pattern 411. Before attaching the second main substrate 404-2 to the third substrate 403, it is preferable to form a contact hole 443 and a conductor film therein. Then, the second main substrate 404-2 is attached to the third substrate 403, the through hole (mass analysis lower chamber) 414 is formed, the conductor films 419 and 440 are stacked, and the conductor film wiring pattern 419 and 440 is formed. The opening 412 of the third substrate 403 is opened thereafter. Alternatively, a contact hole 443 and a conductor film are formed in the contact hole 443 and the conductor film wiring 419 is formed before the second main substrate 404-2 is attached to the third substrate 403, and then the second main substrate 404 is formed. -2 is attached to the third substrate 403. At this time, since the unevenness of the conductor film wiring 419 is formed on the third substrate 403, if this unevenness causes a problem, the relevant portion of the second main substrate 404-2 is previously etched to form the concave portion. It is good to do it. After that, a through hole (lower mass analysis chamber) 414 is formed, and a conductor film wiring pattern 440 connected to the conductor film wiring pattern 419 is formed on the inner surface of the lower mass analysis chamber 414.

Alternatively, a contact hole 443 and a conductor film are formed in the contact hole 443 before attaching the second main substrate 404-2 to the third substrate 403, and then the second main substrate 404-2 is attached to the third substrate 403. A through hole (lower mass analysis chamber) 414 is formed in the second main substrate 404-2, and a conductor film wiring pattern 419 connected to the conductor film in the contact hole 443 is formed on the lower surface of the third substrate. Further, a conductor film wiring pattern 440 connected to the conductor film wiring pattern 419 is formed on the inner surface of the mass analysis lower chamber 414.

On the fifth substrate 406 to which the quadrupole electrode 407 is attached, the conductor film wiring 441 connected to the conductor film wiring pattern 440 is formed. Alternatively, the quadrupole electrode 407 may be attached after the conductor film wiring 441 is formed on the fifth substrate 406. The fifth substrate 406 is attached to the lower surface of the second main substrate 404-2 on which the through hole (mass spectrometry lower chamber) 414 and the conductor film wirings 419 and 440 are formed. The quadrupole electrode 407-3 is aligned and attached so that the position of the quadrupole electrode 407-3 is at a predetermined position and the conductor film wiring 441 is surely connected to the conductor film wiring 440. For the connection between the wirings described above, the method of forming the concave portion 377 shown in FIG. 51F may be adopted. After that, a contact hole 441 connected to the conductor film wiring 441 is formed, a conductor film is laminated inside the contact hole 441, and further an external electrode wiring 418 is formed. (At the same time, a contact hole 416 connected to the quadrupole electrode 407-3, a conductor film can be stacked inside the contact hole 416, and an external electrode wiring 418 can be formed.) The connection wiring to the quadrupole electrode 407-4 is illustrated. Although not included, it can be formed similarly to the quadrupole electrode 407-2.

The quadrupole electrode 407-1 is attached to the fourth substrate 405. The method of attaching the quadrupole electrode 407-1 to the fourth substrate 405 is the same as the method of attaching the quadrupole electrode 407-3 to the fifth substrate 406. For the fifth substrate 406, it is not necessary to form conductive film wiring or external electrode wiring connected to the quadrupole electrodes 407-2 and 407-4. Of course, it is possible to fabricate on the fifth substrate 406 side, but the connection distance becomes long. The second substrate 402 is attached above the main substrate 401 that forms the mass analysis chamber in which the quadrupole electrodes 407-2 and 407-4 are arranged, and the second main substrate 404-1 is attached thereon. A fourth substrate 405 having a quadrupole electrode 407-1 is attached. The quadrupole electrodes 407-2 and 407-4 are attached and fixed to the third substrate 403 (the pedestal may be sandwiched in some cases), and the third substrate 403 is supported by the columns 404-3 and 4 of the second main substrate. Therefore, a cavity may be provided above the quadrupole electrodes 407-2 and 407-4. Therefore, the entire second substrate 402 above the mass spectrometry chamber 413 can be opened. (Aperture 444) Similarly, the space of the mass analysis upper chamber 445 of the second main substrate 404-1 can be set to be the same as or larger than the mass analysis chamber 413.

Although the second substrate 402 is attached to the main substrate 401, the opening 444 of the second substrate 402 may be formed before attaching the second substrate 402, or after the second substrate 402 is attached, the second substrate 402 is attached. The opening 444 of the substrate 402 may be formed. Alternatively, the mass spectrometric upper chamber 445 can be formed after the second main substrate 404-1 is attached onto the second substrate 402, and then the opening 444 of the second substrate 402 can be formed. The mass analysis upper chamber 445 may be formed on the second main substrate 404-1 and then attached to the second substrate 402. Further, the second main substrate 404-1 having the mass analysis upper chamber 445 may be attached to the fourth substrate 405 having the quadrupole electrode 407, and further attached to the second substrate 402. Alternatively, the second main substrate 404-1 may be attached to the fourth substrate 405 to form the mass analysis upper chamber 445, and then the quadrupole electrode 407 may be attached and then attached to the second substrate 402. ..

If the thickness h24 of the main substrate 401 is large and it takes a long time to perform the etching for forming the mass spectrometric chamber, or if the etching is difficult (for example, when the etching mask does not last for a long time), a broken line 446 is used. As shown, a plurality of sheets may be divided and attached to each other. For example, in the case of h24=10 mm, a main substrate (divided) having a thickness of 1 mm is used to etch a portion (a through hole) to be the mass spectrometric chamber 413 (thickness is 1 mm), and 10 sheets are stacked. If combined, h24=10 mm, which can be manufactured by attaching them to the third substrate 403. When electrostatic bonding is used as the attachment method, for example, a 0.2 mm glass substrate or the like is electrostatically bonded to a 0.8 mm main substrate (divided) to form the mass analysis chamber 413 (through hole). By etching (thickness is 1 mm) and stacking 10 of them, h24=10 mm, which can be manufactured by adhering them to the third substrate 403. (If only the lowermost main substrate is attached to the third substrate 403, the third substrate 403 and the glass substrate will not be attached, and all can be attached by electrostatic bonding.)

The lowermost 1 mm-thick main substrate (divided) is attached to the third substrate 403 to etch a part (in the height direction) of the mass analysis chamber 413 (thickness is 1 mm). The main substrate 401 having a thickness of 1 mm, which is obtained by etching the portion to be the analysis chamber 413 (divided), is attached one after another, or a plurality of main substrates attached are attached together. A third substrate 403 having (whole) attached can be manufactured. At this time, when the height of the pedestal 401 is 1 mm (the same as the thickness of the main substrate (divided) in the lowermost layer), the etching process for forming the pedestal is not necessary. Further, the attachment of the quadrupole electrodes 407 (407-2, 4) to the third substrate 403 or the pedestals 401-1 and 401-2 may be performed at the beginning, the middle, or the end of the step of attaching the main substrate (divided). it can.

In the case of the second main substrate 404 (404-1, 404-2) as well, the second main substrate 404 is similarly divided (for example, as indicated by broken lines 447 and 448) to form a mass analysis upper chamber and a lower chamber, respectively. The second main substrate 404 (404-1, 404-2) having a predetermined thickness can be manufactured by forming and attaching it. For example, when h25=10 mm, five second main substrates having a thickness of 2 mm may be stacked. The case of using a glass substrate is the same as that of the main substrate described above. Also when h26=10 mm, it is sufficient to stack 10 second main substrates having a thickness of 1 mm. The case of using a glass substrate is the same as that of the main substrate described above. In the case of the second main substrate 404-2, the conductor film wiring 440 is prepared, but it is possible to form it after stacking it all, or to prepare and connect each time. In this case, on the side surface of the second main substrate 404-2, an insulating film may be formed between the second main substrate and the conductor film for electrical insulation and adhesion improvement. This is necessary especially when the second main substrate is not an insulator. Further, the side surface of the second main substrate 404-2 can be tapered (obliquely) to prevent the conductor film from being stepped. Since the side surface of the second main substrate 404-2, that is, the side surface shape of the mass analysis lower chamber does not have to be a vertical shape, it is tapered to improve the step coverage of the conductor film. The taper is effective not only in the CVD method and the PVD method but also in the plating method and the electroforming method. Of course, the same applies to the second main substrate 404-1 and the mass spectrometric upper chamber, but if there is no conductor film stacked here, it is not necessary to take the shape into consideration.

As described above, since four quadrupole electrodes can be arranged at predetermined positions and four quadrupole electrodes can be arranged in one wide space, an ideal quadrupole electric field can be produced accurately. .. Further, since the outer space of the quadrupole electrode can be widened (in particular, the outer space of the quadrupole electrodes 407-2 and 407), the momentum of the ions passing through the gap between the quadrupole electrodes can be reduced, Damage to the substrate surrounding the mass spectrometry chamber 413, the mass spectrometry upper chamber 445, and the mass spectrometry lower chamber 414 can also be reduced. Reference numeral 449 denotes an evacuation line opening. By providing a large number of evacuation line openings 449, ions that have passed through the gap between the quadrupole electrodes can be immediately ejected to the pump side. Can be further reduced. Further, as shown in FIG. 51F, if a sixth substrate and a seventh substrate to which a third main substrate having a space is further attached are provided outside the fourth substrate 405 and the fifth substrate 406, the fourth substrate is provided. Since the opening can be widened in the substrate 405 and the fifth substrate 406, damage to the fourth substrate 405 and the fifth substrate 406 by ions can be further reduced. Further, in the third substrate 403, an opening communicating with the mass analysis lower chamber 414 (414-2, 414-3) may be partially provided outside the quadrupole electrode 407 (407-2, 407-4). it can. Although it is possible to provide openings in all of them, in that case, a conductor film/wiring is formed on the side surfaces of the pillars (404-3, 404-4). Note that the quadrupole electrode 407 can be directly formed instead of the method of attaching the rod material to the substrate. An example thereof will be described below.

FIG. 23 is a diagram showing a method for manufacturing a quadrupole electrode. The example shown in FIG. 23 is an example of a method for manufacturing the quadrupole electrodes 407-2 and 407-4 shown in FIG. 22D, but the same method can be used for other cases. Therefore, the same parts as those in FIG. 22D are indicated by common reference numerals. 23A to 23D show a method of manufacturing by a plating method. The third substrate 403, the conductor film 411, the main substrate 401-2, the contact 410 and the groove 408 formed on the main substrate 401-2 in FIGS. 23A to 23D are the same as those already described. The groove 408 may be omitted in the plating method. When the main substrate 401-2 and the third substrate 403 are not insulators, an insulating film is interposed between the conductor film 411 and the in-contact conductor film 410.

As shown in FIG. 23A, a conductor film for improving adhesion and a barrier seed conductor film and a plating seed layer 450 are laminated with the conductor film 410 in the contact being exposed. For example, when the plating film is Cu, the plating seed layer is a Cu film, which is laminated by the CVD method or PVD method. The adhesion improving and barrier conductor films are, for example, Ti/TiN and Ta/TaN films, which are laminated by a CVD method or a PVD method. After the adhesion improving and barrier conductor films are stacked, for example, about 50 nm to 500 nm, a plating seed layer is stacked, for example, 500 nm to 5000 nm. Next, the photosensitive film 451 is laminated on the substrate 403 by a coating method or a sheet attachment method, and an opening 452 is formed at a place where a quadrupole electrode is to be formed by a photolithography method. The depth of the opening 452 is about the size of the quadrupole electrode. For example, if the height of the quadrupole electrode is 0.1 mm, the depth is about 0.1 mm, and if the height of the quadrupole electrode is 1.0 mm, the depth is about 1.0 mm, and the height of the quadrupole electrode is 5.0 mm. If so, the depth is about 5.0 mm. After that, the substrate 403 is immersed in the plating solution or is sprayed with the plating solution, and the plating seed layer is energized to form the plating film 453 in the opening 452. (The Cu plating solution is, for example, copper sulfate.) This plating film 453 becomes a quadrupole electrode. After forming the plating film 453 having a predetermined thickness in FIG. 23B, the plating is stopped and the photosensitive film 451 is removed. Using the plating film 453 as a mask, the plating seed layer on which the plating film 453 is not formed and the conductor film for improving adhesion and for the barrier are removed. Usually, the plating seed layer and the plating metal are the same material, but since the thickness of the plating seed layer is much smaller than the thickness of the plating metal, even if the entire surface is etched (wet etching or dry etching), the thickness of the plating metal hardly changes. .. That is, the thickness of the plating metal is reduced by the thickness of the plating seed layer+the amount of over-etching.

In the method using the photosensitive film pattern shown in FIGS. 23A and 23B, the side surface shape of the photosensitive film 451 can be freely changed by the photosensitive mask pattern in the direction perpendicular to the paper surface. The shape in the depth direction cannot be changed freely. At best, it can only be graded. Therefore, the shape of the plated film 453 can be freely changed in the direction perpendicular to the paper surface, but the shape in the depth direction and the shape on the upper side cannot be changed freely. Therefore, as shown in FIGS. 23(c) and 23(d), a mold 454 having a space 455 similar to the final plating shape is produced, and as in the case described with reference to FIG. After laminating the conductor film for plating and the plating seed layer 450, the mold 454 is pressed against the substrate 403 in alignment with the formation portion of the contact 410 which is the mounting position of the quadrupole electrode. In addition to the space 455, the mold 454 is formed of an insulating material such as plastic, polymer resin, or brazing material, and a plating solution injection port 456 and a plating solution discharge port 457 (these are also spaces) are also formed. In addition, since the contact portion side between the mold 454 and the substrate 403 is formed of a flexible material, even if the mold 454 is pressed against the substrate 403, the substrate 403 will not be damaged, and the patterns (411, 401) formed on the substrate 403 will not be damaged. -2 etc.) is firmly covered so that the plating solution does not enter the contact portion between the substrate 403 and the mold 454. The plating solution is flown from the plating solution injection port 456 formed above the space 455 of the mold 454, and the plating solution is discharged from the plating solution discharge port 457 formed below the space 455 of the mold 454. When electricity is applied to the plating seed layer, the plating film grows from the plating seed layer, and a plating film having a shape similar to the space 455 is formed. When the plating film 458 having a predetermined size and shape is formed, the energization of the plating seed layer and the injection of the plating solution are stopped, and the mold 454 is removed to form a quadrupole electrode 458 having a predetermined shape. (FIG. 23(d)) After this. Using the plating film 458 as a mask, the plating seed layer on which the plating film 453 is not formed and the conductor film for improving adhesion and barrier are removed. In FIGS. 23A to 23D, before the plating step, a photolithography method and an etching method are used to form a plating seed layer and an adhesion improving and barrier conductor film in a region where the plating film is not formed. May be removed. In the case of FIGS. 23A and 23B, the plating can be performed without the photosensitive film pattern, but if the conductive film remains in part, the plated film grows in that part. Better to form.

FIG. 24 is a diagram illustrating a method of attaching the quadrupole electrode rod 407 to the substrate. The quadrupole electrode rod 407 is formed in advance in a desired shape. The advantage of this method is that the electric field characteristics of the quadrupole electrode are very good, since the quadrupole electrode using the optimum material can be used. 24A and 24B are views showing a state in which the quadrupole electrode rod 407 is mounted using a flip chip mounting machine (bonder). The vertical cross-sectional view shown in FIG. 24(a) is a schematic cross-sectional view of the contact portion, and FIG. 24(b) is a schematic cross-sectional view perpendicular to the paper surface of FIG. 24(a). That is, FIG. 24(b) is the longitudinal direction of the quadrupole electrode rod 407 and is the traveling direction of ions, and FIG. 24(a) is a vertical cross section thereof. A groove (or recess) 408 is formed in a portion of the first main substrate 401-2 attached to the third substrate 403, to which the quadrupole electrode rod 407 is attached, and the surface of the contact 410 is exposed in that region. .. When viewed in the longitudinal direction of the quadrupole electrode rod 407, the region of the contact 410 is described as a part, but the contact 410 is formed at the portion where the entire quadrupole electrode rod 407 contacts unless the electric field characteristics are impaired. It is also possible to apply a voltage from this contact portion to the quadrupole electrode 407.

A conductive adhesive, a solder metal, a conductive paste, or the like 460 is attached to a portion of the first main substrate 401-2 attached to the third substrate 403, to which the quadrupole electrode rod 407 is attached. As this application method, there are various methods such as application by a dispenser, screen printing, patterning with a photosensitive adhesive, and the like. Although the adhesive or the like 460 is not shown in FIG. 24B to make the drawing easy to see, it is applied to the entire groove portion 408 (shown by a broken line in FIG. 24B) where the quadrupole electrode rod 407 is mounted. To be done. The shape of the groove 408 is preferably formed so that the quadrupole electrode rod 407 just fits in the groove portion, and can be formed by a wet etching method, a dry etching method, a laser method, or the like. When the first main substrate 401 is a semiconductor substrate such as a Si substrate or a conductor substrate such as a Cu substrate, the contact portion with the quadrupole electrode rod 407 is covered with an insulating film. Therefore, it is desirable to stack the conductor film in the contact 410 after forming the insulating film. Alternatively, one main substrate 401 in the portion where the quadrupole electrode rod 407 is mounted may be attached to the third substrate 403 which is an insulating substrate as an isolated pattern (that is, not in contact with other conductor portions or semiconductor portions). For example, the insulating film may not be formed on the first main substrate 401. Note that the adhesive or the like can also be attached to the quadrupole electrode rod 407. That is, an adhesive or the like can be attached to the region where the quadrupole electrode rod 407 is attached to the contact portion 410 and the first main substrate 401-2.

The quadrupole electrode rod 407 is attracted to the attraction portion 459 of the flip-chip mounting machine (bonder) and is attached to the attachment portions of the third substrate 403 and the first main substrate 401 while being aligned. In the case of adhesion using an adhesive, heat treatment at a temperature higher than the curing temperature of the adhesive is performed to solidify and fix. Alternatively, in the case of attachment using an ultraviolet curable adhesive, ultraviolet irradiation is performed to solidify and fix. When a metal is used, it is attached at a temperature equal to or higher than the melting point and then lowered to a temperature equal to or lower than the melting point to be solidified and fixed. If self-alignment is possible by the surface tension of an adhesive or the like, even if the quadrupole electrode rod 407 and the third substrate 403 or the first main substrate 401 are not fixed securely, the flip chip mounting machine (bonder) The adsorption part 459 can be separated from the quadrupole electrode rod 407. When the self-alignment is not possible, after the quadrupole electrode rod 407 is securely fixed to the third substrate 403 and the first main substrate 401, the suction portion 459 of the flip chip mounting machine (bonder) is removed. It is desirable to separate from the heavy pole electrode rod 407. The contact 410 may be formed together with the contact of the third substrate 403 after attaching the quadrupole electrode rod 407. In FIG. 22D, the quadrupole electrode rods 407-1 and 407-3 are directly attached to the second substrates 405 and 406, but in FIGS. 24A and 24B, the first main substrate 401 is used. It is sufficient to consider the case where no is attached. The groove 409 is formed in the second substrate 405 or 406 when necessary. The quadrupole electrode rod 407 may be attached after the contact hole 416 and the outer electrode/wiring 417 are formed in advance in the attachment portion of the quadrupole electrode rod 407.

24C and 24D are views showing a method of attaching the quadrupole electrode rod 407 attached to the support substrate 461 to the fourth substrate 405 or the fifth substrate 406. An adhesive agent 462 is attached to the support substrate 461, and the portion to which the quadrupole electrode rod 407 is to be attached is made the opposite side (lower side in the figure) and attached to the support substrate 461. In the fourth substrate 405 to which the quadrupole electrode rod 407 is attached, the groove portion 409 is formed in the attachment portion. The method of forming the groove portion 409 is the same as that shown in FIGS. The groove 409 is also preferably shaped so that the quadrupole electrode rod 407 can be fitted securely. The contacts 416 and the electrodes/wirings 417 may be formed in advance on the fifth substrate 405. A conductive adhesive or the like (not shown, referred to as 460) is formed on the contact portion of the quadrupole electrode rod 407 in the groove portion 409, and the quadrupole electrode rod 407 attached to the support substrate 461 is attached to the first position. 4 Align and attach to the contact portion of the substrate 405. The adhesive film 462 to which the support substrate 461 and the quadrupole electrode rod 407 are attached is, for example, a thermoplastic adhesive having a softening temperature T1. Further, the adhesive 460 between the quadrupole electrode rod 407 and the fifth substrate 405 is a thermosetting adhesive having an effective temperature T2. A material that satisfies T1>T2 is selected. After the quadrupole electrode rod 407 attached to the support substrate 461 is brought into contact with a predetermined portion of the fourth substrate 405, the ambient temperature is maintained between T1 and T2, and the adhesive 460 is hardened to cure the quadrupole. The electrode rod 407 and the fifth substrate 405 are fixed. Next, the temperature is raised to T1 or higher to soften the adhesive film 462 and separate the support substrate 461. As a result, the quadrupole electrode rod 407 is firmly attached to a predetermined portion of the fifth substrate 405. After that, the contact 416 and the electrode/wiring 417 can be formed. The area of the contact 416 can be widened if the wider the area, the better the electric field characteristics. That is, in FIG. 24D, the region of the quadrupole electrode 410 may be extended in the longitudinal direction. Also in FIG. 24C, the region of the quadrupole electrode 410 may be extended in the width direction. Note that the same method can be applied to the fifth substrate 406, and also for the second substrates 402 and 403, the quadrupole electrode rod 407 can be attached by the same method after attaching the first main substrate 401. it can. As described above, the quadrupole electrode rod 407 having a desired shape and made of a desired material can be fixed to the substrate.

FIG. 25 is a diagram illustrating a method of arranging a quadrupole electrode inside a mass spectrometry chamber using a thin film forming method. The manufacturing method is similar to that of FIG. An electrode pattern 463 is formed on the lower substrate 472, and the main substrate 471 is attached to the lower substrate. At this time, a concave portion 464 is formed on the attachment surface side of the main substrate 471 so as not to come into contact with the electrode pattern 463 formed on the lower substrate 472. The electrode pattern 463 (463-1) is one of the quadrupole electrodes, and the recess 464 will be a mass spectrometry room in the future. The electrode pattern 463 (463-2) and the electrode pattern 463 (463-3) will become a part of the quadrupole electrode in the future, and although not shown in FIG. The electrode pattern 463 (463-2) and the electrode pattern 463 (463-3) that are formed do not contact the main substrate 471. Penetration chambers 473 (473-1, 2) for forming two quadrupole electrodes in the left-right direction are formed in the main substrate 471 attached to the lower substrate 472. At this time, the electrode pattern 463 (463-2) and the concave portion 464 around the electrode pattern 463 (463-3) are included in the through chamber 473 (473-1, 2). That is, the penetration chamber 473 (473-1, 2) is larger than the recess 464 around the electrode pattern 463 (463-2) and the electrode pattern 463 (463-3). When the anisotropic etching for forming the penetration chamber 473 (473-1, 2) is performed, the concave portion 464 penetrates first, so the conductor film 463 (463-2, 3) and this conductor film 463. The lower substrate 472 exposed between (463-2, 3) and the recess is exposed to the etching of the main substrate 471. Therefore, the etching selection ratio between the lower substrate 472 and the conductor films 463 (463-2, 3) and the main substrate 471 is set sufficiently large, and the thicknesses of the lower substrate 472 and the conductor films 463 (463-2, 3) are set. Is set to be not less than the etching amount.

Next, when the main substrate 471 is not an insulator, for example, a Si semiconductor substrate, the insulating film 474 is laminated so as not to be electrically connected to the conductor film 475 formed later. The insulating film 474 is also laminated in the through chamber 473. The thickness of the insulating film is 500 nm to 5000 nm stacked on the side surface of the through chamber 473. With 500 nm, it has a withstand voltage of 200V. In the case of high voltage, the thickness of the insulating film may be increased. The through chamber 473 (473-1, 2) is preferably vertically etched so that the size does not change. The insulating film 474 is also laminated on the bottom of the through chamber 473, and the conductor films 463 (463-2, 3) are also covered with the insulating film 474. Therefore, in order to etch the insulating film 474 in this portion, the substrate surface” Vertical etching (dry etching) is performed on. At this time, the insulating film 474 stacked on the upper surface of the main substrate 471 is also etched, but is thicker than the insulating film 474 stacked on the conductor film 463 (463-2, 3) at the bottom of the through chamber 473. Therefore, even if the insulating film 474 stacked on the conductor film 463 (463-2, 3) at the bottom of the through chamber 473 is completely etched, the insulating film 474 stacked on the upper surface of the main substrate 471 remains slightly. .. However, even if the insulating film 474 laminated on the upper surface of the main substrate 471 is completely etched, the main substrate 471 is exposed. However, if the etching selection ratio between the main substrate 471 and the insulating film 474 is set sufficiently large, the main substrate 471 becomes It is not so much etched, and since the main substrate 471 itself is thick, there is no problem even if it is etched. Moreover, since the insulating film laminated on the side surface of the through chamber 473 is considerably thick in the depth direction, it is hardly etched in the lateral direction.

The conductor film 475 is stacked with the conductor film 463 (463-2, 3) at the bottom of the through chamber 473 exposed. The conductor film 475 is connected to the conductor film 463 (463-2, 3). The conductor film 475 is a conductor film for improving adhesion with the insulating film 474, the conductor film 463 (463-2, 3) and the plating seed conductor film, for example, Ti, TiN, Ta, TaN. The film thickness may be about 100 nm. A conductor film for plating seed is laminated after the conductor film for improving adhesion. When the plating film is Cu, a Cu film is preferable, and a 500 nm to 5000 nm layer is formed by the CVD method, PVD method, or the like. (FIG. 25A) Next, a fluid resin film 465 such as a photoresist film is applied and heat-treated to be hardened to flatten the surface of the main substrate 471. At this time, it is important to put and fill the resin film 465 inside the through chamber 473 as well. The width of the penetrating chamber 473 can be made relatively large, and may be set according to the depth of the penetrating chamber 473, for example, 0.1 mm to 0.5 mm to 5 mm. Therefore, even if the depth of the through chamber 473 is 1 mm to 10 mm, the aspect ratio can be set to about 1 to 5, so that the coverage (step coverage) of the insulating film 474 and the conductor film 475 does not cause any problem and is within the range of 0.5 to 1.0. Can be set. In addition, there is no problem in filling the space of the through chamber 473 with the resin film 465. (Fig. 25(b))

Next, the flattened resin film 465 is removed by etching from above to expose the conductor film 475 stacked on the upper surface of the main substrate 471. At this time, the resin film 465 is filled inside the penetration chamber 473, and the resin film 465 covers 475 laminated on the inner surface of the penetration chamber 473. (FIG. 25C) Therefore, the exposed conductor film 475 is etched (wet or dry) to remove the conductor film 475 laminated on the upper surface of the main substrate 471. However, the 475 laminated on the inner surface of the through chamber 473 can be left as it is. (FIG. 25D) or in the state of FIG. 25B, the resin film 465 and the conductor film 475 which are planarized by a polishing method (CMP method or BG method) are removed in a planarized state, The state of 25(d) can also be set. Next, after removing the resin film 465 remaining in the penetration chamber 473, the contact 466 (466-1, 2, 3) to the conductor film 463 (463-1, 2, 3) is formed on the lower substrate 472. Form. Further, a conductor film 467 connected to the contacts 466 (466-1, 2, 3) is laminated on the lower surface of the lower substrate 472. This conductor film 467 can be laminated simultaneously with the conductor film of the contact 466. This conductor film 467 will be electrodes and wiring for applying a voltage to the quadrupole electrode in the future, but here it is not patterned yet and is laminated on the entire lower surface of the lower substrate 467. A plating solution or a plating spray is flown into 473 (473-1, 2) to grow and fill the plated film 468 into the through chamber 473 (473-1, 2). (Fig. 25(e))

Next, the main substrate 471 side is polished or etched by a polishing method (CMP method or BG method) or an etch back method to flatten the surface of the main substrate 471. Next, a photosensitive film 469 is formed on the surface of the main substrate 471 by a coating method, a photosensitive sheet, or the like, and a portion 470 to be a mass spectrometric chamber is opened by a photolithography method. The opening 470 is opened to the through chamber 473 (473-1, 2), and the main substrate 471 located between the through chamber 473 (473-1, 2) is entirely opened. (FIG. 25F) After that, the main substrate 471 is etched down to the lower substrate 472 to form the through chamber 476. Since the main substrate 471 between the penetration chambers 473 (473-1, 2) is entirely etched, the penetration chamber 476 is formed by filling the conductor film 475 and the plating filling in the penetration chamber 473 (473-1, 2). Face the membrane 468. When the main substrate 471 (the insulating film 474 is interposed therebetween) is a Si substrate, an insulating film 474 (for example, a SiO 2 film, a SiN film) that surrounds the side surface periphery of the through chamber 473 (473-1, 2) is used. Since a large etching selection ratio can be obtained, the insulating film 474 surrounding the side surface of the through chamber 473 (473-1, 2) is not etched much. Since the periphery of the conductor film 463 (463-1) is the recess 464, the lower substrate 472 and the conductor film 463 (463-1) in this portion are more exposed to etching of the main substrate 471 than other portions, but Since the selection ratio with respect to the lower substrate 472 and the conductor film 463 (463-1) can be made high, it is not so much etched. Further, the lower substrate 472 and the conductor film 463 (463-1) may be thickened. (Figure 25 (g))

The main substrate 471 is etched (vertical etching) from the opening 470 of the photosensitive film 469 to form the through chamber 476, the photosensitive film 469 is removed, and then the main substrate 472 shown in FIG. An upper substrate 477 having a conductor film electrode 478 attached to a temporary surface is attached to the upper surface of the substrate 471. Since the conductor film electrode 478 serves as one of the quadrupole electrodes, it is arranged in the through chamber 476 which is a mass spectrometry chamber. The conductor film electrode 478 formed on the upper substrate 477 is formed by, for example, a CVD method, a PVD method, a plating method, a screen printing method or the like. Alternatively, a conductor film may be attached using a dispenser. For example, when the upper substrate 477 is an insulator, a conductor film Ti/TiN film for improving adhesion is laminated in a thickness of 100 nm to 1000 nm, then a Cu plating seed film is laminated in a thickness of 500 nm to 10,000 nm, and an electrode forming portion is formed by a photolithography method. Open the window and perform Cu plating (100 μm ~ 5 mm). Using this thick Cu plating as a mask, the thin Cu plating seed film and the conductor film Ti/TiN film are removed by etching. An adhesive or the like is attached to the portion of the plating film 468 and the upper substrate 477 is attached. When the main substrate 471 is a Si substrate and the upper substrate 477 is a glass substrate or the like, they can be attached by electrostatic anodic bonding. After that, a contact 479 connecting to the plating film 468 and the conductor film electrode 478 is formed on the upper substrate 477. Further, conductor film electrode wirings 480 (480-1 to 48-3) connected to the contacts 479 are formed on the upper surface of the upper substrate 477. Further, conductor film electrode wiring 467 (467-1 to 3) is also formed on the lower substrate side. In this manner, the quadrupole electrode 463-1 and the quadrupole electrode 478 facing the quadrupole electrode 463-1 and the two quadrupole electrodes 468 on the left and right sides are formed in the mass analysis chamber 476. It is desirable that the upper and lower quadrupole electrodes 478 and 463-1 have a symmetrical shape with respect to the left-right center line of the through chamber 476. Further, it is desirable that the left and right quadrupole electrodes 468 be symmetrical with respect to the upper and lower center lines of the through chamber 476. As a result, it is desirable that the center point M1 of the center distance between the upper and lower quadrupole electrodes 478 and 463-1 and the center point M2 of the center distance between the left and right quadrupole electrodes 468 match. As a result, a stable quadrupole electric field is likely to be formed. The mass spectrometric chamber can be manufactured by stacking the structure shown in FIG. (The photosensitive film 469 is naturally removed.) Thereby, the height of the mass spectrometric chamber 476 can be increased. When adhering, a conductive adhesive or solder metal may be applied to the surface of the plating film 468, and an insulating adhesive may be applied to other portions, or they may be adhered without using an adhesive. Since the quadrupole electrode is arranged in the mass analysis chamber, a more stable quadrupole electric field can be formed in the mass analysis chamber 476.

The present invention can also be applied to a multipole having more electrodes than a quadrupole electrode. Examples of the multipole electrode type ion guide include a hexapole electrode type ion guide and an octapole electrode type ion guide. FIG. 26 is a diagram showing an octopole electrode type structure. Four electrodes are further added to the quadrupole electrode shown in FIG. The same components as those used in FIG. 22A are denoted by the same reference numerals. The difference from FIG. 22A is that the octopole electrode 394-1 (lower side) is attached not on the upper substrate 392 but on the third lower substrate 482. The upper side of the octopole electrode 394-1 is attached to the second upper substrate 483. (Here, unless otherwise specified, the term "adhesion" used herein includes both the case of externally attaching and the case of forming a thin film.) However, similar to FIG. , It can be attached to the upper substrate 392 (the same applies to the other electrodes 393-2, 398-8, and the lower side as well), so the details will not be described. Three octopole electrodes 394 (394-5, 1, 8) are attached on the second lower substrate 482. When the octopole electrode 394 (394-5, 1, 8) is attached externally (by attaching a separately prepared octopole electrode), the octopole electrode 394 (394-5, 394-5, Grooves or recesses that match the shapes of 1 and 8) are formed (formed by a photolithography method and an etching method, or grooves and recesses are formed by a laser), and are attached to the grooves or recesses with an adhesive or the like. The second upper substrate 483 is also attached to the upper side of the octopole electrode 394 (394-5, 1, 8) to securely fix the octopole electrode 394 (394-5, 1, 8). At this time, a groove or recess corresponding to the shape of the octupole electrode 394 (394-5, 1, 8) is also formed on the lower surface of the second upper substrate 483, and an adhesive or the like is used to form the groove or recess. Attach it.

The second main substrate 481 is attached between the second lower substrate 482 and the second upper substrate 483 (at this time, the upper substrate 392 is the first upper substrate 392, and the lower substrate 393 is the first lower substrate), and then the second main substrate 481 is attached. It is also possible to form the penetrating chambers 485-1, 2, 3 on the main substrate 481 and arrange the octopole electrodes 394 (394-5, 1, 8) in the penetrating chambers 485-1, 2, 3 respectively. it can. There are various methods for arranging these. For example, the second main substrate 481 is attached to the second lower substrate 482 to form the through chambers 485-1, 2 and 3, and the groove 395 is formed in a predetermined portion of the second lower substrate 482. (It is also possible to form the groove 395 in a predetermined portion of the second lower substrate 482 and then attach the second main substrate 481 to form the penetration chambers 485-1, 2 and 3.) Here, the penetration chamber The substrate side wall plate 481-1 of the second main substrate 481 is present between the 485-1 and the through chamber 485-2, and the second main substrate 481 of the second main substrate 481 is provided between the through chamber 485-1 and the through chamber 485-3. There is a sidewall plate 481-2. In the through chamber 485-2, the substrate side wall plate 481-1 faces the substrate side wall 481-3. In the through chamber 485-3, the substrate side wall plate 481-2 faces the substrate side wall 481-3.

Next, the octupole electrode 394 (394-5, 1, 8) is put into each through chamber 485 (485-1, 2, 3) by a flip chip mounting machine and attached to the second lower substrate 482, and then Then, the second upper substrate 483 is attached to the second main substrate 481. At this time, the upper part of the octopole electrode 394 (394-5, 1, 8) is also attached to the second upper substrate 483. Grooves or recesses 395 are formed in predetermined portions of the second upper substrate 483, and an adhesive or the like is attached to these portions to fit the upper portions of the octupole electrodes 394 (394-5, 1, 8) into these grooves or the like. Just do it. Alternatively, a groove or a recess 395 is formed at a predetermined position of the second upper substrate 483, and an adhesive or the like is attached to this portion so that the upper part of the octupole electrode 394 (394-5, 1, 8) is fitted into these grooves or the like. Attach so that they fit together. The second upper substrate 483 having the octopole electrode 394 (394-5, 1, 8) attached thereto is formed on the second main substrate 481 attached to the second lower substrate 482, and the through chamber 485 (485-1, 2, 3) is formed. ) And the octupole electrode 394 (394-5, 1, 8) is inserted into the second main substrate 481 attached to the second lower substrate 482. At this time, the lower part of the octopole electrode 394 (394-5, 1, 8) is fitted and attached to the groove or the like 395 formed in the second lower substrate 482. In this way, the octupole electrode 394 (394-5, 1, 8) can be attached to the second upper substrate and the second lower substrate. Here, the second upper substrate may be made of the same material as the first upper substrate. The first lower substrate may be made of the same material as the first lower substrate. Also, the second main substrate may be made of the same material as the first main substrate.

A contact is provided on the second upper substrate 483 at a portion where the three octupole electrodes 394 (394-5, 1, 8) and the second upper substrate 483 are attached, and a voltage is externally applied to the second upper substrate 483. It is possible to produce an outer electrode/wiring that can be applied. The direction perpendicular to the main substrate surface, the upper substrate surface, and the lower substrate surface is the Z direction, and the advancing direction of the charged particles is the X direction (in FIG. 26, the direction perpendicular to the paper surface, provided that the advancing direction of the charged particles draws a curve, The octupole electrodes 394-5, 1 and 3 are arranged in the Y direction when the Y direction is the direction perpendicular to both the tangential direction) and the X and Z directions. Portions of the substrate side wall plates 481-1 and 481-2 between the through chambers 485 (485-1, 2, 3) that are not necessary may be removed. Since the second lower substrate 482 and the second upper substrate 483 are also supported by the three octupole electrodes 394 (394-5, 1, 8), they can all be removed. In this case, the side wall of the second main substrate is only the second main substrate 481-3, 4 outside the three octupole electrodes 394 (394-5, 1, 8). Further, the second main substrate 481 can be omitted. Further, the second upper substrate 483 can be eliminated. At this time, the outer electrodes/wirings for supplying voltage to the three octopole electrodes 394 (394-5, 1, 8) are directly supplied to the octopole electrodes 394 (394-5, 1, 8) or the second lower part. The outer electrode/wiring can be formed on the substrate side. The second lower substrate may be omitted, but in that case, since the three octupole electrodes 394 (394-5, 1, 8) are attached to the upper surface of the first upper substrate 392, the first upper substrate 392 may be omitted. The outer electrode/wiring can be formed on the upper surface of the.

As described above, the three octupole electrodes 394 (394-5, 1, 8) mounted in the penetration chamber formed on the second main substrate 481 attached to the second lower substrate 482 and attached to the upper portion thereof. The electrode module substrate including the second upper substrate 483 is attached to the upper surface of the first upper substrate 392. When the first upper substrate 392 has a contact wiring, the contact wiring may be formed on the second lower substrate 482 and connected to the contact wiring of the first upper substrate 392. When this module is attached to the first lower substrate 393, the lower side shown in FIG. That is, the three octupole electrodes 394 (394-6, 3, 7) mounted in the penetration chamber formed on the third main substrate 484 attached to the third lower substrate 486, and the third upper substrate attached to the upper part thereof. The electrode module substrate 485 is attached to the lower surface of the first lower substrate 393. The octupole electrode 394-6 is in a through chamber surrounded by the substrate side wall 484-3 and the substrate side wall plate 484-1 of the third main substrate 484, and the octopole electrode 394-3 is the substrate side wall 484 of the third main substrate 484. -2 and the substrate side wall plate 484-1, the octopole electrode 394-7 is surrounded by the substrate side wall 484-2 and the substrate side wall plate 484-4 of the third main substrate 484. Is located in.

The main charged particles pass near the center of the through chamber 396-1 in the middle. Therefore, it is desirable that the electric field in the through chamber 396-1 by the eight octopole electrodes 394-1 to 394-1 be symmetrical. Therefore, it is preferable to arrange the eight octopole electrodes 394-1 to 394-1 to be as symmetrical as possible with respect to the center of the through chamber 396-1. However, in the case of the present invention, since the frequency and voltage can be individually applied to each electrode while being changed, the electrodes may be symmetrical to some extent. For example, the center of the distance between the facing electrodes (394-1 and 3, 394-5 and 7, 394-2 and 4, 394-6 and 8) is located near the center of the through chamber 396-1. Further, in the case of FIG. 26A, the three electrodes 394-4, 1, 8 and the two electrodes 394-2, 4 and the three electrodes 394-6, 3, 7 are aligned in the Y direction, and three electrodes are provided. The electrodes 394-5, 2, 6 and the two electrodes 394-1, 3 and the three electrodes 394-8, 4, 7 are arranged so as to be aligned in the Z direction. In addition, openings for vacuuming and purging/cleaning are formed in each of the through chambers in the first and second upper substrates and the first and second lower substrates.

The octopole electrode 394 (394-1 to 8) is formed in a rod shape in the X direction, but since it does not need to be entirely supported by the upper substrate or the lower substrate in the X direction, the octopole electrode 394 (394 The second lower substrate 486, the third main substrate 484-3, the first main substrate 391-3, the second main substrate 481-3, the second upper substrate, and the second upper substrate, which surround the outer sides of (394-1 to 8). Inside the main substrate 481-4 and the first main substrates 391-4 and 484-4, only a portion that partially supports the octupole electrode 394 (394-1 to 8) is left, and another upper substrate (the first upper substrate). Substrate 392, third upper substrate 485) and lower substrate (first lower substrate 393, second lower substrate 482), and substrate side wall plates 391-1, 2 of the first main substrate 391, substrate side wall plate of the second main substrate It is also possible to remove 481-1, 481 and the side wall plates 484-1, 484-1 of the third main board. Since the main substrate, the upper substrate, and the lower substrate, which obstruct the electric field generated from the octopole electrode 394 (394-1 to 8), are eliminated, stabilization of the electric field in the mass spectrometry chamber 396-1 can be enhanced. Further, in this case, the pressure also becomes the same in the through chamber around the mass spectrometric chamber 396-1. Further, the space of the through chamber outside the octupole electrode 394 (394-1 to 8) is expanded, and the upper and lower substrates to which the main substrate having the through chamber is further attached are attached on the second upper substrate 483. To expand the penetration room. As a result, a constant space can be present outside the octopole electrode 394 (394-1 to 8). In this case, an opening for vacuuming is provided in the outermost upper substrate or lower substrate so that the pressure in the mass spectrometry chamber can be lowered.

FIG. 26B is a modification of the structure of the octopole electrode 394 (394-1 to 8) shown in FIG. In this embodiment, the distances between the facing electrodes are all (approximately) equal, and the middles are approximately the same. It is desirable that the midpoint (M) be located at the substantially central portion of the mass spectrometry chamber. Therefore, the eight octopole electrodes 394 (394-1 to 8) are arranged on the circumference of the center of M (with the radius R). Further, since it is desirable that the electrodes adjacent to each other have the same relationship, it is desirable that the central angle between the electrodes be approximately 45 degrees. Further, it is desirable that the size and shape of each electrode be uniform and that the shape in the direction facing the intermediate point M be the same or similar. In FIG. 26( b ), since the electrode has a circular cross section and a rod shape (that is, a cylindrical shape), it has the same shape even when rotated, but when the shape is a hyperbolic shape, it is in the direction facing the intermediate point M. It is desirable that the shape is a hyperbolic shape. Therefore, when the electrode is arranged, it is attached to a predetermined place so as to have such a shape. When the height of the electrodes 394-2 and 4 is smaller than the height of the mass analysis chamber, the center of the electrodes 394-2 and 4 is located at the center of the height of the mass analysis chamber. As in the case shown, the pedestal 397 is arranged. Further, in order to make the distances between the electrodes 394-5 to 8 on the diagonal side of FIG. 26(b) and the electrodes 394-1 and 3 in the Z direction substantially the same, the electrodes 394-5 to 8 are provided on the first upper part. It is attached on the substrate 392 and the lower surface of the first lower substrate, and/or the electrodes 394-1, 3 are attached to the upper surface of the second lower substrate 482 and the lower surface of the third upper substrate 485, and in addition to this, a pedestal It is also effective to use. The electrodes 394-2 and 4 located at the same level as the mass spectrometric chamber 396-1 can change the distance relatively freely.

An octupole electrode can be manufactured by using the method of forming the electrodes 425-2 and 3 in FIG. 22C or the method described in FIG. That is, for all the electrodes in FIG. 26A, an octupole electrode can be manufactured by using the method of forming the electrodes 425-2 and 42 in FIG. 22C or the method described in FIG. Further, the arrangement of the octopole electrode shown in FIG. 26(b) can be similarly manufactured. For example, the electrodes 394-5-8 on the diagonal side are also between the second lower electrode 482 and the second upper electrode 483, or between the third lower electrode 486 and the third upper electrode 485, as in FIG. For the electrodes 394-1 and 394-3 formed at the center, a pedestal may be arranged to raise the position of the electrodes. This allows the midpoints of the distances from all the electrodes to be substantially the same.

A hexapole electrode type mass spectrometry room can also be produced using the substrate of the present invention. For example, using the octupole electrode type shown in FIG. 26(a), description will be given in the same manner in the Y direction of the mass spectrometry chamber 396-1, and the electrode 394-1 in FIG. 26(a) will be used. And 394-3, and with respect to the other four electrodes (394-2 and 394-4), two electrodes (394-394) are provided on the upper side in the direction of the central angle 60 degrees from the midpoint M with respect to these electrodes (394-2 and 394-4). 5 and 8), two electrodes (394-6, 7) are arranged on the lower side in the direction of the central angle of 60 degrees from the midpoint M. These electrodes can also be arranged on the same circumference. That is, they are arranged at the same distance from the point M. Alternatively, the upper surface of the first upper substrate and the lower surface of the first lower substrate may be arranged as shown in FIG. As for the quadrupole electrode, it is desirable that the adjacent electrodes are arranged at 90 degrees with respect to the midpoint M and the four electrodes are arranged on the same circumference. If the mass spectrometry chamber and the quadrupole electrode (or multipole electrode, collectively referred to as quadrupole electrode below) are separated by the side wall of the substrate, the electric field due to the quadrupole electrode becomes weak, so the quadrupole electrode It is also possible to remove the other substrate while leaving only the substrate that supports at least. In that case, of course, the periphery of the quadrupole electrode may be further covered with a substrate so as not to deteriorate the vacuum degree of the mass spectrometry chamber.
<Fan type electric field>

The mass spectrometer of the present invention can use a fan-type magnetic field system as the mass spectrometer. FIG. 27 is a schematic view showing a fan-type magnetic field type mass spectrometer having a penetration chamber on which a fan-shaped magnetic field acts on the main substrate of the present invention. FIG. 27A shows a type having one ion detection chamber, and FIG. 27B shows a type having a plurality of ion detection chambers. The mass spectrometric chamber 683-2 of the present invention is a fan-shaped through chamber formed in the main substrate 682, and an upper substrate 688 and a lower substrate 689 are attached to the upper and lower sides thereof. The penetration chamber (adjacent chamber) 683-1 on the input side of the ion beam 685 to the mass spectrometry chamber 683-2 is, for example, the extraction electrode/acceleration chamber 307 in FIG. Ions having a velocity v accelerated by are incident on the mass analysis chamber 683-2 from the adjacent chamber 683-1 through the central hole 690-1 of the substrate side wall 682-1.

An electromagnet 684 is arranged above and/or below the mass analysis chamber 683-2, and the magnetic field B generated by the electromagnet 684 is in the vertical direction of the penetration chamber 683-2, that is, the main substrate 682, the upper substrate 688, and the substrate of the lower substrate 689. It is applied in the direction perpendicular to the plane. Due to this magnetic field B, the ions incident at the velocity v draw a circular orbit of (substantially) radius R0, pass through the central hole 690-2 of the substrate side wall 682-2 serving as the exit of the mass analysis chamber 683-2, and enter the adjacent chamber. Go to 683-3. In this way, in the mass analysis chamber 683-2, the upper and lower parts of the through chamber are sealed by the upper and lower substrates 688 and 689, and the lateral direction (the ion beam traveling direction) is sandwiched by the substrate side walls (of the main substrate) having the central hole. Further, the side direction of the main substrate 682 (the direction perpendicular to the traveling direction of the ion beam) is surrounded by the main substrate. However, the upper and lower substrates 688 and 689 of the mass analysis chamber 683-2 have openings for evacuation, and the inside of the mass analysis chamber 683-2 has a predetermined pressure (for example, 10 ⁻⁴ to 10 ⁻⁸ torr). To Further, an opening for introducing a cleaning gas such as an inert gas (N2, He, Ar, etc.) for cleaning the inside of the mass spectrometry chamber 683-2 can be provided.

The penetrating chamber 683-2, which is a mass spectrometric chamber, is a cavity having an orbit 685 of the ion beam as the center and a width (lateral direction) of about r1 from the center. Therefore, as shown in FIGS. 27(a) and 27(b), the penetrating chamber 683-2 has a fan-shaped cylindrical cavity (cavity having a width r1 centered on a fan-shaped radius R0) in plan view. Is. However, in reality, the through chamber 683-2, which is a mass spectrometric chamber, does not necessarily have to be a fan-shaped cavity, and may be at least a larger cavity including the fan-shaped cylindrical cavity. .. Then, in the cavity, a magnetic field is applied in the vertical direction of the penetrating chamber 683-2, that is, in the direction perpendicular to the substrate surfaces of the main substrate 682, the upper substrate 688, and the lower substrate 689, so that the ion beam trajectory is almost the same. A circular orbit having a radius R0 (fan type: the angle can be selected, for example, from 30 degrees to 180 degrees). For example, if the velocity of ions upon incidence is v (m/sec), the mass of ions is m (kg), the number of charged ions is z, and the magnetic field (magnetic flux density) is B{N/(Am)}, In the mass spectrometry room 683-2, the centrifugal force and the Lorentz force of the ions take a circular orbit with a radius R0, so that mv ² /R0=Bzev (1) holds. If accelerated with voltage V (volts) at an accelerating chamber before entering the mass spectrometer chamber ^{683-2, zeV = mv 2/2} ··· (2) holds. From (1) and (2), m/(ze)=B ² R0 ² /2V (3) is derived. (e is the elementary charge, about 1.6×10 ⁻¹⁹ C (coulomb))

The ions 685 entering the mass analysis chamber have various masses m and electric charges (ze), but have various trajectories R when subjected to the magnetic field force in the mass analysis chamber. (It can be seen from equation (3).) For example, as can be seen from FIG. 27(b), for the same magnetic field B and accelerating voltage V, a small (m/z) becomes an orbit smaller than R0 (for example, 685- 3), orbits with a large (m/z) are larger than R0 (for example, 685-2). The adjacent chamber 690-3 of the mass spectrometry chamber 683-2 is an ion selection chamber, and the substrate side wall 686 having the central hole 690-3 is arranged therein. The central hole 690-3 of the substrate side wall 686 is formed so that an ion beam that has traveled along an orbit of radius R0 can pass through. That is, the trajectory of the ion beam that has traveled along the central trajectory under the force of the magnetic field B corresponds exactly to the central hole 690-3. That is, the ions 685-1 satisfying the expression (3) pass through the central hole 690-3. Therefore, the substrate side wall 686 having the central hole 690-3 may be referred to as an ion selection slit, and when the formula (3) is not satisfied, for example, the ions of the trajectories 685-2 and 685-3 in FIG. I cannot pass 690-3. The ions 685-1 that have passed through the central hole 690-3 enter the adjacent chamber 683-4 through the central hole 690-4 of the substrate side wall 682-3. The adjacent chamber 683-4 is, for example, an ion detection chamber, and the amount of ions selected by the mass analysis chamber 683-2 and the ion selection chamber 683-3 is detected. Thus, the ion selection chamber 690-3 is surrounded by the substrate side walls 682-2 and 682-3. Since ions that cannot pass through the ion selection chamber 683-3 remain, it is desirable to provide an opening for vacuuming or an opening for cleaning in the upper and lower substrates to perform sufficient vacuuming or proper cleaning. Usually, the size of the central hole 690-3 of the ion selection slit is smaller than the size of the central hole 690-2 of the substrate side wall 682-2. Since the ion sorting chamber 683-3 is more dirty than the other rooms, it is desirable to surround it with the substrate side walls 682-2 and 682-3, but since it is a little larger, you can omit it if you do not care about the dirt. However, the ion selection slit 686 is necessary. As described above, the fan-type magnetic field type mass spectrometry shown in FIG. 27A detects ions while changing the magnetic field B and the acceleration voltage V.

The fan-type magnetic field type mass spectrometry shown in FIG. 27(b) is provided with a plurality of ion detection chambers {683-1-1, 2, 3,...} In addition to ions having a radius R0, It is also possible to detect ions having the orbit of. For example, when the center of the mass detection chamber 683-2 (near the position where the ion beam passes) has a radius R0 and the distance from the center to the side surface of the main substrate is r1 on one side and r2 on the other side, FIG. In the mass detection chamber 683-2 in FIG. 27, r1=R1 (constant) and r2=R2 (constant), and in the mass detection chamber 683-2 in FIG. Even if it bends due to this, it does not collide with the side surface of the main substrate 682, and advances to the ion selection chamber 683-3 which is a chamber next to the mass detection chamber 683-2. Further, the substrate side wall (682-2 in FIG. 27A), which is the partition wall of the mass detection chamber 683-2 and the ion selection chamber 683-3, is made smaller (that is, the central hole 690-2 is made larger) or removed. .. Further, in the ion selection chamber 683-3, the orbits other than the central orbit 685-1 (for example, 685-2 and 685-3) spread out, so that as shown in FIG. The side surface of the third main substrate 682 is widened in the traveling direction of the ion beam so that the ion beam does not collide with the side surface of the main substrate 682 as much as possible. Further, the substrate side wall 686 which is an ion selection slit is also removed so that as many ions as possible enter the ion detection chamber 683-4. In the ion detection chamber 683-4, a large number of individual ion detection chambers 683-4-1, 2, 3,... Are in the side surface direction of the main substrate 682 (the direction parallel to the substrate surface of the main substrate 682, and the ion traveling direction). It is aligned vertically with the (central orbit).

Various methods can be adopted as the ion detection chamber, but in particular, all of those described in this specification can be used. Substrate side walls 687 exist between the individual ion detection chambers 683-4-1, 2, 3,... Of the ion detection chamber 683-4 so as not to interfere with each other. Naturally, the collector electrode is also arranged independently for each individual ion detection chamber. The inlet widths of the individual ion detection chambers are w1, w2r, w2l, w3r, w3l,.... Here, w1 is the entrance width of the individual ion detection chamber (683-4-1 in FIG. 27B) along the ion center trajectory 685-1. w2r is an ion detection chamber next to the individual ion detection chamber (683-4-1 in FIG. 27(b)), and the individual ion detection chamber (Fig. 27) arranged outside the ion center orbit 685-1. It is the entrance width of 683-4-2) in (b). w3r is the entrance width of the outer individual ion detection chamber (not shown in FIG. 27B). w2l is an ion detection chamber next to the individual ion detection chamber (683-4-1 in FIG. 27(b)), and the individual ion detection chamber (FIG. 27( It is the entrance width of 683-4-3) in b). w3l is the entrance width of the outer individual ion detection chamber (not shown in FIG. 27B). Let s be the width of the side wall of the substrate between the individual ion detection chambers. The height of the individual ion detection chamber is the thickness of the main substrate 682. The overall width D of the ion detection chamber 683-4 is w1+(w2r+W3r+...)+(w2l+W3l+...)+n×s (n is the number of substrate side walls 687). If the individual ion detection chambers have the same width, the number of the individual ion detection chambers is n+1, so the overall width D of the ion detection chamber 683-4 is D=(n+1)×w1+n×s. Ions are counted whenever they enter any of the individual ion detection chambers, but ions that collide with the partition 687 are not counted. Ions that collide with the outermost and innermost side surfaces of the main substrate 682 of the ion detection chamber (and the side surfaces of the ion selection chamber, etc.) are not counted either. It becomes n+1)×w1/D. For example, if w1=500 μm, s=100 μm, and n=20, D=10500+2000 (μm)=1.25 cm, and the capture rate is 84%.

In the present invention, it is possible to increase the size of the cavity of the mass analysis chamber 683-2, which is a fan-shaped magnetic field chamber, and to increase the size of the curved cavity 683-2 in the traveling direction of the ion beam 685. Since it can be easily performed by using the etching method and the etching method, a desired mass spectrometric chamber 683-2, ion selection chamber 683-2, and ion detection chamber 683-4 can be manufactured. Further, since each ion orbit is tilted with respect to the ion orbit 685-1 traveling in the central orbit, the trapping area is different when the entrance area of the individual ion detection chamber is made constant. It is also easy to change the entrance area of the individual ion detection chamber. For example, the entrance area of the individual ion detection chamber can be increased as the ion trajectory becomes more outward. Further, since it is easy to align the direction of the individual ion detection chamber with the ion trajectory, it is possible to make the entrance area of the individual ion detection chamber the same and make the ion penetration area the same in each individual ion detection chamber. Even with a mass spectrometer having a plurality of ion detection chambers as shown in FIG. 27B, the values of the acceleration voltage V and the magnetic field B can be continuously changed to perform more precise measurement.

The sector magnetic field 684 has permanent magnets or electromagnets arranged in the upper part and/or the lower part of the mass analysis chamber 683-2, and is perpendicular to the mass analysis chamber 683-2 (direction from the top to the bottom or vice versa). A magnetic field (magnetic field) is applied to. That is, the south pole or north pole of the magnet is arranged outside the upper substrate or the lower substrate covering the mass spectrometric chamber 683-2, and/or the opposite side to the outer side of the lower substrate or the upper substrate facing the opposite pole. Deploy. For example, when the mass spectrometry chamber 683-2 is curved clockwise as shown in FIGS. 27A and 27B, it is necessary to bend the ion beam 685 in the same clockwise direction. Arranges the S pole on the upper side and the N pole on the lower side so that the magnetic field (magnetic field) goes from the lower side of the mass analysis chamber 683-2 (lower substrate 689 side) to the upper side (upper substrate 688 side). (Fleming's left-hand rule) The magnets are arranged only in a region that applies a magnetic field to exert a force on the ions, for example, a fan-shaped magnetic field region 684 in FIGS. 27A and 27B.

The electromagnet may be a coil, and the coil is formed in a substrate, and the substrate is provided on the main substrate 682 and/or the main substrate 682 having a cavity (through chamber) through which the mass analysis chamber 683-2 or another ion beam 685 passes. It may be attached to the bottom. 27C is a view showing a cross section taken along line A1-A2 of the mass spectrometry chamber 683-2 in FIG. 27A or 27B, and is shown on the upper surface of the main substrate 682 having the mass spectrometry chamber 683-2. A board module 699 (699-1) having a coil built in is attached to the upper surface of the attached upper board 688, and/or a board module 699 (699) having a coil built in to the upper surface of a lower board 689 attached to the lower surface of the main board 682. 2 is a diagram in which (2) is attached.

In the board module with a built-in coil, the coil 695 is mounted between the upper board 693 and the lower board 692, and the electrodes/wirings 697 (697-1, 2) are formed on the outer surface of the upper board 693 or the lower board 692. A current can be passed from the electrodes/wirings 697 (697-1, 2) to the conducting wire of the coil 695. A coil-embedded substrate 691 is attached between the upper substrate 693 and the lower substrate 692, and the coil 695 is mounted in the substrate 691. The winding conducting wire of the coil 695 is wound in parallel with the substrate surface of the substrate 691, and the conducting wire is laminated and connected in the direction perpendicular to the substrate surface. Therefore, when a current is made to flow from the electrode/wiring 697 (697-1, 2) to the coil 695, the current I in the coil flows parallel to the substrate surface, and as a result, the conducting wire of the coil is oriented in the vertical direction, that is, the cylinder (where the coil is wound). ), the magnetic field (magnetic field) penetrating in the axial direction is generated. If the coil has n turns and the radius of (the cylinder of) the coil is a, the magnetic field (magnetic field) H at the center of the coil is H=nI/(2a).

The material surrounding the coil 695 such as the upper substrate 693, the lower substrate 692, and the built-in substrate 691 is a non-magnetic material in order to transmit the magnetic field generated by the coil to the outside. On the built-in substrate 691 and/or the upper substrate 693 on which the coil 695 is mounted, a conductor film wiring 698-1 connected to a conductor wire at one end of the coil 695 is formed, and the conductor film wiring 698-1 is an upper substrate or a lower portion. The contact hole 696 (696-1) formed in the substrate and the conductor film formed therein are connected, and the contact hole 696 (696-1) and the conductor film formed therein are connected to the upper substrate. Alternatively, it is connected to the electrode/wiring 697-1 formed on the lower substrate. Further, a conductor film wiring 698-2 connected to a conductor wire at the other end of the coil 695 is formed on the built-in substrate 691 and/or the upper substrate 693 on which the coil 695 is mounted, and the conductor film wiring 698-2 is formed on the upper substrate. Alternatively, the contact hole 696 (696-2) formed in the lower substrate and the conductor film formed therein are connected, and the contact hole 696 (696-2) and the conductor film formed therein are The electrodes/wirings 697-2 formed on the upper substrate or the lower substrate are connected.

As the method of forming the coil-embedded substrate, for example, after the substrate 691 is attached to the lower substrate 692, a coil mounting cavity (through chamber) 694 is formed at a position where the coil 695 should be mounted. An insulating film is stacked in the cavity 694, the inner surface of the cavity is covered with an insulating film, a conductor film is formed, and conductor film wiring 698 (698-1, 2) is formed in the cavity 694. When the substrate 691 is an insulator, stacking of an insulating film in the cavity 694 is not essential. Next, the coil 695 is inserted into the cavity, and the conductor wire terminal of the coil 695 is connected to the conductor film wiring 698 (698-1, 2). This connection can be made by interposing a low melting point alloy such as solder or a conductive paste. On the other hand, conductor film wiring 698 (698-1, 2) is formed on one surface of the upper substrate 693. Next, the upper substrate 693 is attached to the lower substrate 692 and then attached to the coil-embedded substrate 691 having the cavity 694 formed therein. At this time, the conductor film wiring 698 (698-1, 2) formed in the cavity and the conductor film wiring 698 (698-1, 2) formed on one surface of the upper substrate 693 are connected. Next, a contact hole/conductor film 696 and an electrode/wiring 697 are formed in the upper substrate 693. These may be formed on the upper substrate 693 in advance and then attached to the coil-embedded substrate 691. Here, the upper substrate 692 and the lower substrate 693 are usually insulators. When these are a semiconductor substrate or a conductor substrate, the electrodes and wiring are electrically connected by forming an insulating film in the contact hole 696 or the cavity 694, or before forming the conductor films 697 and 698 on the substrate surface. Try not to. Thus, the coil surrounded by the substrates 691, 692 and 693 is completed.

Although a large number of coils can be mounted in this module substrate 699-1, there are places where coils do not need to be arranged in the mass spectrometer, so the module substrate 699-1 is replaced with the module substrate on which the mass spectrometer is formed (for example, 19, it is formed by the substrates 301, 302, 303. Alternatively, in FIG. 27, it is formed by the substrates 682, 688, 689.) The coil 695 is arranged at a necessary position when fitted to the substrate. Thus, the coil 695 is arranged on the module substrate 699-1. In this case, the module substrate 699-1 may be provided in an unnecessary place, but since the module substrate 699-1 and the module substrate on which the mass spectrometer is formed can be attached at once, a large number of mass spectrometers can be used in a series of processes. It has the advantage that it can be formed. In order to make unnecessary places in the module substrate 699-1 as little as possible, a large number of blocks in which the coils necessary for the module substrate 699-1 are arranged are produced (for example, in FIG. 27, a fan-shaped portion 684 is formed). Is a single block. In practice, it may be easier to cut the block into a block having a minimum rectangular portion including the fan-shaped portion 684.), and then these blocks are cut into individual blocks. Is attached to the module substrate on which the mass spectrometer is formed. In this case, the portion to which the coil block is attached has a large thickness. According to this method, the entire module substrate 699-1 having the coil built therein can be effectively used. The coil shown here is described as a coil of only a conductor wire in which a conductor wire is spirally wound, but this is only drawn to simply show that it is a coil, and various coils (inductors) are Can be used. For example, a package type such as a chip inductor having a coil mounted therein may be used. Since the terminal electrodes of the chip inductor are exposed to the outside, when the chip inductor is inserted into the cavity 694 shown in FIG. 27C, it is easy to connect with the upper substrate, the lower substrate, and the conductor film wiring 698 in the cavity. Becomes Alternatively, the chip inductor can be directly attached to the upper substrate 688 attached on the mass analysis chamber 683-2.

In the case of chip inductors, various characteristics such as winding type, laminated type, film type, type having ferrite core, non-magnetic substance core, high permeability magnetic substance core, magnetic substance type, etc. Value). Since the wire-wound coil of the type in which the conductor wire is exposed has durability against heat generation even when a large current is applied, a large magnetic field can be generated. Also in this case, if the coil is directly attached to the upper and lower substrates 688 and/or 689, air cooling or the like can be easily performed, so that heat resistance can be improved. Even in the coil insertion type shown in FIG. 27C, the coil inside the cavity can be cooled by air cooling or liquid cooling by opening openings Op for air cooling in the upper and lower substrates. When the coil is attached to the upper and lower substrates 688 and/or 689, a connection wiring pattern may be formed on the upper and lower substrates 688 and/or 689 and both terminals of the coil may be connected to the connection wiring. Further, since the magnetic field in the mass analysis chamber can be increased by bringing the coil as close as possible to the mass analysis chamber 683-2, it is preferable to make the upper and lower substrates 688 and/or 689 as thin as possible. However, the thickness is required to secure the strength and the degree of vacuum. For example, when the substrate is a glass substrate, the thickness is about 50 μm at present, but it can be further thinned in the future by technological improvement. In order to reduce the thickness of the entire upper and lower substrates 688 and/or 689, these substrates may be attached to the main substrate 682 and then these substrates may be polished by using a back grinding device or a CMP device. After thinning these substrates, contact holes, electrodes/wirings, and coils can be mounted. Alternatively, the upper and lower substrates 688 and/or 689 may be thinned only in the region where the coil is mounted and its periphery. For example, a region other than the thinned region is covered with a photosensitive film pattern (mask) and the region is etched to be thinned, or the region of the upper and lower substrates 688 and/or 689 is thinned in advance, and The partial substrate 688 and/or 689 is attached to the main substrate 682, or a small polishing device (for example, a device that applies a polishing liquid containing an abrasive to a flat surface portion of the disk body to rotate the disk body, Attach a plurality of support substrates to the main substrate, bring the support substrate close to the main substrate, and simultaneously apply the rotating disk body to the main substrate at the same time to polish multiple locations simultaneously.) There is also a way to do it.

The module substrate 699-1 with a built-in coil (the lower surface of the lower substrate 692 thereof) is attached onto the upper substrate 688 of the mass spectrometer having the mass spectrometry chamber 683-2 and the like. That is, the coil 695 is arranged immediately above the mass spectrometry room 683-2. That is, the coil 695 of the module substrate 699-1 is arranged in the portion that generates the fan-shaped magnetic field. Although only one coil is shown in FIG. 27C, a plurality of coils may be arranged in the width direction (left and right direction in FIG. 27C) and/or the depth direction (ion traveling direction). For example, the width of the mass spectrometric chamber 683-2 is d1, the width of the coil 695 is d2 (in the case of a plurality of coils, the width obtained by combining a plurality of coils, that is, one coil width is b, and m pieces are arranged in the width direction. In this case, when d2=mb (however, the gap between the coils is ignored), the center of d2 is aligned with the substantial center of d1 so that d2>d1. Since the area of the vertical magnetic field in the mass analysis chamber 683-2 is narrow when only the upper part of the mass analysis chamber 683-2 is arranged, the module substrate 699 having the same coil as 699-1 is also provided in the lower part of the mass analysis chamber 683-2. -2 is placed. As the module substrate 699-2, the same one as the module substrate 699-1 can be turned over and used. That is, the module substrate 699-2 with a built-in coil (the lower surface of the lower substrate 692 thereof) is attached below the upper substrate 689 of the mass spectrometer having the mass spectrometry chamber 683-2 and the like. That is, the coil 695 is arranged immediately below the mass spectrometry chamber 683-2. These can be attached by using room temperature bonding, high temperature bonding, diffusion bonding, an adhesive material, or the like. When using an adhesive or the like, use a non-magnetic material that does not block the magnetic flux generated by the coil. When the substrates 688, 689, 692 are glass substrates, quartz substrates, or the like, they can be attached by electrostatic anodic bonding between these substrates via a Si substrate or a conductor substrate. Needless to say, if there is an opening in the attached substrate at the time of this attachment, the opening should not be blocked. (Excluding an opening that may be closed) Since the coil 695 is arranged immediately below or above the sectoral magnetic field region 684 of the mass analysis chamber 683-2, the upper substrate 688 or the lower portion of the mass analysis chamber 683-2 is disposed. The necessary opening of the substrate 689 may be provided outside the sector magnetic field region 684.

By setting the polarities of the coils arranged immediately above the mass analysis chamber 683-2 and the polarities of the coils arranged immediately below the mass analysis chamber 683-2 to be opposite polarities, a vertical magnetic field is generated between these coils. .. That is, a vertical magnetic field is generated in (the sector-shaped magnetic field region of) the mass analysis chamber 683-2. The magnetic field of the mass spectrometric chamber 683-2 is estimated. When a current I is flowing through a circular coil (n winding) having a radius a, the magnetic field on the central axis (distance b from the center of the coil end) is H=(nI/2)a ² /(a ² +b ² ) ^3/2 . If a=1 mm and b=1 mm, then H=1.8×nI×10 ² [A/m]. If a=5 mm and b=5 mm, then H=35×nI [A/m]. Supposing that the radius of the fan is R0=10 cm, (m=10 ⁻²⁷ kg, e=1.6×10 ⁻¹⁹ C, B2/V=10 ⁻⁶ , B=4π×10 ⁻⁷ ×H, acceleration voltage H=2.5×10 ³ [A/m] when V=10 V. H=10 ⁴ [A/m] when accelerating voltage V=100 V. From the above, assuming that the number of coil turns is 50, a When =1 mm and b=1 mm, (1) acceleration voltage V=10 volt, current flowing in coil is 0.28 A, (2) accelerating voltage V=100 volt, current flowing in coil is 1.2 A, a=5 mm , B=5 mm, (3) accelerating voltage V=10 volt, the current flowing in the coil is 1.4 A, (4) accelerating voltage V=100 volt, the current flowing in the coil is 5.8 A. Therefore, even in a minute coil Since the above calculation is the magnetic field in the case of one-sided coil, the current flowing in the coil can be half of these when two coils are arranged above and below. Since the core to be inserted into the coil is not taken into consideration, the current flowing in the coil can be further reduced by using the insertion core having a large magnetic permeability, and therefore the coil can have a large margin.

As shown in FIG. 27C, the height of the mass spectrometry chamber 683-2 is h1 (equal to the thickness of the main substrate 682), the thickness of the upper substrate 688 is h2, and the thickness of the lower substrate 692 of the module substrate 699-1. Is h3, the height of the cavity 694 is h4 (equal to the thickness of the substrate 691), and the thickness of the upper substrate 693 is h5, the total thickness of the mass spectrometry chamber is h1+2 (h2+h3+h4+h5). (It is assumed that the lower side is the same as the upper side.) For example, if h1=1 mm, h2=h3=0.2 mm, h4=1 mm, h5=0.2 mm, then the thickness of the entire mass spectrometry chamber is 4.2 mm. If h1=10 mm, h2=h3=1 mm, h4=10 mm, and h5=1 mm, the thickness of the entire mass spectrometric chamber will be 36 mm, and the height will be very small. Since the size of the ion beam is at most 10 nm to 100 nm, h1=1 mm, h2=h3=0.2 mm, h4=1 mm and h5=0.2 mm are sufficient. In the present invention, since a substrate having a sufficiently uniform thickness can be used and the substrate is attached and patterned by the LSI process, such a size is sufficient. It should be noted that d1 and d2 can be wide. For example, with respect to h1=1 mm, d1=1 to 10 mm and d2=1.1 to 11 mm can be set. In the case of a circular coil, multiple coils having a diameter of 1 mm and a height of 1 mm to 5 mm are arranged side by side in the magnetic field region. In particular, since the traveling direction of the ion beam becomes long, it is necessary to arrange many coils. In the case of the present invention, even with such a small coil, the electrodes can be arranged on the outside and currents can be individually passed, so that precise current control (that is, precise magnetic field control) is possible. These controls can be controlled by the LSI by connecting the wiring to the LSI chip for each coil. Even if the size of the mass spectrometry chamber becomes large, it is possible to simulate whether the ion beam can be controlled as described above, so it is possible to arrange many small coils, and to increase the size of the coil while adapting to the size of the mass spectrometry chamber. You can also do it. The mass spectrometer and the accelerator according to the present invention are very small in size, and are stacked by laminating the substrates, connecting the substrates side by side, or using an ingot substrate using a mold shown later to obtain a very small size. It can be manufactured from a size to a large size (with an analysis chamber height of 1 mm or more, 10 mm or more, 10 cm or more, 20 cm or more, or more).

FIG. 28 is a diagram showing a mass spectroscope for detecting ions with an ion detector arranged in multiple directions in the mass spectroscope to receive the force by the magnetic field, which is a modification of the mass spectroscope shown in FIG. 27(b). I can say. FIG. 28(a) has outlets on both left and right sides which are at right angles to the advancing direction of the incident ion beam 685 in the mass analysis chamber 683-2 and above (in the same direction as the incident ion beam 685). It is a mass spectrometer. The mass spectrometry chamber 684 (a part of) to the right, the ion selection chamber 683-3, and the ion detection chamber 683-4 are the same as those shown in FIG. The mass analysis chamber 684 (part of) toward the left side, the ion selection chamber 683-5, and the ion detection chamber 683-6 are substantially symmetrical to the one on the right side with respect to the mass analysis chamber 683-2. Therefore, the mass spectrometric chamber 683-2 is wider than in the case of only one side, and the magnetic field generation (application) portion 684 is also wider. In FIG. 28( a ), a rectangular magnetic field is applied, and when ions 685 from the extraction electrode/acceleration chamber 683-1 enter the mass analysis chamber and enter the magnetic field generation (application) part 684, a vertical force is applied. In response to the received ions, the ions bend and proceed to the ion selection chamber 683-3 on the right side or the ion selection chamber 683-5 on the left side, and the ion 685-1 that has advanced to the ion selection chamber 683-3 on the right side is the ion detection chamber 683-4. Then, the ion 685-2 that has proceeded to the ion selection chamber 683-5 on the left side is detected in the ion detection chamber 683-6. When the positive and negative ions enter the ion 685, for example, the positive ion bends to the right side, the negative ion bends to the left side, and both the positive ion and the negative ion can be analyzed with one magnetic field 684. A wide range of positive ions and negative ions can be analyzed simultaneously by scanning the acceleration voltage and magnetic field. Further, the cycle time of measurement can be shortened by alternately using the two right and left ion detection patterns 683-4 and 683-6. For example, the line once measured (for example, the left side) is contaminated, which may cause contamination (contamination) when continuously analyzed. Therefore, it is desirable to insert a purge process (vacuum drawing or gas purging) in between. With two lines, one can be purged while the other is being measured. Alternatively, even if one cannot be used, the other can be used to perform the measurement. Alternatively, since the neutral particles go straight, it is possible to analyze the neutral particles.

In FIG. 28A, another chamber 683-7 is further provided in the traveling direction of the incident ions 685. The separate chamber 683-7 is provided to allow ions 685 coming straight forward without using a magnetic field to enter and perform mass spectrometry by another method. For example, a quadrupole mass spectrometer or an ion trap mass spectrometer can be provided. An accelerating chamber or an accelerating electrode may be provided so as to have an appropriate speed, and the ion beam may be guided to these quadrupole mass spectrometry chambers or ion trap type mass spectrometry chambers. The advantage of this method is that the same sample can be measured using different methods. Therefore, more reliable measurement can be performed. In addition, other open spaces can be used to create additional ion sorting and detection chambers. In the mass spectrometer of the present invention in which a through chamber (cavity) is formed in the main substrate and separate substrates are attached to the upper and lower sides thereof, a large number of ion detection chambers can be simultaneously manufactured in the same process at a time, so the cost is one detection chamber. It is almost the same as the one with.

FIG. 28B is a diagram showing a magnetic field type mass detector having a large number of ion detection chambers by further developing this. There is a mass analysis chamber 683-2 next to the extraction electrode/acceleration chamber 683-1 or in the traveling direction of the ion beam 685. The mass analysis chamber 683-2 is the outlet of the extraction electrode/acceleration chamber 683-1 or the mass analysis chamber 683. -2 has a cavity that expands from the center of the inlet, and the expanded cavity surrounds part or all of the extraction electrode/acceleration chamber 683-1. An extension line (indicated by an alternate long and short dash line) of the side surface (side wall) 682-a of the extraction electrode/acceleration chamber 683-1 (to the mass analysis chamber 683-2) of the main substrate 682 and the spread of the mass analysis chamber 683-2 on the right side. The maximum angle formed by the space (cavity) is α1. Further, an extension line (indicated by an alternate long and short dash line) of the side surface (side wall) 682-b of the main electrode 682 of the extraction electrode/acceleration chamber 683-1 (to the mass analysis chamber 683-2) and the mass analysis chamber 683-2 on the left side. Let α2 be the maximum angle formed by the expansion space (cavity). In FIG. 28B, α1 and α2=180 degrees. As can be seen from the figure, either α1 or α2 may be 0. In other words, mass analysis of ions is possible in only one of the left and right spaces, but if both are available, more accurate and reliable measurements can be made, the measurement cycle time can be shortened, and the life of the measurement device can be extended. The advantage is that it can be held. In this embodiment, the mass spectrometric chamber is a continuous space, and there is no partition (partition wall, etc.), but for example, after detecting ions on the right side, ion detection is performed on the left side, and when both are contaminated, the mass spectrometric chamber is collected. Since the ion detection chamber can be cleaned, the cycle time can be shortened and the device life can be extended.

If α1 and α2 have a small angle, mass analysis by magnetic field is possible, but due to the small number of ion detection chambers and the narrow magnetic field that can be swept, α1 and α2 may be 30 degrees or more. desirable. If α1 and α2 are 45 degrees or more, it is better, further 90 degrees or more is quite good, 120 degrees or more is better, 150 degrees or more is better, and 180 degrees is the capability of the present invention. Make the most of. There is a substrate side wall (partition wall) having a central hole 690-1 between the extraction electrode/acceleration chamber 683-1 and the mass spectrometry chamber 683-2, and the ion beam 685 passes through the central hole 690-1 and the mass spectrometry chamber 683. Incident on -2. A magnetic field application region 684 is provided inside the mass analysis chamber 683-2. In this region, a magnetic field is applied in the vertical direction of the mass analysis chamber 683-2 (the paper surface direction of FIG. 28B), and the incident ions The beam 685 is bent by the Lorentz force. That is, the orbital radius R0 is drawn so as to satisfy m/(ze)=B2R02/2V. A large number of ion detection chambers are arranged around the mass spectrometry chamber 683-2. In FIG. 28(b), the periphery is a rectangular shape, 683-4-1-1 to 683-4-1-n on the right side, 683-4-2-1 to 683-4-2-m on the upper side, The number of ion detection chambers is 683-4-3-1 to 683-4-3-p on the left side and 683-4-4-1 to 683-4-4-q on the lower side. Are m+n+p+q in total. For example, if the size of the mass analysis chamber is 50 mm×50 mm and the width of the extraction electrode/acceleration chamber 683-1 (including the widths of 682-a and b) is 5 mm, the pitch of the ion detection chamber (of the ion detection chamber (Width+width of partition wall 687) is 0.5 mm, m=n=p=100, q=90, and the total number of ion detection chambers is 390. Even if there are many ion species in the ion beam, even if one magnetic field and one accelerating voltage are applied, those ions enter any of the ion detection chambers, so that the identification of many ion species can be measured at one time. .. Further, by scanning the magnetic field and the accelerating voltage, it is possible to detect each time using a large number of ion detection chambers, so that more accurate and precise analysis can be performed. In FIG. 28B, the space (outer shape) of the mass spectrometric chamber is a rectangular shape, but it may be another shape, for example, a polygonal shape or a circular shape. Further, if the entrance of the ion detection chamber is made perpendicular to the trajectory of the bent ions, the incident conditions of a large number of ions will be the same, so more accurate and precise analysis can be performed. Since the inclination angles of the entrance of the ion detection chamber and the incident ions are known, they can be compared by calculation. Further, although the magnetic field region 684 has a rectangular shape, it may have a circular shape or another shape. Such a mass spectrometric chamber, a magnetic field region, and a large number of ion detection chambers can be simultaneously produced at one time. Moreover, since the LSI process (photolithography, etching, film formation, alignment at the time of attaching the substrate, etc.) is used, an extremely accurate and highly accurate mass spectrometer can be manufactured. Therefore, the accuracy of mass spectrometry is much better than that of the conventional apparatus. Further, since the apparatus itself becomes very small, the vacuum system can be made small, and the size of the entire mass spectrometer can be made extremely small.

When the upper and lower substrates 693 and 692 are insulating substrates such as a glass substrate, a quartz substrate, an alumina (Al2O3) substrate, and aluminum nitride (AlN), and the substrate 691 between them is a semiconductor substrate such as a silicon substrate, A cavity (through chamber) can be formed by various methods described in various places, and an insulating film, a conductor film, a protective film, or the like can be formed inside the cavity or on the upper and lower substrates. Further, the coil can be formed without forming the cavity. For example, if an insulating film and a conductive film are alternately laminated on a silicon substrate or an insulating substrate, the conductive film wiring is changed to a circular or polygonal type wiring each time, and a multi-turn coil is formed by connecting vias. It is possible to produce a large number of minute coils (having a small inner diameter) with high density. The substrate can also be used as the substrate module 699-1. Also, by inserting a high-permeability ferromagnetic core in the center of the coil, it is possible to manufacture a high-density micro coil capable of generating a large magnetic field. For example, the details are described in the patent application invented by the inventor and they can be applied to the coil of the invention. (Japanese Patent Application No. 2010-285215)

FIG. 29 is another embodiment of the mass spectrometry room. The mass spectrometer of the present embodiment is a double focusing type, and has an electric field sector that generates an electric field and a magnetic field sector that generates a magnetic field. That is, in this embodiment, the mass analysis chamber having the fan-shaped electric field chamber 710 and/or the fan-shaped magnetic field chamber 711 is formed as a through chamber in the main substrate 701, and the upper and lower parts thereof are the upper substrate 702 and the lower substrate 703. Is attached to form an airtight space. FIG. 29A is a plan view showing a cross section parallel to the substrate surface. In the fan-shaped electric field chamber 710, the penetrating chamber 704 (704-2) has a fan shape, and the conductor films 707 (707-1, 2) are formed on the substrate side surfaces of the left and right main substrates 701 having the fan shape. Are formed and a voltage is applied between these conductor film electrodes 707 (707-1, 2), whereby the trajectory of the ion beam 709 (shown by a broken line) is bent. The adjacent chamber 704-1 of the penetrating chamber 704-2 of the fan-shaped electric field chamber 710 is, for example, the extraction electrode/acceleration chamber 307 or the ionization chamber 325 in FIG. 19, and the partition wall (substrate side wall) having the central hole 712-1 is provided therebetween. ) 705-1, the ion beam 709 is incident on the penetrating chamber 704-2 of the fan-shaped electric field chamber 710 through the central hole 712-1. FIG. 29B shows a cross section (indicated by A1-A2) perpendicular to the side surface of the main substrate 701 having the two conductor film electrodes 707 (707-1, 2) facing each other. The upper substrate 702 and the lower substrate 703 are attached to the upper surface and the lower surface of the main substrate 701, and the penetration chamber 704-2 is opened. The side surface of the through chamber 704-2 is the main substrate 701 and is substantially perpendicular to the upper substrate 702 and the lower substrate 703. An insulating film 713 is formed on both side surfaces of the through chamber 704-2, and a conductor film 707 is laminated on the insulating film 713. The insulating film 713 and the conductor film 707 can be formed by various methods described in this specification.

For example, the divided main substrate 701 is attached to the upper substrate 702 or the lower substrate 703, and then the through chamber 704-2 is formed. At this time, the side surface of the through chamber 704-2 is formed to be substantially vertical. An insulating film 713 is formed on the inner surface of the through chamber 704-2, and a conductor film 707 is further laminated thereon. When the main substrate 701 is an insulating substrate, the insulating film 713 does not necessarily have to be formed, but may be formed to improve the adhesion of the conductor film 707. Since the upper substrate 702 and the lower substrate 703 are usually insulating substrates, the same applies to them. The conductor film 707 is, for example, Cu, Al, Au, Ni, Cr, Ti, W, Mo, Fe, Zn, silicide, conductive PolySi, conductive C, a laminated body of these, an alloy thereof, or a composite film. The CVD method, the PVD method, the plating method, the electroforming method, and a combination thereof are used for the lamination. As shown in FIGS. 29A and 29B, the conductor films 707 on both sides of the side surface of the main substrate 701 are removed by etching, but they may be formed over the entire surface. It can also be formed by dividing it further. In that case, voltage can be applied to each conductor film electrode, and the electric field between the parallel plate electrodes (curved) is controlled by each voltage application, and It is also possible to control the precise trajectory of the beam.

Even when the main substrate 701 is divided and the conductor films 707 are stacked separately on the upper substrate side and the lower substrate side, the surfaces of the substrate sidewalls 705-1 and 2 and the lower surface of the upper substrate 702 that isolate the electric field chamber 704-2. Since the conductor film 707 is also stacked on the upper surface of the lower substrate 703 and the lower substrate 703, it is connected to the necessary electrodes 707-1 and 2 and the outer electrodes 716 and 717 on the side surface side of the main substrate 701 by using the photolithography method+the etching method. The necessary conductor films such as the wirings 707-3 and 4 on the lower surface of the upper substrate 702 and the wirings 707-6 on the upper surface of the lower substrate 703 are removed. After that, an insulating film for protecting the conductor film wiring is laminated, the protective film on the surface to be bonded to the substrate is removed by etching, and the main substrate 701 on the upper substrate 702 side and the main substrate 701 on the lower substrate 703 side are attached. At this time (for example, at the position indicated by the alternate long and short dash line 718), in order to connect the upper and lower conductor films with each other with good adhesion, a conductor film may be further laminated at the joint between the conductor films or a low melting point film may be formed. A metal may be attached and heat-treated to form an alloy at the joint. Alternatively, an adhesive in which a conductive material is dispersed can be used to apply pressure and heat when attaching the upper and lower main substrates 701 to connect the upper and lower conductor films. Further, when anodic electrostatic coupling is performed between the upper and lower main substrates 701 via a glass substrate or the like, a conductor film is formed not only on the side surface of the glass substrate but also on the upper and lower surfaces at the portion where the conductor films are connected to each other. Alternatively, there is also a method of thermocompression-bonding the portion of the conductor film (also in which a low melting point metal may be laminated). Furthermore, after attaching the upper and lower parts to each other, an opening is provided in the upper substrate 702 or the lower substrate 703, a gas for selective CVD is introduced from there, and a metal such as W is laminated only on the conductor film portion, There is also a method of introducing a plating solution and laminating a plating metal only on the conductor film portion. The opened portion may be applied to an opening portion for vacuuming, or the opening portion may be closed with a low melting point glass or the like so as not to interfere with the vacuum maintenance of the through chamber 704-2. In the present invention, since voltages can be individually applied from the electrodes (716, 717) formed on the upper and lower substrates to the conductor film electrodes 707 (707-1, 2) formed on the side surfaces of each main substrate 701, the attachment surface The electric potential of the upper and lower conductor film electrodes 707-1 or 707-2 can be made the same even if the sufficient connection is not made. Therefore, the electric fields of the parallel plate electrodes 707-1 and 707-2 can be made constant. Note that this method can be applied to all of the present invention.

In the upper substrate 702, contact holes 714 connected to the conductive film wirings 707-3 and 407 formed on the lower surface of the upper substrate 702, a conductive film is formed in the contact holes 714, and further, outer electrodes 716-1 connected to the contact holes 714. 2 are formed on the upper surface of the upper substrate 702. Similarly, in the lower substrate 703, contact holes 715 connected to the conductive film wirings 707-5 and 707 formed on the upper surface of the lower substrate 703, a conductive film is formed in the contact holes 715, and further outer electrodes connected to the contact holes 715. 717-1 and 2 are formed on the lower surface of the lower substrate 703. As a result, a voltage can be applied from the outer electrode 716-1 or 717-1 to the parallel plate electrode 707-1 and from the outer electrode 716-2 or 717-2 to the parallel plate electrode 707-2.

As another manufacturing method, conductor film wirings 707-3, 4,5, 6 are formed on the upper substrate 702 or the lower substrate 703. On the other hand, a penetration chamber 704-2 is formed in advance on the main substrate 701, and then an insulating film 713 and conductor films 707-1 and 2 are formed. The conductor films 707-1 and 2 are also patterned. These films may be formed after the main substrate 701 is attached to another substrate. This separate substrate will be removed later. Further, the main substrate 701 may be divided and formed. Next, the main substrate 701 on which the through chamber 704-2 and the conductor film patterns 707-1 and 2 are formed is patterned on the upper substrate 702 or the lower substrate 703 on which the conductor film wirings 707-3 to 707 are formed. Attach it. When another substrate is used, the other substrate is separated. In this method, for example, a softening adhesive (which can be peeled off at a certain temperature or higher) or a low melting point metal may be used for adhesion. Then, the other substrate (upper substrate 702 or lower substrate 703) is attached. When the main substrate 701 is divided into a plurality of parts, the main substrates 701 are attached to each other in order and the upper substrate and the lower substrate are attached at the last or when necessary, or the main substrate 701 is attached to the upper substrate or the lower substrate in order. To go. In that case, a glass substrate or the like may be interposed therebetween, and it is also necessary to previously form the through chamber and the conductor film pattern on the glass substrate or the like. In these cases, a process of laminating a conductor film on the connection portion by using a plating method or a selective CVD method may be introduced every time the connection of the conductor film in the penetration chamber of the attached substrate is ensured. In this case, the conductor film can be selectively formed without patterning with a photosensitive film or the like. After patterning the conductor film 707, a protective film (insulating film) can be stacked on the conductor film 707. A protective film (insulating film) may be stacked on the electrode/wiring 716 to open a window at a necessary place.

As described above, the conductor films 707-1 and 707 formed on the two parallel side surfaces of the main substrate 701, which is fan-shaped in a plan view and whose vertical direction is substantially vertical to the substrate surface, are formed. -2 is a parallel plate electrode having an interval k. When a voltage V is applied between the electrodes 707-1 and 707-2, an electric field of E=V/k is applied between the parallel plate electrodes. When the ion 709 advances to the central portion of the parallel plate electrode, the ion receives a force F=qE due to the electric field E, and the orbit is bent. (Q is the charge that the ion has) Since the electric field E is constant, the trajectory of this ion is circular. If the radius of this circular orbit is r, then r=mv ² /(qE). m is the mass of the ion, and v is the velocity of the ion. Therefore, the orbital radius r differs depending on the velocity of the ion, the mass of the ion, the voltage between the electrodes, and the charge of the ion. When it comes out of the parallel plate electrode, it does not exert a force on the ions, so it goes straight. Next to the electric field chamber 704-2, there is an ion distribution chamber 704-3, in which the central hole 712-3 is arranged so that the ions that have passed through the circular orbit of radius r0, which is the central orbit of the electric field chamber 704-2, pass. A substrate side wall 706 having a.

The electric field chamber 704-2 and the ion distribution chamber 704-3 are separated from each other by a substrate side wall 705-2 having a central hole 712-2, and ions leaving the electric field chamber 704-2 pass through the central hole 712-2. Enter the ion distribution room 704-3. Ions that have passed through the circular orbit of radius r0 that is the central orbit of the electric field chamber 704-2 pass through the central hole 712-3 of the substrate side wall 706. That is, the central hole 712-3 of the substrate side wall 706 is arranged in the direction in which the ions (central orbital ion 1) that have passed through the circular orbit of radius r0 that is the central orbit of the electric field chamber 704-2 leave the parallel plate electrode. ing. Ions passing through other trajectories cannot pass through the central hole 712-3 of the substrate side wall 706 and collide with the side wall of the substrate side wall 706, the side surface of the main substrate 701, the upper substrate or the lower substrate. That is, the size of the hole in the central hole 712-3 of the substrate sidewall 706 is adjusted accordingly. In the ion distribution chamber 704-3, if the left-side penetration chamber of the substrate side wall 706 is 704-3-1 and the right-side penetration chamber is 704-3-2, the central orbit ion 1 is in the left-side penetration chamber 704-3-1. Other ions also exist, but only the ion of the central orbital ion 1 exists in the right penetration chamber 704-3-2. (Of course, it may leak a little and another ion may enter.) The side wall 705-2 of the substrate separating the electric field chamber 704-2 and the ion distribution chamber 704-3 is not necessary, but by providing this, it is possible to some extent. Other ions can also be blocked by this substrate side wall 705-2. Further, the electric field chamber 704-2 and the ion distribution chamber 704-3 can be separately evacuated and cleaned. Further, since the ion 709 not only passes through the central orbit but also has a certain extent of spread, some of these ions also receive a force from the electric field and draw a circular orbit of radius r0. Since the orbital ions 1) are also the same kind of ions as the central orbital ion 1, the spread central orbital ion 1 is located at the position of the central hole 712-3 of the substrate side wall 706 so that the central orbital ion 1 also enters the through chamber 704-3-2 on the right side as much as possible. I take the. For example, the central hole 712-3 of the substrate side wall 706 is arranged on a line connecting the center of the central orbital radius r0 of the parallel plate and the position immediately before the spread of the ions 709. Further, the parallel plate electrodes are formed in a fan shape of 90 degrees, and the adjacent chambers 704-1 and 704-3 are arranged so as to be connected to the fan-shaped electrode chamber 704-2. With such an arrangement, the center orbital ion 1 converges at a convergence point (electrostatic field convergence point (plane)) near the position of the central hole 712-3 of the substrate side wall 706, so that most of the center orbital ions 1 are fan-shaped. It can be placed in the magnetic field chamber 704-4. Further, the size of the central hole 712-2 of the substrate side wall 705-2 is set to be larger than the size of the central hole 712-3 of the substrate side wall 706 so that the expanded central orbit ion 1 is also put into the ion distribution chamber 704-3.

However, in the above method, ions having a kinetic energy in a certain narrow range (central orbital ion 1) can be passed, and the resolution can be improved, but this slit (central hole) causes the size of other ions to increase. Since a part is removed, the ion detection sensitivity is deteriorated. Therefore, a slit (central hole) may be provided at a position slightly deviated from the convergence point (plane) of the electrostatic field so that other ions can pass through. This can also be done by adjusting the size of the slit (central hole).
The distributed ions (central orbital ion 1) enter the distribution chamber 704-3-2 and further enter the fan-shaped magnetic field chamber 704-4 adjacent to the distribution chamber 704-3-2. A substrate side wall 705-3 having a central hole 712-4 is provided between the fan-shaped magnetic field chamber 704-4 and the distribution chamber 704-3-2, and the central orbital ion 1 passes through the central hole 712-4. Although the substrate side wall 705-3 may not be provided, by providing it, the distribution chamber 704-3-2 and the fan-shaped magnetic field chamber 704-4 can be evacuated separately, and each can be set to a predetermined pressure. To measure the pressure, an opening may be provided in the upper substrate or the lower substrate and a pressure sensor may be connected. Further, cleaning and purging can be separately performed. If a temperature sensor is also installed, the temperature condition of the measuring instrument can be grasped.

A magnetic field device is arranged above and/or below the sector magnetic field chamber 704-4, and a sector magnetic field 708 is applied in a direction perpendicular to the substrate surface. The magnetic field chamber 704-4 is a penetration chamber sandwiched between two fan-shaped side surfaces in the lateral direction and sandwiched between an upper substrate 702 and a lower substrate 703 in the vertical direction. The fan-shaped magnetic field does not have to be fan-shaped, and it is sufficient if the vertical magnetic field is uniformly applied to the required region 708 of the fan-shaped magnetic field chamber 704-4. The structure of the fan-shaped magnetic field chamber 704-4 may be the same as that shown in FIG. 27, which is already a single fan-shaped magnetic field chamber. For example, the upper and lower portions of the fan-shaped magnetic field chamber 704-4 may be sandwiched by a C-type electromagnet, an H-type electromagnet, a window frame-type electromagnet, a cylindrical electromagnet, a prismatic electromagnet, or the like. In this case, the polarities of the electromagnet surface on the side facing the upper part or the lower part of the magnetic field chamber 704-4 and the electromagnet surface on the opposite side are opposite. The fan-shaped magnetic field chamber 704-4 of the present invention has an extremely thin thickness (height or vertical depth), and since variations in the thickness can be made extremely small, the strength of the electromagnet can be made small, and as a result, As a result, the size of the electromagnet can be reduced. Also, the width (width in the lateral direction) of the fan-shaped magnetic field chamber 704-4 can be made extremely small, and its variation can be made very small, so that the size of the electromagnet in the lateral direction can be made small. Of course, a large size can be manufactured as described above.

FIG. 29C is a diagram in which module substrates 699-1 and 699-2 having coils mounted on the upper and lower substrates 702 and 703 of the magnetic field chamber 704-4 are attached, and B1-B2 of FIG. It is a figure which shows a cross section. This state is the same as in FIG. 27(c). The polarity of the coil surface of the coil 695 of the module substrate 699-1 on the upper substrate 702 side is opposite to the polarity of the coil surface of the coil 695 of the module substrate 699-2 on the lower substrate 703 side. This can be easily set by changing the winding method of the coil or the direction of current flow. The coil 695 is arranged so that its axis is perpendicular to the substrate surfaces of the main substrate 701, the upper substrate 702, and the lower substrate 703. That is, the axis of the coil 695 is arranged perpendicularly to the board surfaces of the upper and lower boards 692 and 693 of the module board 699 and the board 691 with a built-in coil. As a result, the coil surface (the winding surface of the coil wiring) of the module board 699 is arranged. The upper and lower substrates 692, 693 and the coil-embedded substrate 691 are arranged so as to be parallel to the substrate surfaces. Then, the upper and lower substrates 692 and 693 of the module substrate 699 and the substrate surface of the coil-embedded substrate 691 are arranged so as to be parallel to the substrate surfaces of the main substrate 701 having the magnetic field chambers 704-4 and the upper and lower substrates 702 and 703. .. As a result, the magnetic field generated by the upper and lower coils is generated in the vertical direction of the magnetic field chamber 704-4, and the magnetic field is applied to the ions 709 passing through the magnetic field chamber 704-4 at a right angle.

Ions 709 that have passed through the central hole 712-4 of the substrate side wall 705-3 are bent by receiving a uniform magnetic field in the magnetic field application region 708 in the magnetic field chamber 704-4 to be a circular orbit, and go straight when they leave the magnetic field application region 708. exercise. Next to the magnetic field chamber 704-4 is an ion drift chamber 704-5, and then enters the ion detection chamber through a central hole on the side wall of the substrate which is a collector slit. There is a substrate side wall 705-4 having a central hole 712-5 between the magnetic field chamber 704-4 and the ion drift chamber 704-5, and sorts some ions. In the ion drift chamber 704-5, the ions 709 move straight, and the collector slits are arranged so that the ions converge at the collector slits. In this way, the electric field chamber and the magnetic field chamber, the electric field region (the region in which the parallel plate electrodes are arranged) and the magnetic field region (where the parallel plate electrodes are arranged) have opposite directions of velocity dispersion in the electrostatic field and the magnetic field and have the same dispersion width. By arranging a region to which a magnetic field is applied) and various penetration chambers, the sensitivity and resolution of ion detection can be improved. In some cases, the ion drift chamber 704-5 can also be used as the ion detection chamber.

FIG. 30 is a diagram showing one design guideline for the single-focusing sector magnetic field analyzer and the double-focusing sector magnetic field analyzer. Although these are derived from general guidelines, these design guidelines can be applied to the analyzer using the substrate of the present invention. FIG. 30A is a diagram showing a design guideline of the single-focusing sector magnetic field analyzer. The main substrate includes an ionization chamber 722-1, an ion drift chamber A722-2, a magnetic field analyzer chamber 722-3, an ion drift chamber B722-4, and an ion detection chamber 722-5. The ionization chamber 722-1 and the ion drift chamber A 722-2 are partitioned by a substrate side wall 721-1 having a central hole 723-1, and the ions generated in the ionization chamber 722-1 are central holes 723 of the substrate side wall 721-1. It spreads from -1, spreads, and advances. In the case where the substrate side wall 721-1 also serves as the extraction electrode, the ions are accelerated and proceed here. After this, it is also possible to accelerate on the side wall of the substrate with the central hole. When the position of the central hole 723-1 of the substrate side wall 721-1, which is the origin of ion spread, is P1, various ions are accelerated and spread from this point. Even ions with the same mass-to-charge ratio m/z proceed with various angles. For example, an ion 725-1 traveling in the center, an ion 725-2 swelling outward and traveling (shown by a dotted line), an ion 725-3 traveling inward, and the like. The ion drift chamber A722-2 is a region where the accelerated ions travel straight forward. The ion drift chamber A 722-2 and the magnetic field analyzer chamber 722-3 are partitioned by a substrate side wall 721-2 having a central hole 723-2, and can be individually evacuated, cleaned and purged. Since the ions emitted from the central hole 723-1 of the substrate side wall 721-1 are spread, the size of the central hole 723-2 of the substrate side wall 721-2 is larger than the size of the central hole 723-1 of the substrate side wall 721-1. To make it easier for ions to pass. In some cases, the substrate side wall 721-2 may be omitted.

The magnetic field analyzer chamber 722-3 has a magnetic field region 724, and since a vertical magnetic field is applied to the magnetic field analyzer chamber 722-3, when ions enter this region, the magnetic field region 724 advances in a circular orbit. When the radius of the circular orbit of a predetermined ion 725-1 is R0, the ions 725-2 and 3 having the same m/z and having a spread and entering the magnetic field region 724 also proceed in the circular orbit of R0. Upon leaving the magnetic field region 724, the ions go straight and enter the adjacent room ion drift chamber B722-4. The magnetic field analyzer chamber 722-3 and the ion drift chamber B722-4 are separated by a substrate side wall 721-3 having a central hole 723-3. The central hole 723-3 is sized so that the spread ions 725-2, 3 can also pass through. The ions 725-1, 2 and 3 having the same m/z and spreading spread at the convergence point P3. By disposing the substrate side wall 721-4 having the central hole 723-4 at this convergence point P3, only the ions 725-1, 2-3 having the same m/z and spreading can be passed. The other ions collide with the wall of the substrate side wall 721-4, the side surface of the main substrate 721, the upper substrate and the lower substrate. Therefore, since the ion drift chamber B722-4 becomes dirty, it is desirable to perform vacuuming as well as cleaning and purging as appropriate. Therefore, an opening is provided in the upper substrate and the lower substrate of the ion drift chamber B722-4, and the opening is performed through the opening.

If the contamination of the ion drift chamber B722-4 is not a problem, the substrate side wall 721-3 can be eliminated. Next to the ion drift chamber B722-4 is an ion detection chamber 722-5, and the ion drift chamber B722-4 and the ion detection chamber 722-5 are separated by a substrate side wall 721-5 having a central hole 723-5. However, since the ions that have passed through the convergence point P3 spread again, it is necessary to adjust the size of the central hole 723-5 so as not to block these ions. In some cases, the substrate side wall 721-5 may be eliminated and the ion detection chamber may be arranged immediately after exiting the substrate side wall 721-4 arranged near the convergence point P3. This substrate side wall 721-4 may be called a collector slit. When the central point of the circular orbital radius R0 of the central orbital ion 725-1 passing near the center of the magnetic field analyzer chamber 722-3 in the magnetic field region 724 is P2, the ion spreading origins P1 and P2 and the convergence point P3 are on a straight line. Since it is on (m), it is sufficient to arrange each through chamber in such a manner. Further, the fan-shaped magnetic field region 724 is arranged so as to have a central angle α around P2. This α can be arbitrarily designed in the range of 30 degrees to 180 degrees, but in FIG. 30, it is described as α=90 degrees. At this time, the ion drift chamber A and the ion drift chamber B are arranged so as to form an angle of 90 degrees. In the fan-shaped magnetic field region 724, the ions draw a circular orbit, and as described above, each chamber is designed so as to satisfy mv ² /R0=Bzev, where 1/2mv ² =zeV (V is an accelerating voltage). Good. As described above, the width of each chamber can be 100 μm to 1 mm to 20 mm or more. The height of each chamber is determined by the thickness of the main substrate, and can be 100 μm to 1 mm to 20 mm or more. The thickness of the side wall of the substrate can be appropriately set to 10 μm to 100 μm to 1 mm or more. The size of the central hole can also be set to 10 μm to 100 μm to 1 mm to 10 mm, or larger. The length of each chamber may be set according to the ion velocity. When a Si wafer is used as a main substrate, the maximum Si wafer at present is 450 mm in a single crystal, but since a polycrystal or amorphous can be used in the present invention, a Si wafer (substrate) of 1000 mm square can also be used. The whole can be configured according to. Further, since the present invention can be manufactured by laminating in the vertical direction, it is possible to manufacture a mass spectrometer having a desired thickness, but by using the laminating technique also in the lateral direction, a large-sized mass spectrometer can be manufactured. For example, you can create each room separately and connect them horizontally. Further, since it is possible to divide each chamber and connect them, it is possible to manufacture a mass spectrometer having a desired large size. This can also be said to other things of this invention, but if it is the system which divides and connects each room, each room can also be replaced comparatively easily. For example, the defective penetrating chamber can be replaced, or the penetrating chamber with better performance or a different performance can be replaced. In that case, if the low melting point alloy, resin, or plastic is adhered to the connecting portion, the replacement is easy. Alternatively, if the connecting portion is not attached and the outer substrate is slightly apart from the connecting portion, it is pressed by another member or attached to surround the connecting portion with another member to ensure airtightness and easy replacement. Alternatively, the airtightness can be ensured by sandwiching another member and the sealing material at the substrate outside thereof. For example, it is possible to exchange the electric field chamber and the magnetic field chamber.

FIG. 30B is a diagram showing a design guideline of a double-focusing fan-type analyzer having an electrostatic field analyzer and a magnetic field analyzer. This double-focusing fan-type analyzer is also formed in the main substrate 731, and the region through which the ion beam passes is a through chamber formed in the main substrate 731. In these through chambers, the upper part is the upper substrate and the lower part is the lower substrate. Are attached to the main substrate, and the through chambers are evacuated through the openings provided in the upper substrate and/or the lower substrate to set a predetermined pressure. Each through chamber is partitioned by a substrate partition having a central hole, and the ion beam enters each through chamber through the central hole of the substrate partition. The mass spectrometer shown in FIG. 30B includes an ionization chamber 732-1 including an ion source, an ion drift chamber A732-2, an electrostatic field analyzer chamber 732-3, an ion drift chamber B732-4, and a magnetic field analyzer chamber 732-5. , An ion drift chamber C732-6, an ion detection chamber 732-7, and a substrate partition wall 731-1 having a central hole 733-1 and a substrate partition wall 731-2 having a central hole 733-2 between the through chambers. A substrate partition wall 731-3 having a central hole 733-3, a substrate partition wall 731-4 having a central hole 733-4, a substrate partition wall 731-5 having a central hole 733-5, and a substrate partition wall 731 having a central hole 733-6. -6, a substrate partition wall 731-7 having a central hole 733-7 is arranged to partition each through chamber. Ions are generated in the ionization chamber 732-1 and are accelerated and spread from the central hole 733-1 of the substrate side wall 731-1 which also serves as the acceleration electrode. Although the ions are converged at the starting point P1, the ions spread in the ion drift chamber A732-2 and enter the electrostatic field analyzer chamber 732-3 through the central hole 733-2 of the substrate side wall 731-2. In the electrostatic field analyzer chamber 732-3, the ions move circularly due to the electric field generated by the parallel plate electrodes 734-1 and 734-2 formed on the side surfaces of the parallel through chamber having a fan-shaped center and a radius r0. Its equation of motion is mv ² /r=zeE. (Mv ² /r0=zeE for the ion passing through the center). ) The ions emitted from the central hole 733-1 at the starting point P1 travel with a spread and take a circular orbit in the electrostatic field analyzer chamber according to each kinetic energy. Ions having the same kinetic energy have the same circular orbit radius. The ions whose trajectories are bent in the electrostatic field analyzer chamber 732-3 pass through the central hole 733-3 of the substrate side wall 731-3 and enter the ion drift chamber B732-4 in the adjacent chamber.

When the ion having the same kinetic energy as the ion 736-1 passing through the center is defined as the curvature center point P2 of the parallel plate electrode, it is converged at the point P3 where the line m connecting P1 and P2 and the ion trajectory 736-1 passing through the center intersect. To do. If a converging slit is provided at this converging point P3 and only converging ions are passed therethrough, the resolution can be increased, but ions (736-4, 5) having the same m/z are also removed. However, the ion detection sensitivity will decrease. For example, if the central hole 733-4 of the substrate side wall 731-4 is narrowed and arranged at the convergence point P3, the spread ions 736-4 and 736-5 are also removed. Therefore, by arranging the position of the substrate side wall 731-4 in the ion drift chamber B732-4 behind the point P3 and expanding the central hole 733-4, the expanded ions 736-4 and 736-5 and focused ions 736-1, 2 and 3 can be passed through. If the side wall of the substrate is provided, vacuuming, purging, and cleaning can be performed independently, but it can be omitted for the purpose of passing ions. The spread ions 736-1 to 5 enter the magnetic field analyzer chamber through the central hole 733-5 of the substrate side wall 731-5, and undergo circular motion by receiving the Lorentz force due to the magnetic field in the magnetic field region 735. If the orbital radius of the ion circularly moving in the central orbit is R0, then mv2/R0=zevB holds. The ions 736-1 to 73-5 having the same m/z and having a spread form a circular orbit with the same radius R0, and when they leave the magnetic field region 735, they converge at the convergence point P4. If the substrate side wall 731-7 having the central hole 733-7 serving as a collector slit is arranged at the convergence point P4, the ions passing through the central hole 733-7 become ions having the same m/z. The adjoining chamber 732-6 of the magnetic field analyzer chamber 732-5 is the ion drift chamber C, and the ions move at a constant velocity up to the convergence point of the ions having a specific m/z. Ions that have not passed through the central hole 733-7, which is a collector slit, collide with the walls of the substrate side wall 731-7, the side surface of the main substrate 731, and the like. Gas, powder, etc. generated by these are discharged through a vacuuming line in the ion drift chamber C, or to the outside during cleaning or purging. Ions that have passed through the central hole 733-7, which is a collector slit, enter the ion detection chamber 732-7 and are measured by the ion detector.

It is easy to design if the central angle α of the fan-shaped parallel plate electrode is usually 90 degrees. That is, the ion drift chamber A732-2 and the ion drift chamber B732-4 may be designed to be 90 degrees. However, without specifying this, α may be set within the range of 30 degrees to 120 degrees. Also, the central angle β of the fan-shaped magnetic field region 735 may be designed within the range of 30 degrees to 180 degrees. The present invention can be easily manufactured in various sizes and shapes by mask projection, but since it depends on the size of the main substrate, an optimum layout may be used. Since the size of the ion detection chamber 732-7 can be freely set, a plurality of ion detectors can be arranged. (Array detector, etc.) This double-focusing analyzer is a type (Nier-Jhonson type) in which there is an electric field before the magnetic field, but conversely, the magnetic field may be in front of the electric field. Alternatively, it is easy to arrange two magnetic fields side by side. Moreover, since it can be manufactured collectively, there is almost no increase in cost. Furthermore, it can be freely combined with a quadrupole analyzer, ion trap type, time of flight (TOF), and FTICR (Fourier transform ion cyclotron resonance type).

The present invention can also be applied to FTICR (Fourier transform-ion cyclotron resonance). FIG. 31 is a diagram showing the FTICR of the present invention. FIG. 31A is a cross-sectional view of the ion traveling direction (magnetic field direction) perpendicular to the substrate surface. FIG. 31B is a cross-sectional view perpendicular to the ion traveling direction (magnetic field direction) perpendicular to the substrate surface. An ion source chamber 754-1 and an ICR chamber 754-2 are formed in the main substrate 751. An upper substrate 752 and a lower substrate 753 are attached to a main substrate 751 at the upper and lower portions of these penetration chambers. There is a substrate side wall 751-1 having a central hole 765 between the ion source chamber 754-1 and the ICR chamber 754-2, and the ions 750-1 generated in the ionization chamber are the central holes of the substrate side wall 751-1 also serving as extraction electrodes. It is introduced into the ICR (ion cyclotron resonance) chamber 754-2 through 765. The ICR chamber 754-2 is surrounded by a substrate side wall 751-1 (having a central hole 765) and a side surface 751-2 of the main substrate facing the side wall 751-1 with respect to the ion traveling direction, and the side surface side is the substrate of the main substrate 751. It is surrounded by a side wall 751-4 (closed side surface with no central hole etc.) and a substrate side wall 751-5 of main substrate 751 (closed side surface with no central hole etc.), and the upper and lower sides are an upper substrate 752 and It is surrounded by the lower substrate 753.

In the ICR chamber 754-2, the opposed trap electrodes A 755-1, 3 (the conductor films 755-1, 3 formed on the substrate side wall 751-1)} and the trap electrode B 756-1 (on the substrate side wall 751-2). Conductor film 756-1), counter ion excitation electrode A758, electrode 758 formed on the upper substrate 752) and ion excitation electrode B757 (electrode 757 formed on the lower substrate 753), receiver electrode A756- 2 (a conductor film 756-2 formed on the substrate side wall 751-4) and a receiver electrode B756-3 (a conductor film 756-3 formed on the substrate side wall 751-5). The side surfaces 751-2, 4, 5 of the main board and the board side wall 751-1 are the side surfaces of the main board substantially perpendicular to the board surface of the main board 751, the board surface of the upper board 752, and the board surface of the lower board 753. .. Therefore, the opposing trap electrodes A and B, the opposing receiver electrodes A and B, and the opposing ion excitation electrodes A and B are parallel plate electrodes. The outer electrodes 762 (762-1, 2, 3) and the external electrodes 762 (762-1, 2, 3) are passed through the inner wirings 759 (759-1, 2) and 764 (764-1, 2) or directly through the contact holes 760 and 761 to the respective conductor film electrodes. 763 (763-1, 2, 3) can be connected to apply a voltage from the outside or detect the current or voltage generated inside.

Ions 750-1 that have entered from the ion source chamber 754-1 through the central hole 765 of the substrate side wall 751-1 are trapped by the DC voltage applied between the opposing trap electrodes A and B, and the ions 750-1 are trapped by the trap electrode A 755-1, 3 to the trap electrode B756-1. The magnetic field B is applied in the direction perpendicular to the trap electrodes A and B, and the high frequency voltage (frequency ω) applied between the opposing ion excitation electrode A 758 and ion excitation electrode B 757 causes the ICR chamber 754- Ions 750-1 in 2 undergo cyclotron motion, forming a coherent population of ions. At this time, ω=k×(zeB/m) holds. Due to this ion cyclotron (ICR) motion, an induced current is generated between the receiver electrode A756-2 and the receiver electrode B756-3 for detecting the amount of ions. The frequency of each component of this induced current is the same as the frequency ω of ICR, that is, it is related to the mass m of the ion. This induced current is detected as a signal corresponding to time, and each signal is amplified, digitized, and Fourier-transformed to be converted into a spectrum with respect to the frequency. Since the FTICR of the present invention has a very small size, the external magnetic field B can be small and the electromagnet can be small. Further, even when a superconducting magnet is used, its size is small, so that the volume cooled to an ultralow temperature can be reduced. It can also be easily placed inside a small size coil.

Next, the process of the FT-ICR mass spectrometer of the type shown in FIG. 31 will be described. The main substrate 751 is divided, and the central hole 765 is formed by using the photolithography method and the etching method. Next, a window is opened in the main substrate 751 to be removed, and through holes 754 (754-1, 2) are formed. The through holes 754 (754-1, 2) are vertically etched by using the Bosch method or the DRIE method. When the main substrate 751 is a semiconductor substrate such as Si or a conductive substrate, an insulating film (on the peripheral surface of the substrate side wall 751-1 and the side surfaces (751-2, 3, 4, 5) of the main substrate 751 is formed so as not to cause a short circuit. (Not shown) is formed, conductor films 755 and 756 are laminated, and predetermined patterning is performed to form conductor film electrodes/wirings 755-1, 756-1, 2, 3 and the like. The photosensitive film can be formed by using a method of attaching or coating a photosensitive sheet, or an electrodeposition method, and the exposure can be performed by an oblique exposure method, an oblique rotation exposure method, an exposure method having a large depth of focus, or the like. The conductor film can be patterned by wet etching or dry etching. Conductor film electrode patterns 758, 759 (759-1, 2) and the like are previously formed on the upper substrate 752, and conductor film electrode patterns 757, 764 (764-1, 2) and the like are previously formed on the lower substrate 753. The formed and divided main substrate 751 is attached to the upper substrate 752 and the lower substrate 753. At this time, since the through holes 754 and the conductor film patterns are formed in the main substrate 751, the patterns of the upper substrate 752 and the lower substrate 753 are matched so as to match those patterns. It can be attached using an adhesive, or diffusion bonding, high temperature bonding or room temperature bonding can be used. If the main substrate 751 is a semiconductor substrate such as Si or a conductor substrate, and the upper substrate and the lower substrate are glass substrates, quartz substrates, sapphire substrates, alumina substrates, etc., electrostatic anodic bonding can be used.

Next, in order to securely connect the conductor film patterns on the upper and lower substrates to the conductor film patterns on the main substrate side, after that, the conductor films are laminated and re-patterned to make a connection, especially at the connection portion. A conductor film may be formed, or a conductor film may be laminated only on the conductor film pattern using a selective conductor film forming method such as a plating method or a selective CVD method. No patterning is necessary. An insulating film may be formed as a protective film after forming the conductor film pattern. Next, the divided main substrates 751 are attached to each other. In particular, the substrate side walls 751-1 and 3, 751-2, 4, 5 are aligned to align the through holes 754 (754-1, 2). This attachment can also use the method described above. When the main substrate 751 is a semiconductor substrate such as Si or a conductor substrate, electrostatic anodic bonding can be used by interposing a glass substrate or the like.

At this time, a glass substrate or the like to be sandwiched is also preliminarily formed with a portion such as a through hole and is attached while patterning. By repeating these several times, a through hole having a predetermined depth (height) can be formed. After that, contact holes 760 and 761 are formed in the upper substrate 752 and the lower substrate 753, and a conductor film is stacked in the contact holes (plating method, CVD method, PVD method, selective CVD method, conductor film paste coating method). Etc. can be laminated). Next, electrodes/wirings 762 (762-1, 2, 3 etc.), 763 (763-1, 2, 3 etc.) are formed in the contact holes 760, 761 of the upper substrate 752 and the lower substrate 753 or in predetermined places. To do. After that, a protective film or the like may be formed and a window may be opened. As a result, the electrodes 762-1, 763-2 are connected to the trap electrodes 755, 756-1, the electrodes 762-2, 763-1 are connected to the ion excitation electrodes 758, 757, and the electrodes 762-3, 763-3. Is connected to the receiver electrodes 756-2 and 756-3. The magnetic field B can be applied perpendicularly to the trap electrodes 755 and 756-1, and the ion excitation electrodes 758 and 757 and the receiver electrodes 756-2 and 756-3 can be exchanged with each other.

In the above process, the formation of the central hole 765 and the formation of the through hole 754 in the main substrate 751 are described as if they were formed by the main substrate alone. In particular, the formation of the through holes 754 and the formation of the conductor film do not take the base into consideration, so that the etching is easy (there is no need to consider overetching or stacking on the base). However, it is also possible to deposit the base substrate on the main substrate 751 and then perform the central hole, the through hole, the film stacking, and the patterning. In this case, the base substrate is removed after attaching the upper substrate and the lower substrate. Similarly, it is also possible to attach the upper substrate and the lower substrate to the main substrate 751 and then perform the central hole, the through hole, the film stacking, and the patterning. In this case, it is not necessary to remove the upper substrate and the lower substrate. Further, without forming the conductor film electrodes/wiring patterns 757, 758, 759, 764 which are previously formed on the upper substrate or the lower substrate, the upper substrate or the lower substrate is attached to the main substrate, and then the through holes are formed. Then, the insulating film and the conductor film are formed. Since the conductor film can be formed on the upper substrate and the lower substrate, the conductor film electrodes/wiring patterns 757, 758, 759, 764 may be formed. it can. Alternatively, by using the main substrate alone, a recess is formed in the portion of the main substrate where the conductor film electrodes/wiring patterns 757, 758, 759, 764 are arranged, and the conductor film electrode/ The upper substrate and the lower substrate on which the wiring patterns 757, 758, 759, and 764 are formed may be attached together to the main substrate, and then the through holes, the insulating film, and the conductor film may be formed. In this case, connection with the conductor film electrodes/wiring patterns 757, 758, 759, 764 of the upper and lower substrates is performed when the conductor film on the main substrate side is formed. Such a method of forming the conductor film electrode/wiring patterns 757, 758, 759, 764 on the upper substrate and the lower substrate in advance is performed by forming the conductor film electrode/wiring patterns 757, 758, 759, 764 with a thick and firm film. Since it can be formed, the reliability as an ion excitation electrode to which a high frequency voltage is applied can be enhanced.

FIG. 32 is a diagram showing a structure for increasing the size of the ICR chamber. This can also be applied when increasing the size of various penetration chambers of other mass spectrometers. The first main substrate 751 is formed with the through chambers 754-1 and 754-2, the substrate side wall (partition wall) 751-1 having the central hole 765 (765-1), and the like. The upper substrate 752 on the upper surface and the lower substrate 753 on the lower portion of the through chamber 754-2, which is the ICR chamber, are removed. This removal may be performed before the upper substrate 752 or the lower substrate 753 is attached to the main substrate 751 or may be performed after the attachment. Vertical etching is desirable for etching the portions of the upper substrate 752 and the lower substrate 753 corresponding to the ICR chamber. Conductor films 767 (767-1, 2, 3, 4) and 768 (768-1, 2, 3, 4) are laminated on the side surfaces of the hollowed-out upper substrate 752 and lower substrate 753. When these are a semiconductor substrate or a conductor film, an insulating film is formed to prevent a short circuit, and then a conductor film is formed. When a conductor film is also formed on the surfaces of the upper substrate 752 and the lower substrate 753, the conductor film on the surface is removed by using the photolithography method and the etching method, and the conductor film is formed only on the side surface of the cut-out portion. It is desirable to form.

When the upper substrate 752 and the lower substrate 753 are attached to the main substrate 751 and then the upper substrate 752 and the lower substrate 753 are hollowed out, after forming the through hole 754 of the main substrate 751, the through hole 754 is used as a mask (window) to form the upper substrate. 752 and lower substrate 753 can be etched. After that, an insulating film and a conductor film are formed, and by performing necessary patterning, a conductor film 767 (767-1, 2, 3, 4) is formed on the side surface of the hollowed-out portion of the upper substrate 752 and the lower substrate 753. , 768 (768-1, 2, 3, 4) patterns can be formed. At this time, the conductor film is also formed on the side surface around the through hole 754-2 of the main substrate 751. If necessary, a plating method or a selective CVD method may be used to form a thick conductor film, particularly at the connection portion. After that, the second lower substrate 773 is sequentially attached to the first upper substrate 752, the second lower substrate 773 thereunder is removed by etching from the cut-out portion, and the second main substrate 771 is further attached, The second main substrate 771 thereunder is removed by etching from the cut-out portion to form a through chamber 779, and a conductor film 774 (774-1, 2, 3, 4) is further formed on the side surface of the through chamber. .. Next, the second upper substrate 772 on which the pattern of the conductor film 776 (776-1, 2, 3, 4, 5) is already formed is attached, and the connecting portion of the conductor film is plated by a plating method, if necessary. The connection is ensured with a conductor film using the CVD method or the like. After that, a protective film may be covered on the conductor film inside the penetration chamber. Further, a contact hole 777 is formed in the second upper substrate, a conductor film is formed therein, and further a conductor film electrode/wiring pattern 778 (778-1, 2, 3, 5) is formed. Before the conductor film is laminated on the inner surface of the through chamber 779 of the second main substrate 771, the second upper substrate 772 is attached, and then the conductor film is laminated to form the conductor film pattern 774 (774-1, 774-1). 2, 3, 4) and a pattern of the conductor film 776 (776-1, 2, 3, 4, 5) may be formed.

The divided main substrate 751 side is also sequentially subjected to the same deposition, film formation, and pattern formation by the same process, the third upper substrate 782 is attached, the upper substrate 782 is subsequently subjected to hollow etching, and the third main substrate 781 is attached. A lower ICR chamber formed through processes such as formation of the through chamber 789, subsequent film formation and pattern formation, attachment of the third lower substrate 783, subsequent film formation, and patterning is formed. By attaching such two upper and lower ICRs, the FT-ICR mass spectrometer shown in FIG. 31 can be manufactured.

In the above, the substrates are sequentially attached, but it is also possible to produce the through chambers separately for each substrate and attach them. A through chamber 779 is formed in the second main substrate 771, the second lower substrate 773 is attached to the second main substrate 771, and the second lower substrate 773 is also hollowed out. The second upper substrate 772 also attaches to them. The conductor films 774 (774-1, 2, 3, 4), the conductor films 775 (775-1, 2, 3, 4), and the conductor films 776 (776-1, 2, 3, 4, 5) are also included. Form. This forming method is the same as the method used for the first main substrate 751, the first upper substrate 752, and the first lower substrate 753. The contact hole 777 of the second upper substrate 772, the conductor film formation therein, and the electrode/wiring pattern 778 (778-1, 2, 3, 4, 5) are formed in advance, and the second upper substrate 772 may be attached to the second main substrate 771. The through chamber 754 is hollowed out, and the upper substrate (first upper substrate) 752 on the upper side of the first main substrate (or the divided upper side) on which the conductor film pattern is formed on the inner surface thereof is also formed as the through chamber 779. It is attached to the second lower substrate 773 of the hollowed second main substrate 771. An adhesive, a room temperature bonding method, a diffusion bonding method, a high temperature bonding method, or the like can be used for the adhesion. When the first upper substrate 752 is an insulating substrate such as a glass substrate or quartz and the second lower substrate 773 is a semiconductor substrate such as a Si substrate or a conductive substrate, they can be attached by electrostatic anodic bonding. Alternatively, when the second main substrate 771 is a semiconductor substrate such as a Si substrate or a conductor substrate, the second main substrate 771 is attached to the first upper substrate 752 without using the second lower substrate 773, and the It can also be attached by electroanode bonding. When the protective film is used, the protective film on the conductor film at the connecting portion is removed. In the connection portion of the conductor film, for example, the connection portion of the conductor film 767 and the conductor film 775, in addition to increasing the size of the connection region or connecting the conductor film thick to increase the contact area, a plating method is also used. Alternatively, a selective CVD method, or further stacking and patterning of a conductor film can be performed. Further, heat treatment near the melting point is performed for fusion, a low melting point alloy (solder or the like) is plated or a selective CVD method, or the low melting point alloy (solder or the like) is laminated, and the portion of the conductor film pattern is again formed. There is also a method in which a low melting point alloy is attached by patterning and heat treatment is performed to assist the joining of the conductor films with the low melting point alloy.

Similarly, a through chamber 789 is formed in the third main substrate 781, the third upper substrate 782 is attached to the third main substrate 781, and the third upper substrate 782 is also hollowed out. The third lower substrate 783 also attaches to them. The conductor film 784 (784-1, 2, 3, 4), the conductor film 785 (785-1, 2, 3, 4), and the conductor film 786 (786-1) are also formed. This forming method is the same as the method used for the first main substrate 751, the first upper substrate 752, and the first lower substrate 753. The contact hole 787 of the third lower substrate 783, the conductor film formed therein, and the electrode/wiring pattern 788 (788-1) are formed in advance, and the third lower substrate 783 is formed on the third main substrate 781. It may be attached. Such a through chamber 754 is hollowed out, and the lower lower substrate (first lower substrate) 753 on the lower side of the first main substrate (or the divided lower side thereof) having the conductor film pattern formed on the inner surface thereof is also similarly penetrated into the through chamber. 789 is attached to the third upper substrate 782 of the hollowed third main substrate 781. The attachment method is also the same, and the connection between the conductor films is also the same. In addition, use both conductive and insulative adhesives, use conductive adhesives for the connecting parts of the conductor film, and insulative adhesives for the other parts. Can also These can be patterned and attached separately. Alternatively, a low melting point alloy or the like may be attached to the connecting portion of the conductor film and the other portion may be attached using an insulating adhesive. Alternatively, a conductive adhesive or a low melting point solder alloy may be attached to the conductor film portion, and the other adhesive portions may be bonded at room temperature, diffusion bonded, high temperature bonded, electrostatic anodic bonded, or the like.

Next, the upper side and the lower side are attached. The main substrates 751, 771, 781 are semiconductor substrates such as Si substrates or conductor substrates, and even if the transmittance of visible light is low, the first to third upper substrates and the first to third substrates are glass substrates or the like. If the material has a high transmittance to visible light, the through chamber 769 (collectively 754 of 754-2, 779, and 789) is free, so that accurate mask alignment is possible, and thus the variation is minimized. It is possible to attach the conductor films attached to the through chambers 754-2, 779, 789 and the inner surfaces thereof. After the attachment, a heat treatment, a plating method, a selective CVD method, or the like can be performed to reliably connect the conductor films. When visible light cannot be used, infrared rays, ultraviolet rays, etc. can be used for matching. In order to make the ICR chamber 769 have a predetermined low pressure, an opening for vacuuming can be provided in the second upper substrate 772 or the third lower substrate 783 and can be connected to a vacuum pump. An opening may be provided for cleaning or purging the inside. When the ion source chamber 754-1 has an atmospheric pressure or a relatively high pressure, a required number of intermediate chambers are provided between the ion source chamber 754-1 and the ICR chamber 769, and each of these chambers is provided. It is also possible to reduce the pressure stepwise to bring the ICR to a desired low pressure. In that case, an accelerating electrode or an extracting electrode (which may have a central hole) for accelerating the ions emitted from the ion source can be provided, or can be extracted by a pressure difference. As described above, the FT=ICR mass spectrometer having the ion source chamber 754-1, the ion introduction hole 765, and the wide ICR chamber 769 is completed.

In the ICR chamber 769, the conductor film electrodes 755 (755-1, 3), 756 (1, 3, 4), 767 (1, 2, 3, 4), 775 (1, 2, 3, 4), 774. (1, 2, 3, 4), 776 (2, 3, 4, 5), 768 (1, 2, 3, 4), 785 (1, 2, 3, 4), 784 (1, 2, 3) , 4), etc. are respectively connected to form a trap electrode 778 (778-2, 3) and a receiver electrode 778 (778-4, 5). Further, the conductor film electrodes 776 (776-1) and 786 (786-1) become the ion excitation electrodes (power sources) 778 (778-1) and 788 (788-1). In the FT-ICR using the substrate of the present invention, the two-dimensional (plane) direction can be increased to the same size as the substrate surface, but the height direction is limited by the substrate thickness. For example, when the main substrate is a Si substrate, the Si substrate has a thickness of about 1 mm, which is the maximum thickness that is normally used. Therefore, the maximum height is 1 mm, but the structure and method shown in FIG. 32 are used. By stacking the adhesion layers on top of each other, it is possible to fabricate an ICR chamber having a desired height. (In the case of a Si wafer, since any thickness can be used, for example, a wafer with a thickness of 1 cm to 10 cm can be manufactured. For example, the thickness of the first main substrate 751 is h4, the thickness of the first upper substrate 752 is h3, the thickness of the first lower substrate 753 is h5, the thickness of the second main substrate 771 is h1, and the second upper substrate is h1. If the thickness of 772 is h8, the thickness of the second lower substrate 773 is h2, the thickness of the third main substrate 781 is h7, the thickness of the third upper substrate 782 is h6, and the thickness of the third lower substrate 763 is h9, then the total thickness is Is the sum of h1 to h9, and the height of the ICR chamber 769 is the sum of h1 to h7. For example, if h1=h4=h7=1 mm and h2=h3=h5=h6=h8=h9=0.2 mm, then the total thickness is 4.2 mm and the height of the ICR chamber 769 is 3.8 mm. If h1=h4=h7=3 mm and h2=h3=h5=h6=h8=h9=0.5 mm, the total thickness is 12.0 mm and the height of the ICR chamber 769 is 11.0 mm. Incidentally, the through chamber having a considerably high height can be manufactured all at once by the substrate ingot method using a mold as described later.

The magnetic field B is directed from the trap electrode A755 to the trap electrode 756. In order to generate such a magnetic field B, there are two methods in the present invention. One is to arrange an electromagnet or a permanent magnet having an N pole on one side and an S pole on the other side of the trap electrode of the ICR chamber 754-2. As a result, a magnetic field B is generated from the trap electrode A 755 to the trap electrode 756 or to the excitation electrodes 757 and 758. The other method is to arrange the ICR chamber 754-2 inside the coil so that the axial direction of the coil coincides with the direction from the trap electrode A 755 to the trap electrode 756. FIG. 33 shows an FTICR in which the coil of the present invention is arranged. FIG. 33(a) is a view of the ICR chamber viewed in parallel with the traveling direction of the charged particles, and FIG. 33(b) is a cross-sectional view of the ICR chamber viewed from the traveling direction of the charged particles. A coil is wound around the outside of the ICR chamber of the FTICR device shown in FIG. That is, the contact wiring (coil wiring) 766-3 in the upper substrate 752 that is connected to the coil wiring 766 (766-1) is formed on the upper substrate 752, and is connected to this coil wiring 766-3. Main substrate coil wiring 766-4 is formed, contact wiring (coil wiring) 766-5 in the lower substrate 753 connected to the coil wiring 766-4 is formed, and further coil wiring connected to the coil wiring 766-5. 766 (766-2) is formed on the lower surface of the lower substrate 753. In this way, the coil wiring 766 spirally surrounds the periphery of the ICR chamber.

The coil wirings 766-1 and 766-2 can be formed together with the electrodes 762 and 763. For example, when the upper substrate 752 or the lower substrate 753 is an insulator, the SiO2 film, the SiN film or the SiNO film is directly formed on the upper substrate 752 or the lower substrate 753 when the upper substrate 752 or the lower substrate 753 is other than the insulator. After forming an insulating film such as the above, a conductor film is laminated and patterned. The conductor film is formed by a CVD method, a PVD method, a plating method, a squeegee method, a screen printing method, or a combination thereof. The contact wirings (coil wirings) 766-3 and 766-5 can be formed simultaneously with the contact hole wirings 760 and 761. For example, if contact holes are formed in the upper substrate 752 and the lower substrate 753 and then the upper substrate 752 and the lower substrate 753 are made of an insulator, the upper substrate 752 and the lower substrate 753 are made of a material other than the insulator directly. In some cases, an insulating film such as a SiO2 film or a SiN film is formed thereon, and then a conductor film is laminated and patterned. The conductor film is formed by a CVD method, a PVD method, a plating method, a squeegee method, a screen printing method, or a combination thereof. For example, by PVD method, after stacking 50 nm to 5000 nm, a photosensitive film is formed only inside the contact hole, then the entire surface is etched (anisotropic dry etching), and the photosensitive film in the contact is removed. A plating film is formed only in the contact by the plating method. Thereby, the coil wiring in the contact can be formed. Alternatively, the in-contact coil wiring can be formed by laminating a conductor film after forming the contact hole and further plating the entire surface. At this time, although it is also formed on the upper substrate 752 and the lower substrate 753, this conductor film can also be used as the coil wirings 766-1, 2.

Alternatively, the conductor film is formed thick after forming the contact hole. For example, when the contact hole is 200 μm, the inside of the contact hole is almost filled by stacking layers with a thickness of 100 μm or more. Although formed on the upper substrate 752 and the lower substrate 753, this conductor film can also be used as the coil wirings 766-1, 2. Alternatively, after forming the contact hole, a conductor film may be laminated and the inside of the contact hole may be filled with a conductor film (paste) by a squeegee method. At this time, if a gap is provided between the upper substrate 752 and the lower substrate 753, wiring can be formed on the upper substrate 752 and the lower substrate 753 at the same time. If the electrodes 762 and 763 cannot be formed at that location due to the coil wirings 766-1 and 762, they may be formed outside the coil wirings 766-1 and 2 as shown in FIG. If the contact wirings 760 and 761 cannot be formed at that place, they may be formed outside the coil wirings 766-1 and 762. Therefore, the electrode wirings 758, 757, 759, 764 and the like in the ICR chamber need only be routed to some extent. The coil wiring 766-4 in the main board can be formed by the same method.

34 is an FTICR in which the coil of the present invention different from that of FIG. 33 is arranged. In FIG. 34, the second upper substrate 792 is attached on the upper substrate 752 via the columns 791 (791-1, 2), and the second substrate 792 is attached on the lower substrate 753 via the columns 793 (793-1, 2). 2 The lower substrate 793 is attached, then the FTICR device is cut from the substrate, and the periphery of the ICR chamber is surrounded by the coil wiring 795. The electrodes 762 and 763 can be formed freely in the spaces 796 and 797 surrounded by the columns 791 and 793 and the second upper substrate 792 and the second lower substrate 794 regardless of the arrangement state of the coil 795. At the same time, the spaces 796 and 797 can be closed, so that they are not exposed to the external environment. Further, as the coil wiring 795, a commercially available wiring can be used, so that the wiring size can be arbitrarily set and the current to be flown can be freely selected. When the coil wiring 795 is covered with an insulating film, the upper substrate 752, the lower substrate 753, the main substrate 751, the columns 791 and 793, the second upper substrate 792, and the second lower substrate 794 which are in contact with the coil wiring 795 are made of an insulator. However, even if it is a conductor or a semiconductor, it need not be covered with an insulator film. The support 791 can be attached to the upper substrate 752 by various methods. For example, there is a method in which a substrate to be the pillar 791 is attached to the upper substrate 752 and then a through hole to be the space 796 is formed. When the substrate to be the pillar 791 is attached to the upper substrate 752, the electrode 762 has a convex portion. Therefore, a recess may be formed in this portion of the substrate to be the pillar 791 in advance and then to be attached. After forming the space 796, the second upper substrate 792 is attached.

Alternatively, after the substrate to be the pillar 791 is attached to the second upper substrate 792, the through hole to be the space 796 is formed, and then the pillar 791 attached to the second upper substrate 792 while being aligned is attached to the upper substrate 752. To do. Alternatively, a through hole that becomes the space 796 is formed in the substrate that becomes the pillar 791, and the pillar 791 is attached to the upper substrate 752 and the second upper substrate 792. Similarly, the pillar 793 and the second lower substrate 794 are attached to the lower substrate 753 side. In addition, openings are provided in the upper substrate 752, the lower substrate 753, the second upper substrate 792, and the first upper substrate 794 for purging or cleaning in order to reduce the pressure in the ICR chamber and the like. Further, the electrodes 762 and 763 are stretched so that a voltage can be applied from the outside. After that, the substrate is cut in order to manufacture the FTICR device in units. The substrate can be cut by a dicing method, a wire saw method, a laser cutting method, or the like. The scribe line part can be easily cut at the last dining if the board is shaved thin in each process. Then, if necessary, an insulating film or the like is formed on the outside of the device, and the coil wiring 795 is wound around the ICR chamber. In order to obtain the required magnetic field, the diameter of the coil wiring, the material of the coil, the number of turns, and multiple turns are selected. Since the ICR device of the present invention is very small, the coil material can be made of a superconductor. Since the size of the container containing the liquid He or the like for containing the apparatus itself can be reduced, the running cost and the manufacturing cost can be made very low. As the superconductor, a Nb-based or Mg-based metal superconductor, a high-temperature superconducting material such as a copper oxide, or an iron-based superconductor can be used.

In the case of the structure shown in FIG. 33, as in the case of FIG. 34, after the FTICR device is manufactured, the electrodes 762 and 763 can be removed and the coil wiring can be wound so as to surround the ICR chamber. If the ICR chamber is 10 mm×40 mm and the size of the entire apparatus is 15 mm×60 mm, 12 pieces can be taken from a 6 inch wafer (150 mm diameter). If the material + manufacturing cost is 240,000 yen, the price of one piece will be 20,000 yen, and the conventional product will be 2.4 million yen or more, so the size and cost will be 1/100. In FIG. 33 and FIG. 34, the coil wiring is wound around the substrate. However, a coil is prepared so that the ICR device as shown in FIG. 31 can be placed inside, and the coil axis and the direction of the ICR chamber are aligned in the coil. It may be placed in. However, at this time, the coil wiring and the ICR device do not come into close contact with each other, and in some cases the coil wiring is separated from the ICR device, so that the entire size including the coil becomes larger than that shown in FIGS. 33 and 34. ..

FIG. 35 is a diagram showing an ionization method different from that described in FIG. This ionization method is a kind of matrix-assisted laser desorption/ionization method. Through holes (chambers) 454, 455, 456, 457 and the like formed in the main substrate 451 are formed, and the through holes (chambers) 454 are partition walls 451-having a thick main substrate body 451-1 and a central hole 481-1. Surrounded by two. (The side surface is surrounded by the main substrate 451.) This through hole (chamber) 454 is a sample chamber, and the second substrate (upper substrate) 452 or the third substrate (lower substrate) 453 is used for sample insertion. An opening 470 is vacant, and a sample plate (sample plate) 475 is inserted through the opening 470 and is applied to the sample back plate 451-1 of the main substrate 451. An evacuation line 468 is vacant in the sample back plate 451-1 and an opening is formed in the upper substrate 452 or the lower substrate 453 so that the sample back plate 451-1 can be connected to a vacuum pump to adsorb the sample plate 475. A sample 476 is attached to the central portion of the sample plate 475, and the sample 476 is irradiated with laser light 478 from an opening 471 opened in the upper substrate 452 or the lower substrate 453. The laser beam 471 guides the laser beam 478 from the outside, condenses it with the lens 477, and irradiates the sample 476. The laser beam 478 causes a rapid temperature rise of the sample 476, and the sample substance (matrix) is vaporized and ionized. It is also possible to form a through chamber next to the sample chamber 454 (lateral side, vertical to the drawing) and irradiate the laser beam from the through chamber.

A conductor film 459 is formed around the main substrate partition wall 451-2 facing the main substrate 451-1 of the sample back plate on which the sample plate 475 is leaned, and the conductor film 459 is formed on the upper substrate 452 or the lower substrate. It is connected to the contact hole 462 formed in 453, the conductor film formed there, and the external electrode/wiring 464 formed on the upper substrate 452 or the lower substrate 453 connected thereto. When a voltage is applied to the external electrode/wiring 464, a positive or negative voltage is applied to the conductor film 459. The generated ions are extracted by the voltage of the conductor film (the conductor film 459 is also referred to as an extraction electrode), and a part thereof passes through the central hole 481-1 and enters the adjacent low pressure chamber 455, and further, the main substrate. It passes through the central hole 481-2 of the partition wall 451-3 and enters the ion focusing chamber 456 adjacent thereto, and further passes through the central hole 481-3 of the main substrate partition wall 451-4 to the adjacent through hole 457. Get burned. This through hole 457 is, for example, the extraction electrode and the acceleration chamber 307 or the mass spectrometry chamber 308 in FIG.

Since the sample chamber 454 is in an atmospheric pressure state, the adjacent chamber 455 is, for example, a low pressure chamber 455 of about 1 torr and is lowered by a vacuum pump connected to the opening 472 for vacuuming formed in the upper substrate 452 or the lower substrate 453. To be pressured. A conductor film 460 is formed on the inner surface of the adjacent chamber 456. The conductor film 460 includes the contact hole 465 formed in the upper substrate 452 or the lower substrate 453, the conductor film formed there, and It is connected to the external electrode/wiring 466 formed on the upper substrate 452 or the lower substrate 453 to be connected. A voltage is applied to the conductor film 460 from the external electrode/wiring 466, but a voltage having the same sign (positive or negative) as that of the ion beam 479 is applied to focus the ion beam 479. If the conductor film 460 is divided into several regions so that a voltage can be applied to each region, the orbit can be adjusted while focusing the ion beam 479 by adjusting those voltages. .. Therefore, since the position of the ion beam entering the adjacent chamber 457 can be adjusted, the ion beam can be more accurately passed through the central hole 481-3, and further, the ion beam 479 can be almost guided to the mass analysis chamber, and ion detection sensitivity can be improved. Can be increased. Also in the ion focusing chamber 456, an opening 473 for a vacuuming line is formed in the upper substrate 452 or the lower substrate 453, so that the inside of the ion focusing chamber 456 can be evacuated to a low vacuum. For example, the pressure of the ion focusing chamber 456 is 10 ⁻³ to 10 ⁻⁴ torr. (Note that the mass spectrometric chamber is, for example, 10 ⁻⁵ to 10 ⁻⁶ torr.) Since the conductor film 459 faces the sample plate 475 in FIG. 35, ions are attracted to the electrode of the conductor film 459. In such a case, the electrode is divided in such a case, and the voltage applied to the electrode in the vicinity of the central hole is increased so that ions are not attracted to the electrode facing the sample plate 475. Is also good. Alternatively, a voltage having the same polarity as that of the ions may be applied to the electrode facing the sample plate 475 to repel the ions, and most of the ions may be directed to the electrode side of the central hole. Alternatively, the part of the conductor film facing the sample plate 475 may be removed. In that case, the external electrode 464 and the like may be provided in the low-pressure chamber adjacent to the sample chamber 454. Alternatively, a partition without an electrode having a central hole may be placed in front of the partition electrode 451-2 and ions can be extracted by a pressure difference. At that time, the ions may be pushed out by applying a voltage having the same potential as the ions applied to the conductor film 458 formed on the side surface of the sample back plate 451-1.

A conductor film 458 may be formed on the side surface of the sample back plate 451-1 of the main substrate. The conductor film 458 includes a contact hole 461 formed in the upper substrate 452 or the lower substrate 453, a conductor film formed therein, and an external electrode formed on the upper substrate 452 or the lower substrate 453 connected thereto. -Connected to wiring 463. The sample plate 475 is a conductor, and a voltage is applied from the conductor film 458. When the sample 476 is irradiated with the laser beam 478, various ions are generated, but ions having the same potential as the voltage applied to the sample plate 475 jump out from the sample. When a voltage opposite to the voltage of the sample plate 475 is applied to the conductor film 459, most of the ions having the same sign as the voltage of the sample plate 475 are attracted to the conductor film 459 and pass through the central hole 481-1.

Since the ion irradiation generates heat, the sample chamber 454 becomes hot. Therefore, a recess 469 is formed in the vicinity of the sample back plate of the main substrate wall 451-1 on which the sample plate is leaned, and the recess 469 is cooled. For this cooling, for example, cooling water or cooling gas can be used. Further, it is possible to form a similar concave portion around the sample chamber 454 for cooling, and it is also possible to perform cooling from the side of the upper substrate 452 and the lower substrate 453. Since the conductor film 458 is also a good conductor of heat, the heat of the sample plate 475 can be effectively absorbed. Particularly, since the sample plate 475 is in close contact with the conductor film 458 by the vacuum line 468, electrical connection and heat transfer are also improved.

FIG. 36 is a diagram showing another embodiment of the ionization method. The upper substrate (second substrate) 502 and the lower substrate (third substrate) 503 are attached to the upper and lower surfaces of the main substrate (first substrate) 501, and the upper substrate (second substrate) 502 to the lower substrate (second substrate) 502 are attached to the main substrate 501. (Three substrates) 503 are formed with penetrating chambers 504 (504-1, 504-2, 504-3). 504-1 is an ionization chamber, and a spray gas introduction line 516 for introducing a spray gas is connected to the ionization chamber 504-1. Next to the ionization chamber 504-1 is an extraction electrode/acceleration chamber 504-2, which is separated by a substrate partition wall 501-2 having a central hole 505-1. The extraction electrode/acceleration chamber 504-2 is a penetration chamber separated by a substrate side wall 501-2 having a central hole 505-1 and a substrate partition wall 501-4 having a central hole 505-2 separated from an adjacent chamber 504-3. is there. In the extraction electrode/acceleration chamber 504-2, a substrate side wall 501-3 serving as an extraction electrode having a central hole 505-3 is arranged. A conductor film electrode wiring 508 is formed on the surface of the substrate side wall 501-3, and the conductor film electrode wiring 508 is also formed on the upper surface of the lower substrate 503, and is provided on the lower surface of the lower substrate 503 through the contact 510 of the lower substrate 503. It is connected to the formed outer electrode 511. Spray gas is the gas that contains what is to be analyzed.
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When the spray gas introduction line 516 is formed near the center of the main substrate 501, the spray gas introduction line 516 can be manufactured by the same process as the central hole 505. However, when the size is different from that of the central hole 505, photolithography and etching may be performed separately. The spray gas introducing line 516 is connected to the spray gas introducing opening 518 opened in the upper substrate 502 or the lower substrate 503 through another spray gas introducing line 517. After opening the spray gas introduction opening 518 by a photolithography method+etching method or the like, the main substrate 501 can be subsequently etched using the opening portion as a mask to form the spray gas introduction line 517. The spray gas introduction line 517 may be formed in the main substrate 501 in advance and/or the spray gas introduction opening 518 may be formed in the upper substrate or the like, and then the upper substrate or the like may be attached to the main substrate. Alternatively, an opening may be formed in the upper substrate 502 or the lower substrate 503 and the opening may be used as a spray gas introduction line.

A spray gas containing a sample liquid or a sample gas (also referred to as an atomizing gas or a nebulizer gas) is introduced from a spray gas introduction opening 518, and a spray gas 525 is introduced into the ionization chamber 504-1. A conductive film 506 is formed on the inner surface of the ionization chamber 525, and the conductive film 506 has a contact hole 512 (upper substrate 502 side) and/or a contact hole 510 (lower substrate 503 side) formed in the conductive film. The body film, the electrode/wiring 513 (upper substrate 502 side) and/or the electrode/wiring 511 (lower substrate 503 side) connected thereto are connected, and a voltage is applied from these electrodes/wiring 511 and 513 to the conductor film 506. Can be applied, and the spray gas 525 introduced into the ionization chamber 525 can be ionized into ions having the same sign as the applied voltage. The conductor film 509 on the upper substrate 502 or the lower substrate 503 may be formed before being attached to the main substrate 501, that is, after the conductor film 509 is formed on the upper substrate 502 or the lower substrate 503, the penetrating film may be formed. The main substrates 501 having holes or recesses may be attached together. Similarly, the conductor film 509 on the side surface of the main substrate may be formed on the side surface of the main substrate 501 having a through hole or a recess, and then attached to the upper substrate 502 or the lower substrate 503 and the main substrate 501. It is also possible to divide the main substrate 501 into two or more parts, separately form the upper substrate 502 side and the lower substrate 503 side, and attach them together. A conductor film 526 can be formed on the inner surface of the spray gas introduction line 516 and a voltage can be applied thereto. In that case, since the spray gas is ionized also in the spray gas introduction line 516, the ionization can be performed more efficiently. As a method of forming the conductor film 526 also on the inner surface of the spray gas introduction line 516, the main substrate 501 is divided and half of the recesses 516 are formed therein, as described in this specification, and then, A conductor film 526 may be formed on the surface of the concave portion 516, and the upper and lower portions may be bonded together. A conductor film can also be formed on the inner surface of the spray gas introduction line 517.

As a forming method, for example, after forming the spray gas introduction line 517, the conductor film can be formed by the CVD method, the PVD method, or the plating method. Incidentally, these conductor films are, for example, conductor films such as Cu, W, Mo, Ni, Cr, Al, Au, Ti, high-concentration poly-Si, conductive carbon (including conductive nanotubes and graphene), Alternatively, it is a composite film or a laminated film of these. A high voltage (for example, 100 V to 10 KV) is applied to the ionization chamber 504-1 to generate ions, and thus heat is also generated. The main substrate 501 is, for example, silicon or the like, and the upper substrate 502 or the lower substrate 503 is, for example, glass or quartz. The conductor film and the insulating film can have a temperature of 300° C. or higher without any problem, but this high temperature causes the mass analysis chamber. It is desirable to prevent the temperature from rising as much as possible, because the characteristics will be affected if it is transmitted to the. Since this mass spectrometer is small, it is easy to cool the whole by applying cold air, but it is particularly desirable to cool only the part that becomes hot. Since the ionization chamber 504-1 and the like become relatively hot, a recess 519 is formed in the main substrate 501 around the ionization chamber 504-1 and the like, and cooling water and cooling water are introduced into the recess 519, and the ionization chamber 504-1 and the like. Can be cooled. The recess 519 may be formed by forming an opening 521 in the upper substrate 502 or the lower substrate 502 and etching the main substrate 501 from the opening 521. Alternatively, after forming the recess 519, the upper substrate 502 or the lower substrate 502 is formed. The opening 521 may be formed on the main substrate 501 in advance, or may be formed after the attachment.

It is also possible to apply a high frequency voltage to the electrode 513 or 511 to plasmaize (ionize) the gas present in the ionization chamber 504-1. At this time, plasma can be formed even at a low pressure below atmospheric pressure (for example, 1 torr to 100 torr). You can also Alternatively, a high voltage (for example, 100 V to 10 KV) is applied between the conductor film 508 of the extraction electrode partition wall 501-3 and the conductor films 506 and 509 in the ionization chamber 504-1, and the ionization chamber 504- It is also possible to ionize the gas and mist inside 1. In this case, it is desirable that the partition wall 501-2 is not provided. In the case of FIG. 36 as well, like the case of FIG. 37, the conductor films 506 and 509 can be used as heaters. In that case, a high voltage can be applied between the extraction electrode side and the heater side conductor films 506 and 509 to ionize the gas or mist in the ionization chamber 504-1.

Ions ionized in the ionization chamber 504-1 are extracted by the substrate side wall 501-3 having the central hole 507 formed in the adjacent chamber across the partition wall 501-2 having the central hole 505-1, and pass through the central hole 507. Further, the ion beam 528 travels through the central hole 505-2 of the partition wall 501-4 having the central hole 505-2 to the penetrating chamber 504-3 of the adjacent chamber. A contact hole 510 and an electrode/wiring 511 are formed in the conductor film 508 in the extraction electrode/acceleration chamber 504-2, and a voltage can be applied from the outside. For example, when a potential opposite to that of the ions is applied, the ions are extracted and accelerated, and become an ion beam 528 that passes through the central hole 507. The extraction electrode/acceleration chamber 504-2 may be further provided with an acceleration electrode (having a central hole) or a focusing electrode. Further, the ion focusing chamber 456 of FIG. 35 may be provided before and after the extraction electrode/acceleration chamber 504-2 to focus the ions. The adjacent room 504-3 is, for example, a mass spectrometry room (308 in FIG. 19). The partition wall 501-2 between the ionization chamber 504-1 and the extraction electrode/acceleration chamber 504-2 may be omitted if there is no problem when extracting the ions with the extraction electrode 501-3. For example, when generating positive ions, a positive voltage is applied to the conductor films 506 and 526, but the generated positive ions are focused near the center by the positive voltage applied to the conductor film 506 of the ionization chamber 504-1. To be done. The focused positive ions are extracted by the extraction electrode 501-3 applied with a negative voltage. At this time, the size of the central hole 505-1 of the partition wall 501-2 is adjusted to facilitate the extraction by the extraction electrode 501-3. For example, the size of the central hole 505-1 can be made smaller than that of the central hole 507 so that the extraction electrode 501-3 can easily pass through the central hole 505-1. Although the pressure in the ionization chamber 504-1 is near atmospheric pressure, the pressure in the extraction electrode/acceleration chamber 504-2 can be lowered by the partition wall 501-2. For example, the evacuation line 522 (522-1) can be provided between the partition wall 501-2 and the partition wall 501-3 of the extraction electrode to evacuate.

The method described in FIG. 36 is a type of electrospray method (ESI). Since the electrospray method (ESI) is an atmospheric pressure ionization method, the ionization chamber 504-1 is in an atmospheric pressure state. You may exhaust it to the extent that it does not affect. Further, the ionization chamber 504-1 can be cleaned by providing another opening and purging with nitrogen or drying. The chamber on the right side of the extraction electrode/acceleration chamber 504-2 (between the partition wall 501-3 and the partition wall 501-4) is provided with a vacuuming line 522 (522-2) to evacuate.

In FIG. 36, the upper electrode 509 and the lower electrode 506 are separated, and a conductor film electrode is not formed on the side surface to form a so-called parallel plate type electrode, and a high frequency voltage is applied between the upper electrode 509 and the lower electrode 506. By applying, plasma is generated and the spray gas 525 injected from the central hole 516 is ionized. In particular, when the distance between the upper electrode 509 and the lower electrode 506 is as small as 500 μm to 1 mm to 2 mm, a high electric field is generated between the upper electrode 509 and the lower electrode 506, so that plasma is easily generated. When the distance between these electrodes is 2 mm or more, plasma is generated by increasing the magnitude of the high frequency voltage accordingly. If the upper electrode 526 and the lower electrode 526 formed on the inner surface of the central hole 516 are separated to form parallel plate electrodes, the distance between these electrodes is the electrode 509 formed on the upper substrate 502 and the electrode 506 formed on the lower substrate 503. Less than the distance between. If the upper electrode 526 and the lower electrode 526 formed on the inner surface of the central hole 516 and separated, the electrode 509 formed on the upper substrate 502 and the electrode 506 formed on the lower substrate 503 are connected at the side surface, the inner surface of the central hole 516 is formed. By applying a high-frequency voltage between the upper electrode 526 and the lower electrode 526 that have been formed and separated, plasma can be generated in the central hole with a smaller voltage. Since the inside pressure of the through chamber 504-1 can be set to a low pressure, it is easy to set the conditions under which plasma can be generated.

FIG. 37 is a diagram for explaining the atmospheric pressure chemical ionization method. The same materials and the like as those in FIG. 36 are denoted by the same reference numerals. A place where the spray gas 525 enters is a heating chamber 504-6, and next to the heating chamber 504-6, there is an ionization chamber 504-7 via a partition wall 501-6 having a central hole 505-1. Conductor films 506 and 509 are laminated on the inner surface of the heating chamber 504-6. These conductor films 506 and 509 are thin-film resistors, and electrodes 511-1 and 511-2 (contact holes 510-1 and 510-2) and electrodes 513-1 and 513-2 sandwich the resistors. (Contact holes 512-1, 512-2) are connected. When a current is passed between the electrodes 511-1 and 511-2 and/or between the electrodes 513-1 and 513-2, the thin film resistor 509 generates heat. The heating chamber 504-6 is heated to, for example, about 300 to 500° C., the spray gas 525 is vaporized into the solvent and sample molecules, and enters the ionization chamber 504 through the central hole 505-1. (There may be no substrate side wall 501-6) If a thin film resistor 526 is also formed in the spray gas introduction lines 516 and 517 and a current is passed to generate heat, the vaporization efficiency of the spray gas 525 to the solvent and sample molecules is further increased. Will get better.

In the ionization chamber 504-7, electrodes (pointed electrodes) 529 and 530 having sharp tips (thinned tips) are arranged to face each other. The electrode 529 is arranged on the lower substrate 503 side and is connected to the external electrode/wiring 511-3 through the contact hole 510-3. The electrode 530 is disposed on the upper substrate 502 side and is connected to the external electrode/wiring 513-3 through the contact hole 512-3. When a voltage is applied between them, a discharge occurs, the vaporized solvent molecules are ionized and become reaction ions, proton exchange occurs between the reaction ions and the sample molecule (ionization reaction), and the sample molecule is protonated or deprotonated. It becomes separated and becomes an ion. These ions pass through the central hole 505-2 of the partition wall 501-4 and are extracted to the extraction electrode arranged in the adjacent chamber 504-8. That is, the adjacent chamber 504-8 is an extraction electrode/acceleration chamber and is similar to the extraction electrode/acceleration chamber 504-2 in FIG. As a result, the ion beam 528 is introduced into the mass spectrometry room or the like. Since the temperature of the heating chamber 504-6 and the ionization chamber 504-7 rises, a recess 519 is formed in the main substrate 501 around them so that the heat from these chambers does not pass to the outside through the cooling water or the cooling gas. It is desirable to do. In FIG. 37, the outlet of the spray gas introduction line 516 is described as facing the central hole 505-1 of the partition wall 501-6 and the spire electrodes 529 and 530, but the mist that does not vaporize is the ionization chamber 504-7. In order to prevent the electric field voltage of the ionization chamber from decreasing due to the entry into the electrode or the attachment to the pinnacle electrodes 529 and 530, the side surface of the heating chamber 504-6 (for example, the paper surface in FIG. It is desirable to install it on the front or back side. In addition, a discharge port for mist or gas may be provided in the upper and lower substrates 502 or 503 of the heating chamber 504-6, or a small amount of gas may be exhausted by a pump from there. Further, at the time of maintenance, the discharge port may be used to perform purging including drying with N2 or the like. Further, the ionization chamber 504-7 may be similarly provided with an exhaust port and an opening for purging and vacuuming.

The method of forming the steeple electrodes 529 and 530 will be described below. FIG. 38 is a diagram showing a method for manufacturing an ionization chamber having a steeple electrode. As shown in FIG. 38A, the photosensitive film 543 is patterned in order to reduce a part of the main substrate 541 having the thickness h25 attached to the lower substrate 542 to the thickness h26. Between the main substrate 541 and the photosensitive film 543, the adhesion of the photosensitive film 543 may be enhanced, or a film serving as an etching stopper (for example, an insulating film such as SiO 2) may be laminated. Using the pattern 543 as a mask, a recess 544 having a thickness h26 of the main substrate 541 is formed. (FIG. 38B) Next, the photosensitive film 545 (545-1) for forming the substrate side wall 541-1 of the main substrate 541 having a thickness of h25 is patterned. At the same time, patterning is performed on the photosensitive film 545 (545-2) for leaving the main substrate in the recess 544 where the spire 541-3 is formed. (FIG. 38C) The main substrate 541 is etched using the photosensitive film 545 (545-1, 2) as a mask to form a through hole 546 penetrating the lower substrate 542. When the main substrate 541 is a Si substrate and the lower substrate is a glass substrate or a quartz substrate, they can be firmly attached by electrostatic anodic bonding, and even if the Si substrate is etched at a high speed in a nearly vertical direction, overetching It is possible to select a dry etching condition in which the glass substrate 542 is not so much etched. By this etching, the substrate partition wall 541-1 having a thickness h25, the unetched main substrate 541, and the main substrate 541-2 of the portion where the spire electrode 541-3 is to be formed are formed. (Fig. 38(d))

Next, the photosensitive film 547 is patterned, and the photosensitive film 547-1 is patterned on a portion such as the substrate side wall 541-1 where the main substrate 541 should not be etched. At this time, in order to prevent the side surface of the substrate side wall 541-1 from being etched, the side surface of the substrate side wall 541-1 is also covered with the photosensitive film 547-1. At the same time, the photosensitive film 547-2 for forming the steeple electrode 541-3 is patterned on the main substrate 541-2 in the portion where the steeple electrode 541-3 is to be formed. (FIG. 38E) The main substrate 541-2 is etched by using the photosensitive film 547-2 as a mask. This etching is etching that also performs side etching. The side etching amount and the vertical etching amount are controlled under the controlled conditions. In this side etching method, the side etching amount becomes h27 when the vertical etching amount h26 is performed. Therefore, if the width (diameter) of the photosensitive film 547-2 is set to 2×h27 and h27=h26, the main substrate 541-3 is vertically etched by h26 and the lower substrate 542 is exposed. 3 has a conical shape with a steeple tip. {Fig. 38(f), (g)}

Next, as shown in FIG. 38(h), a conductor film is laminated and patterned, and as shown in FIG. 38(h), a conductor film pattern 548 covering the entire conical main substrate 541-3 and the conductor film pattern 548 connected thereto and extending on the lower substrate. A wiring pattern 549 is formed. The wiring pattern 549 is connected to the conductor film electrode/wiring 551 formed on the lower surface of the lower substrate 542 through the contact hole 550 formed in the lower substrate 542 and the conductor film formed therein. A similar pattern is also formed on the upper substrate 540 side, and as shown in FIG. 38I, the substrate sidewall 552 (552-1) on the upper substrate 540 side and the substrate sidewall 541 (541-1) on the lower substrate 542 side. When it is overlapped with, the ionization chamber where the conical steeple electrodes face each other can be formed. It goes without saying that not only the substrate side wall 552 (552-1) and the substrate side wall 541 (541-1) are superposed, but also the main substrates 552 and 541 formed at the same height are superposed. As described in this specification, the main substrates 552 and 541 can be attached to each other by various methods such as a method using an adhesive, room temperature bonding, diffusion bonding, high temperature bonding, and electrostatic bonding. Particularly, when the main substrate is a Si substrate or a conductor substrate, a glass substrate or a quartz substrate 553 can be sandwiched between the substrates to firmly attach them using electrostatic anodic bonding.

In FIG. 38, a pair of pinnacle electrodes is shown, but by providing a plurality of pairs of pinnacle electrodes, the discharge region can be increased, so that the ionization efficiency is increased. Since it is necessary to overetch the main substrate 541-2 to some extent when manufacturing the steeple electrode, the height h27 of the steeple electrode varies to some extent when the perfectly sharpened steeple electrode is smaller than h26. Therefore, the distance between the tips of the pinnacle electrodes after the upper and lower substrates are attached varies slightly, and the discharge voltage also varies, but since voltage can be applied individually to each electrode, even when multiple pinnacle electrodes are formed, the voltage By changing the value, stable discharge can be performed.

In FIG. 38, the upper substrate or the lower substrate is attached to the main substrate and then the steeple electrode is formed using the main substrate. However, the steeple electrode is attached to the upper substrate or the lower substrate by holding the front substrate and then the recess is formed. It is also possible to attach the main substrate to produce the state shown in FIG. In this case, the entire steeple electrode can be used as a conductor electrode, and an electrode resistant to high voltage can be manufactured. Further, the upper substrate or the lower substrate is attached to the main substrate, and the main substrate in the region where the steeple electrode is to be formed is completely removed by etching (that is, a complete penetrating chamber in FIG. 38B). It is also possible to attach the pinnacle electrode in place with a mounting device. When the entire steeple electrode is a conductor, the contact holes can be formed in the upper and lower substrates directly below the steeple electrode, so that the conductor films 548 and 549 need not be formed. Further, it is also possible to directly form the steeple electrode and adjust the height h27 of the steeple electrode during side etching without forming the recess 544 as shown in FIG. 38(b). In particular, when the facing surface is not a spire electrode but a parallel plate electrode, it is effective because the distance between the spire electrode and the parallel plate electrode can be made relatively large. Further, the main substrate of h26 is first used to form a steeple electrode and the side wall of the substrate (the height at this time is smaller than h25), and another main substrate having a height necessary for the portion to be attached later such as the side wall of the substrate or a substrate such as glass. Can be attached to realize a structure as shown in FIG.

In FIG. 38, the spire electrodes are formed on the upper and lower substrates, but even if one of them is a parallel plate electrode, discharge (corona discharge or the like) can be performed to ionize the vaporized gas. In this case, the parallel plate electrode can be formed on the upper substrate or the lower substrate like a conductor film 549 shown in FIG. 38(h), but a conductor film pattern can be formed on the upper substrate or the lower substrate in advance. It is possible to attach a plate electrode and then attach it to a main substrate having a through hole, and then attach a lower substrate side and an upper substrate side as shown in FIG. 38(f). In this case, the person who forms the steeple electrode can also form a plurality of steeple electrodes.

In FIG. 37, the ions generated in the ionization chamber 504-7 enter the adjacent chamber 504-8, but the adjacent chamber 504-8 is, for example, the extraction electrode chamber, and the ions 528 generated by the extraction electrode are pulled. However, since the ionization chamber 504-7 is partitioned from the adjacent chamber 504-8 by the substrate side wall plate 501-4 having the central hole 505-2, the ion extraction force is not so strong. Therefore, a conductor film electrode is formed on the side wall of the main substrate on the side facing the substrate side wall plate 501-4, and a voltage having the same sign (positive or negative) as the ions to be put into the adjacent chamber 504-8 is applied and generated. Ions can be pushed out and ions having a desired sign can be emitted to the adjacent chamber 504-8. In FIG. 37, it is the substrate side wall plate 501-6 that faces the substrate side wall plate 501-4, but the conductor film formed on the side surface of the substrate side wall plate 501-6 due to the central hole 505-1. Since the area of is small, the force to push out the ions may be weak. Alternatively, when the substrate side wall plate 501-6 is not provided, the facing surface is the substrate side wall 501-1, but since the distance is too large, the force for pushing out the ions becomes weak. Therefore, the position of the adjacent chamber 504-8 is not arranged on the opposite side of the substrate side wall plate 501-6, but for example, the relationship between the adjacent chamber 504-8 and the substrate side wall plate 501-6 is set to a 90-degree positional relationship. Then, the facing surface of the adjacent chamber 504-8 is the side wall of the substrate (in the ionization chamber 504-7, the position is perpendicular to the paper surface in FIG. 37), and the conductive film electrode is formed on the entire side surface of the side wall of the substrate. Therefore, the force for pushing out the ions is sufficient, and most of the generated ions enter the adjacent chamber 504-8.

In FIG. 19, the solid sample is irradiated with ions to generate ions and neutral particles. (In this case, if ionization is sufficient, laser irradiation or the like is not always necessary. FIG. 39 shows an embodiment in which continuous flow (CF)-FAB ionization, which is a type of fast atom bombardment method (FAB), is applied to the present invention. The main substrate 561 is attached to the upper substrate 562 and the lower substrate 563 to form penetration chambers 564-1, 564-2, 564-3, etc. Penetration chambers 564-1 and 564-2. Are separated by a substrate side wall 561-3 having a central hole 565-1, and the through chambers 564-2 and 564-3 are separated by a substrate side wall 561-10 having a central hole 565-4. Is an ionization chamber, and a sample introduction hole 566 is formed in the center of the substrate side wall 561-1 on the side surface side thereof, and a vertical direction sample introduction hole 567 connected to the sample introduction hole 566 is formed. It can be formed by the same method as that of 565-1 etc. The vertical sample introduction hole 567 has an opening 568-1 formed in the upper substrate and is connected thereto.

The component to be detected enters the ionization chamber 564-1 together with the mobile phase from the sample introduction opening 568-1 through the vertical sample introduction hole 567 and the sample introduction hole 566. As the mobile phase, for example, an organic solvent or organic solvent/water to which a highly viscous liquid (matrix) such as glycerin is added so as to have a concentration of 0.1 to several% is used. At the outlet portion 573 of the sample introduction hole 566, the organic solvent and water are volatilized, and the matrix exudes to the side surface of the substrate at the outlet portion 573 of the sample introduction hole 566 in a state where the components to be detected are dissolved. At this time, the components to be detected are concentrated in the matrix due to vaporization of the solvent or the like. The upper substrate of the ionization chamber has an opening 568-2, and the FAB gun 570 placed on the opening 568-2 irradiates the matrix 574 with a neutral high-speed atomic beam 571 such as Xe or Ar accelerated to several kV. To be done. The kinetic energy of these fast atoms ionizes the matrix, solvent molecules remaining without volatilization, and the transfer of protons and electrons between the ions and the component to be detected. As a result, positive and negative ions of the component to be detected are generated. The generated ions enter the extraction electrode/acceleration chamber 564-2 adjacent to the ionization chamber 564-1, are accelerated and focused, and are guided to the adjacent chamber 564-3 as an ion beam 575. This adjacent chamber 564-3 is, for example, a mass spectrometry chamber. In the extraction electrode/acceleration chamber 564-2, a plurality of acceleration electrodes, focusing (converging) electrodes 561-4, 5 and the like are arranged, vacuum drawing openings 568-3 are opened in some places, and the extraction electrode/acceleration chamber 564- 2 is brought to low pressure. The accelerating electrodes and focusing (converging) electrodes 561-4, 5 are formed with conductor films around the side walls of the substrate having central holes 565-2, 3 etc., and a voltage can be applied. The ionization chamber 564-1 can also be set to a low pressure by providing an opening for vacuuming the upper substrate and the like. Furthermore, the ionization chamber including the ion gun itself can be housed in a vacuum box to lower the pressure of the ionization chamber. Further, when the side surface of the main substrate irradiated by the atomic beam 571 generates heat, a cooling chamber can be provided on the back side thereof. On the side surface of the main substrate irradiated with the atomic beam 571, a conductor film can be formed in addition to various insulating films, and the generated heat or the like can be quickly transmitted to the outside. The ionization method shown in FIG. 39 is called the CF-FAB method, and when the present invention is used, it can be made extremely small and can be easily manufactured, and accurate measurement can be performed.

<Collision cell>
In a mass spectrometer, multiple multipole electrode chambers such as multiple quadrupoles are arranged along the ion beam axis in order to increase the analysis accuracy and sensitivity, and the ions emitted from the preceding (four) multipole chambers are analyzed. The one with higher efficiency to be taken into the next (four) multipole chamber is also in practical use. Among them, the collision cell manufactured by using the present invention will be described. In the quadrupole mass spectrometric chamber shown in the present specification, the Coryjan cell introduces a collision gas or a reaction gas such as Ar, N2, O2, and NH3 from the outside through an opening provided in the upper substrate or the lower substrate, and enters from the previous stage. The produced ion beam is made to collide with these introduced gases to dissociate or react with the ions to generate product ions. A high-frequency voltage (a DC bias voltage may be applied) applied to the quadrupole electrode is applied to the product ions, and the ions are sent to the next-stage quadrupole chamber or the like. Therefore, in the present invention, the quadrupole electrode chamber can be changed to a collision cell very easily. That is, the collision gas and the reaction gas are externally provided with an inlet and an outlet (the outlet is connected to a vacuum pump).

Since gas is introduced into the collision cell, the pressure becomes higher than that of the through chamber in the preceding or subsequent stage (for example, the mass spectrometry chamber). It is also possible to further provide a through chamber with the through chamber and to connect a vacuum sweeping line to the through chamber for vacuum sweeping. In addition, the central hole (where the ion beam passes) provided in the partition between the through chambers can be made smaller or larger, or the length can be adjusted to adjust the gas flow. When the central hole (where the ion beam passes) provided in the partition walls of the through chambers is made small, in order to prevent the ion beam from colliding with the partition walls, the partition walls themselves may be provided with electrodes to focus the ion beam. Alternatively, a partition wall (substrate side wall) having a central hole for focusing the ion beam may be separately arranged in front of the penetration chamber. In the present invention, even if a plurality of through chambers, partition walls, and conductor films are provided, the steps are almost the same, so there is little increase in manufacturing and manufacturing costs. (Although the area increases a little, but it is not a problem because it is small.) Therefore, it is necessary to provide a penetrating chamber, a partition, and a conductive film partition (this may be called an ion (accelerating or focusing) lens) just in case. In such a case, a voltage is applied from the outside, and if unnecessary, nothing is done.

<Ion trap mass spectrometer>
Next, the present invention can also be applied to an ion trap mass spectrometer. FIG. 40 is a diagram showing a method for manufacturing an ion trap mass spectrometer. The main substrate 601 is attached to the support substrate 602. As the support substrate 602, various substrates such as an insulating substrate made of glass, ceramic, plastic or the like, a semiconductor substrate made of Si or the like, a conductive substrate made of Cu, Al, Fe or the like can be used. As a method of attaching the support substrate 602 and the main substrate 601, the support substrate 602 is attached with an adhesive or a low melting point solder (metal) so that it can be separated from the main substrate 601 as described later. In the case of an adhesive, an adhesive that can be peeled off by irradiation with ultraviolet rays or an adhesive that can be detached by applying heat can be used. A photosensitive film 603 is formed on the surface of the main substrate 601 attached to the support substrate 602, and a region where an ion trap mass spectrometer is to be formed is opened. (FIG. 40(a)) Next, the main substrate 601 in the portion where the window is opened is etched to a predetermined thickness to form a recess 604 in the main substrate 601. This predetermined thickness is approximately equal to the radius of the ring electrode of the ion trap mass spectrometer. (FIG. 40(b)) (main substrate thickness h31, predetermined thickness h32)

Next, the photosensitive film 603 is removed, the photosensitive film 605 is applied (or attached) again, and the portions 605-3 and 4 to be left as the substrate side wall and the main substrate and the ion trap mass spectrometer are formed by the photolithography method. Ring electrode forming patterns 605-1 and 605-2 are formed. The ring electrode forming patterns 605-1 and 605-2 of the ion trap mass spectrometer are formed in the recess 604 of the main substrate 601. The plane pattern at this time is a circular pattern in which the photosensitive film patterns 605-1 and 605-2 are connected as shown in FIG. (Note that even with a square or rectangular pattern, the quadrupole electric field can be formed by adjusting the voltage condition of the electrode of the ion trap mass spectrometer.) (FIG. 40(c)) Next, these The main substrate 601 is etched using the photosensitive film pattern 605 as a mask. At this time, some of the main substrates 601-1, 2 and 3 are left. (Thickness h33) The main substrate 601 is etched by isotropic etching using wet etching or dry etching so that side etching is performed. Alternatively, alkali wet etching is performed along the crystal axis of silicon, and etching is also performed in the lateral direction. Various methods are known for etching while leaving a constant thickness h33 with good controllability. For example, if a high-concentration P-type diffusion layer is formed in advance in a silicon substrate (it is also possible by a substrate bonding method), that portion becomes an etching stopper. (FIG. 40(d)) The state where the photosensitive film 605 is removed is shown in FIG. 40(e). Next, the main substrate 601-2 in the central cavity 606-2 of the ring electrode is removed by etching. This etching is performed by vertical (anisotropic) etching after forming a photosensitive film and opening a window only in this portion. At this time, the main substrates 601-4, 601-7, 601-1, 601-3, etc. are not etched. Portions 601-5 and 6 to be the ring electrodes may be etched to some extent if the height can be controlled. (Characteristics can be adjusted by changing the voltage) (Fig. 40(f))

Next, a conductor film is laminated on the main substrate 601, and a conductor film pattern 607 is formed. The unnecessary conductor film is removed by etching, leaving the portions (601-5, 6) to be the ring electrodes and the wiring portions connected to the portions. When the main substrate is a semiconductor substrate such as Si, an insulating film is formed and then a conductor film is formed. The conductor film is a metal film of Cu, W, Mo, Cr, Ti, Al, Au or the like, or an alloy film or a laminated film of these, and is laminated by a CVD method, a PVD method, a plating method, an electroforming method or the like. (FIG. 40(g)) Next, the upper substrate or the lower substrate 608 to which the end cap electrode 609 is attached is attached to the main substrate 601 while being aligned. (FIG. 40(h)) This attachment may be performed by using an adhesive, or when the upper substrate or the lower substrate 608 is glass or quartz and the main substrate is Si or the like, the electrostatic anode diameter may be adjusted. .. After that, the support substrate 602 is removed. There are various methods for removing the support substrate. For example, when the support substrate 602 and the main substrate 601 are attached to each other with a thermosoftening adhesive or a low melting point alloy (softening temperature or melting point T1), the main substrate 601 and the upper and lower substrates are hardened adhesive or electrostatic anodic bonding (hardening temperature). Or, when attaching at an electrostatic anodic bonding temperature T2), select an adhesive such as T1>T2, first attach the main substrate 601 and the upper and lower substrates at the temperature of T2, and then raise the temperature to support T1 or higher. The substrate 602 and the main substrate 601 are separated. (Fig. 40(i))

Next, a groove (central hole) 610 which serves as an ion beam passage is formed in the main substrate 601. Since the main substrates 601-4 and 601-7 have a height of h31, they are attached to the upper and lower substrates 608, but the portions of the main substrates 601-5 and 6 serving as ring electrodes are not attached to the upper and lower substrates 608. However, since the ring electrode wiring 607 extends to the portions of the main substrates 601-4 and 601-7, a contact hole 611 is opened in the upper and lower substrates 608 at this portion, and a conductor film is formed in the contact hole. Electrode wiring 612 is formed on the upper and lower substrates 608. At the same time, a contact hole 611 and an electrode wiring 612 which are electrically connected to the end cap electrode 609 are formed. After this. The ion trap portion is completed by adhering the upper substrate side and the lower substrate side. At the time of this attachment, a glass substrate or the like may be interposed between the main substrates. The ring electrodes 601-5 and 601-6 are integrated, and the upper and lower conductor films 607 are also connected by adhesion. Further, the ring electrodes 601-5 and 601-6 are supported by 601-3 and 601-4 and appear unstable, but the thickness h33 of 601-3 and 601-4 can be adjusted, and the ion trap is Since the supporting portion can be appropriately formed in a portion that does not affect the characteristics, and the upper and lower substrates 608 can be partially formed and connected, there is no problem in terms of strength. Further, in FIG. 40, the ring electrode portions 601-5 and 6 are thinned. However, if there is no problem in the ion trap characteristics without thinning, it does not need to be thinned. In that case, the upper and lower substrates 608 and the ring electrode portions are Since 601-5 and 601 can be directly attached, the strength can be further increased. Further, in this case, since the contact hole and the electrode wiring can be directly taken out from the ring electrode, it is not necessary to provide 601-3 and 601 and the ring electrode can be an independent ring electrode. (Fig. 40(j))

Thus, the present invention can be used to fabricate an ion trap mass spectrometer by a simple process. This ion trap mass spectrometer is composed of one ring electrode 601-5 and 6 and two opposing end cap electrodes 609-1 and 609-2. A high frequency high voltage is applied to the ring electrodes 601-5 and 6 and is formed in a space (ion trap space 613) surrounded by the ring electrodes 601-5 and 6 and the pair of end cap electrodes 609-1 and 609. An ion trapping space 615 is formed by the quadrupole electric field, and ions are trapped there. On the other hand, an appropriate auxiliary AC voltage is applied to the end cap electrodes 609-1, 2 in accordance with the analysis mode at that time. Charged particles (ions, electrons) enter from a passage on the left side of the central hole 610 formed in the ring electrode 601-5 and the main substrate 601-4 connected thereto (charged particle G1). The charged particles G1 enter from the ionization chamber on the left side of the substrate 601-4 having the central hole 610, for example, by being accelerated by the extraction electrode. The charged particles G1 exit from the central hole 610 of the ring electrode 601-5 to the ion trap space 613 (charged particles G2) and are trapped in the ion trapping space 615 by the ion trapping electric field. The ions trapped in the ion trapping space 615 are appropriately swept (charged particles G3) and enter the central hole 610 of the opposing ring electrode 601-6, and further pass through the central hole 610 of the substrate 601-7 connected thereto. And then emitted (charged particles G4) to, for example, the adjacent ion detection chamber, and the amount of ions is counted.

Further, an opening 617 is provided in the upper substrate 608 or the like, and a target gas (Ar, Xe, N2, NH3, O2, or the like) is introduced into the ion trap chamber 613 from there, and an electric field formed inside the ion trap chamber 613 Ions are decomposed or reacted by colliding the ions in the specific mass number range collected at the center with the target gas. That is, a collision cell can also be formed. After the dissociative decomposition is sufficiently performed, the voltage applied to the electrodes 601-5, 6, 609-1, 2 is changed, and an electric field for ejecting ions is formed inside the ion trap 615 to release the ions. .. Ions emitted from the ion trap are guided to a mass spectrometer and an ion detector. Further, if the opening 616 for evacuation is formed in the upper and lower substrates 608, the ion trap chamber can have a desired degree of vacuum.

In the ion trap mass spectrometer shown in FIG. 40, the charged particles G enter the ion trap chamber 613 through the central hole 610 of the ring electrode 601-5, and further pass through the central hole 610 of the ring electrode 601-6. Exits from the ion trap chamber 613, but can also pass through the end cap electrode 609. FIG. 41 is a diagram showing an ion trap mass spectrometer in which charged particles pass through the end cap electrode 609. Since the same process can be used up to FIG. 40(i), FIG. 40(h) and subsequent figures are shown. The part different from FIG. 40 will be described in detail. In FIG. 41H, an opening 614 is formed in the upper substrate 608, and a passage 618 is formed in the end cap electrode 609. When the end cap electrode 609 is attached to the upper substrate 608, the opening 614 and the passage 618 are attached so that they are aligned with each other. As a result, the opening 614 and the passage 618 become a passage that passes in the direction perpendicular to the substrate surface of the upper substrate 608. Others are the same as the contents described in FIG. 40(h), FIG. 40(i), and FIG. 40(j). In FIG. 40(j), when the upper substrate 608-1 side and the lower substrate 608-2 are attached, the upper passages 614-1 and 618-1 and the lower passages 614-2 and 618-2 are aligned. It is desirable that they are aligned and the center line thereof passes through the center of the ion trapping space 615.

Next, as shown in FIG. 41K, a second upper substrate 620 to which the second main substrate 619 is attached is produced, and a through chamber 621 is formed. An ionization chamber and an extraction electrode are arranged in this penetration chamber 621. The components are arranged so that the generated ions pass through the passages 614-1 and 618-1. The columns 619-1, 2 of the second main substrate 619 having the through chamber 621 attached to the second upper substrate 620 having those functions are attached to the (first) upper substrate 608-1. Ions generated in the penetration chamber 621 are aligned and attached so as to enter the ion trap chamber 613 through the passages 614-1 and 618-1.

Next, the second lower substrate 623 to which the third main substrate 622 is attached is manufactured, and the through chamber 624 is formed. An ion detection chamber is arranged in this penetration chamber 624. Each component is arranged so that the ions emitted from the ion trap chamber 613 through the passages 614-2 and 618-2 to the through chamber 624 enter the detection chamber. The columns 622-1 and 62-2 of the third main substrate 622 having the through chambers 624 attached to the second lower substrate 623 having these functions are attached to the (first) lower substrate 608-2. The ions emitted through the passages 614-2 and 618-2 are aligned and attached so as to enter the detection chamber.

In the ion trap mass spectrometer shown in FIG. 40, charged particles (ions) travel parallel to the substrate surface, but in the case of FIG. 41, charged particles (ions) travel perpendicularly to the substrate surface. When the size (height) of each chamber is insufficient with one main substrate, the main substrates having a required thickness may be stacked and attached. In this way, an ion trap mass spectrometer capable of moving ions through the passage opened in the end cap electrode can also be manufactured.
In the ion trap mass spectrometer shown in FIGS. 40 and 41, the ring electrodes 601-5 and 6 are separated from the upper substrate and the lower substrate 608, but they can be formed in a state of being adhered without being separated. In that case, the ion trap space is surrounded by the ring electrodes 601-5 and 6. Therefore, the occupied area (volume) of the ring electrode can be small. The ring electrode manufacturing process can also be simplified.

FIG. 49 is a view showing an ion trap mass spectrometer formed in the vertical direction similarly to FIG. 41. In the ion trap shown in FIG. 49, the ring electrode is not floating but fixed. The mass spectrometer is composed of a substrate region A having an ion trap chamber, a substrate region B having an ionization chamber and an extraction electrode chamber, and a substrate region C having an ion detection chamber. In the substrate region B, a penetration chamber 914-2 serving as an extraction electrode chamber and a penetration chambers 914-1 and 91-3 serving as ionization chambers for supplying ions to the extraction electrode chamber 914-2 are arranged in the central portion. The extraction electrode chamber 914-2 and the ionization chamber 914-1 are separated from each other by a substrate side wall plate 911-3 having a central hole 915-1. The extraction electrode chamber 914-2 and the ionization chamber 914-3 are partitioned by a substrate side wall plate 911-4 having a central hole 915-2. As the ionization chamber, an ionization chamber using various ionization methods described in this specification can be adopted. A sample supply chamber can also be connected to this ionization chamber. Although two ionization chambers are described here, one ionization chamber may be used, or three or more ionization chambers may be connected to the extraction electrode chamber 914-2. Alternatively, ions generated outside may be connected to the extraction electrode chamber 914-2.

The extraction electrode chamber 914-2 has a function of accelerating ions into the ion trap chamber and sending them to the ion trap chamber at a certain speed. The upper surface of the main substrate 911 is attached to the upper substrate 912, and the lower surface of the main substrate 911 is attached to the lower substrate 913. On the lower substrate 913 are formed disc-shaped electrodes 917-1 and 97-2 whose center is hollowed out, and an insulating film 918 is formed between the disc-shaped electrodes 917-1 and 2. An insulating film 918 is also formed on the disk-shaped electrodes 917-1 and 2 as needed. When a voltage having a sign opposite to that of the ions is applied to the disk-shaped electrodes 917-1 and 92-2, the ions are extracted from the opening 919 opened at the center of the disk-shaped electrodes 917-1 and 2 and accelerated to accelerate the ion trap. Enter the room 904. If a push-out electrode 916 is formed on the upper substrate 912 immediately above the disk-shaped electrodes 917-1 and 2, when a voltage having the same sign as the ion is applied to the push-out electrode 916, the ions are pushed out and enter the opening 919. To go. If this push-out electrode 916 is provided, the efficiency with which ions travel to the opening 919 can be increased.

The substrate area A is different from FIG. 41 in that the ring electrodes are attached to the upper and lower substrates. That is, a through chamber 904 having a narrow center is formed in the main substrate 901, and tapered substrate side walls 901-1, 90-2 are formed. There are various methods of forming this. For example, if a Si substrate is attached to a support substrate, masked with photoresist or the like, and Si is etched from the upper side, half of the through chamber having a tapered inclined surface can be manufactured. .. This taper angle can be controlled by changing the etching conditions. Next, if the support substrate is removed and the same ones are stacked and attached (for example, by the alternate long and short dash line M), the substrate region A having the through chamber 904 having the shape shown in FIG. 49 can be manufactured. The conductor films 905 (905-1, 2) to be the ring electrodes are laminated on the side surfaces of the substrate side walls 901-1, 902 of the main substrate 901. When the main substrate 901 is a conductor film or a semiconductor substrate made of Si or the like, the conductor film is laminated after the insulating film is laminated on the main substrate 901. Here, the ring electrode 905 (905-1, 2) has a substantially circular cross section parallel to the substrate surface, and is a continuous electrode.

An end cap electrode 906 is formed on the upper substrate 902 and arranged in the through chamber 904 which is an ion trap chamber. In addition, an end cap electrode 908 is formed on the lower substrate 903 and arranged in the through chamber 904 which is an ion trap chamber. An opening 907 is formed in the center of the end cap electrode 906. With respect to the substrate regions A and B, the upper substrate 902 in the substrate region A and the lower substrate 913 in the substrate region B are separated from the openings 907 and 919. The shafts are attached so that they align. Therefore, the ions that have advanced through the openings 919 and 907 are trapped in the ion trapping space 910 at the center of the ion trap chamber 904.

The substrate region C has a penetration chamber 924 which is an ion detection chamber, and an upper substrate 922 is attached to the upper surface of the main substrate 921 and a lower substrate 923 is attached to the lower surface of the main substrate 921. A part of the main substrate 921 is left on the upper substrate 922, 921-3 and 4 are left, and an opening 928 is opened in the central portion. Conductor films 925-1 and 92-2 are formed on. The opening 928 on the side of the upper substrate 922 has a hole shape, but the openings of the main substrate portions 921-3 and 4 are parallel groove-shaped and are formed on the side surfaces of the main substrate portions 921-3 and 4. The formed conductor film becomes a parallel plate electrode. A part of the main substrate 921-5, 6 is left in the through chamber 924, and the surfaces thereof are parallel to each other to form a parallel space 924-2. Secondary electron emission material films 926 (926-1, 2) are formed on the surfaces of the parts 921-5, 6 of the main substrate (via an insulating film when the main substrate is a semiconductor or a conductor), Conductor films (up and down) are formed on both ends thereof. With respect to the substrate regions A and C, the lower substrate 903 of the substrate region A and the upper substrate 922 of the substrate region C are attached so that the axes of the openings 909 and 928 are aligned.

The ions trapped in the ion trapping space 910 are attracted by the potential of the end cap electrode 908 and enter the opening 928 of the substrate region C through the opening 909. Since the conductor film electrodes 925-1 and 925-1 formed on the side surfaces of the main substrates 921-3 and 4 of the opening 928 in the substrate region C are parallel plate electrodes, the ion trajectory is bent by adjusting the voltage. be able to. Therefore, the bent ions collide with the secondary electron emission material film 926-2 of the lower electrode and emit the electron e. The emitted electrons e are attracted by the electric field of the upper electrode and collide with the secondary electron emission material film 926-1 to emit the electrons e. The emitted electrons e are attracted to the lower electric field and collide with the secondary electron emission material film 926-2 to emit the electrons e. Since the number of electrons emitted by collision is much larger than the number of electrons before the collision, the number of electrons increases each time the collision is repeated. The last electron emitted by colliding with the edge of the secondary electron emission material film collides with the conductor film formed on the side surface (inner surface) of the substrate side wall 921-2 at the right end of the through chamber 924 (924-3). And generate an electric current. By measuring this current, the amount of ions can be obtained.

The space 924-2 may be a central hole, and in this case, a secondary electron emission material film is formed on the inner surface of the central hole. If a conductor film is formed on both ends of the conductor film, a (high) voltage is applied to the conductor film, and ions are made to collide into the central hole 924-2, secondary electrons are similarly emitted and the conductor film is formed. The change in current can be measured with the membrane electrode 927. In the substrate area C, the area of the lower main board 921-6 is larger than the area of the upper main board 921-5, but even when the central hole is formed, there is no particular problem because the upper and lower parts are attached to each other. .. As described above, a vertical ion trap mass spectrometer having a plurality of ionization chambers can be manufactured. Although wirings, contact wirings, and outer electrodes that are connected to the conductor film are not shown in the drawing, the wirings can be designed by being rotated, so that the outer electrodes can be formed at desired positions. Further, although neither a gas introduction hole nor an opening for a vacuum drawing line is shown, these can also be formed at desired positions.

<Electron multiplier>
In FIG. 19, the ion beam 331 distributed in the mass analysis chamber 308 enters the ion detection chamber 309. Various methods can be used for the ion detection system arranged in the ion detection chamber. Here, it is assumed that the plate is a parallel plate type or a pipe type channel type secondary electron multiplier. The ion detection chamber 309 is a through chamber formed in the main substrate and is separated by a substrate side wall (partition wall) 301-5 having a central hole 310-5. The upper substrate 302 is attached to the upper part of the through chamber 309, the lower substrate 303 is attached to the lower part of the through chamber 309, and the side face side is surrounded by the main substrate 301. An electrode 333 is formed on the lower surface of the upper substrate 302, and an electrode 332 is formed on the upper surface of the lower substrate 303. These electrodes 332 and 333 are made of a secondary electron emitting material. The secondary electron emitting substance is a substance which, when hit by a charged particle such as an ion or an electron, easily obtains its energy and emits an electron. Examples of secondary electron emitting materials include magnesium oxide (MgO), Mg, Au, Pt, BeO, Cr, PolySi, Al, Al2O3, TiN, and composite films of these.

In the case of the parallel plate type, a secondary electron emission material film is also formed on the side surface of the main substrate 301 (in this case, it is desirable to interpose an insulating film). Two side surfaces of the main substrate 301 are used as parallel plate electrodes. You can also In the case of a pipe-shaped channel type secondary electron multiplier, an electrode 333 on the lower surface of the upper substrate 302, an electrode 332 on the upper surface of the lower substrate 303, and an electrode formed on the two side surfaces of the main substrate 301 also serve as secondary electrons. It is sufficient to connect the emitting substances in series. Further, like the side wall of the substrate having the central hole, the side wall of the substrate having the central hole is formed, and the parallel plate type electrode made of the secondary electron emitting material is formed on the side wall of the substrate or the secondary electron emission continuous to the inner surface of the central hole. An electrode made of a material can be formed to form a secondary electron multiplier.

Contact holes 323 (having a conductor film formed therein) are formed at both ends of the electrodes 332, 333, and the external electrodes 324 (324-1, 2, 3, 4) are the upper substrate 302 and the lower substrate 303. Is formed on the outside of. When a high voltage DC voltage is applied between the external electrodes 324-1, 3 of the electrodes 332, 333 on the introduction side of the ion beam 331 and the external electrodes 324-2, 4 of the electrode 332 on the exit side of the ion detection chamber, As indicated by an arrow, 331 collides with an electrode 332 or 333 made of a secondary electron emitting substance, a secondary electron 334-1 is emitted, and the secondary electron 334-1 collides with the facing electrode 332 or 333. , Secondary electrons 334-2 are emitted, and this is repeated to multiply by an avalanche, and the final secondary electrons 334-n are collected in the collector 335. The collector 335 is a portion where the secondary electrons 334-n emitted from the output ends of the electrodes 332 and 333 made of the secondary electron emitting substance of the ion detection chamber 309 collide, for example, the longitudinal end of the ion detection chamber 309. It is a conductor film formed on the side surface of the main substrate 301-6. The collector 335 is connected to the external electrode 324-5 through the contact hole 323. DC voltage for guiding secondary electrons 334-n between the output end electrodes 324-2, 4 of the electrodes 332, 333 made of secondary electron emission material of the ion detection chamber 309 and the collector electrode 324-5 connected to the collector 335. Is applied, most of the secondary electrons 334-n gather in the collector 335 and are detected as a collector current through the collector electrode 324-5.

Incidentally, in the case of the parallel plate type, a gradient electric field can be formed by shifting both ends of the electrodes 332, 333 with respect to each other, so that a motion close to a cycloidal motion of secondary electrons can also occur, so that the collector current can be increased. it can. (Japanese Patent Publication No. 08-003984)

FIG. 42 is a diagram showing an ion detection chamber in which a large number of dynodes according to the present invention are arranged. 42A shows a schematic sectional view in a direction parallel to the substrate surface, and FIG. 42B shows a schematic sectional view in a direction perpendicular to the substrate surface. The chamber next to the ion detection chamber 637 is a mass spectrometry chamber, and both chambers are substrate side walls (partition walls) 631-2-1 and 631-3-1 (these are connected side walls and the central hole 630 (630-1). The ion detection chamber 637 has a low pressure through an evacuation opening 647 opened in the upper and lower substrates 641 or 642. The ion beam 630 exiting the mass analysis chamber and entering the ion detection chamber is of the side walls 631-2-2 and 631-3-2 of the substrate having the central hole 630 (630-2) (these are connected side walls). It passes through the central hole 630 (630-2). Conductive films 633-1 and 633-2 forming parallel plate electrodes are formed on the left and right sidewalls of the central hole 630 (630-2). One electrode 633-1 is connected to the outer electrode 646-0 through a contact hole (conductor film is laminated) 645 opened in the upper substrate 641, and the other electrode 633-2 is opened in the lower substrate 642. It is connected to the outer electrode 644-0 through a contact hole (a conductive film is laminated) 643. By applying a voltage to these outer electrodes 644-0 and 646-0, an electric field is generated between the parallel plate electrodes 633-1 and 633-2, and the trajectory of the ion beam 639 is bent. If a parallel plate electrode is formed in the central hole, the distance between the electrodes is small, so that the electric field is large even when a small voltage is applied, and the ion beam can be bent easily. Therefore, if a small voltage is not required, even if the central hole provided in the side wall of the substrate is not used, a conductive film for parallel plate electrodes is formed on a part of the side surfaces 631-2 and 631-3 of the normal main substrate 631. It is sufficient to form 633-1 and 633-2. The conductor film is, for example, Cu, Al, W or the like.

In the ion detection chamber 637, a plurality of main substrates 631-2-3-1 to 631-2-3-n (main substrate side faces) protruding from the left and right main substrate side faces 631-2 and 631-3 to the inside of the ion detection chamber 637. 631-2 side) and 631-3-3-1 to 631-3-3m (main substrate side surface 631-3 side) are formed, and their protrusions 631-2-3-1 to 631-2-3. -N and 631-3-3-1 to 631-3-3m have a secondary electron emission material film 632 (632-1) through an insulating film (for example, SiO2 film, SiNxOy film or SiNx film) on the surface. ,..., 632-n) and 635 (635-1,..., 632-m) are formed. This secondary electron emission material film is formed by, for example, a photolithography method + an etching method after being laminated by a CVD method or a PVD method, and a protrusion 631-2-3 from side surfaces 631-2 and 631-3 of the main substrate. 1-631-2-3-n and 631-3-3-1 to 631-3-3-m at least cover the surface. Since the secondary electron emission material film is a semiconductor or a conductor, it should not be electrically connected to each other. Therefore, an insulating film (SiO2 or the like) is usually stacked between the main substrate 631 and the secondary electron emission material film 632, and the protrusions 631-2-3-1 to 631-2-3-n and 631- are formed. The unnecessary portions of the secondary electron emission material films 632 formed in 3-3-1 to 631-3-m are removed by etching using photolithography or the like or etching or the like so that they are not electrically connected to each other. Next, a conductor film is laminated, and the secondary electron emission material formed on the protrusions 631-2-3-1 to 631-2-3-n and 631-3-3-1 to 631-3-3-m. Conductor film wirings 634 (634-1,..., N) and 636 (636-1,..., M) are formed so as to be in contact with part of the film 632. This can be performed simultaneously with the formation of the conductor films 633-1 and 633-2 for the parallel plate electrodes.

The protrusions 631-2-3-1 to 631-2-3-n and 631-3-3-1 to 631-3-3-m can be formed when the penetration chamber (ion detection chamber) 637 is formed. .. The pattern formation of the secondary electron emission material film 632 and the conductor film 633 is performed by forming a photosensitive film pattern on a side surface substantially perpendicular to the surface of the main substrate 631 (or the surfaces of the upper substrate 641 and the lower substrate 642), It is necessary to etch and remove the secondary electron emission material film 632 and the conductor film 633 using the mask as a mask. However, after exposure using a photosensitive sheet or after forming a photosensitive film pattern by an electrodeposition resist method. , Can be formed by isotropic etching (dry or wet). The exposure method can be performed using an oblique irradiation exposure method or an oblique rotation exposure method, and vertical irradiation is also possible if the depth of focus is deep. Electron beam irradiation exposure can also be used. In addition, since a thick resist film can be exposed by an exposure method having a deep depth of focus, the photosensitive film can be formed by a coating method. These conductor film patterns 633, 634, 636 are also formed on the lower surface of the upper substrate 641 and the upper surface of the lower substrate 642 as shown in FIG. And contact holes 645 and 643 are formed in the lower substrate 642, the conductor film formed therein is passed therethrough, and conductor film electrode wiring 646 (646-0, 1,..., N, n+1) is further formed thereon. And the conductor film electrode wiring 644 (644-0, 1,..., M) is formed. Accordingly, a voltage can be applied to the conductor film patterns 633, 634, 636.

When the ion beam 639 enters the ion detection chamber 637, the trajectory is bent by the electric field generated by the parallel plate electrodes 633 (633-1, 2) described above, and the secondary of the closest protrusion 631-2-3-1. The electron emission material film can be irradiated. In particular, if a potential opposite to the charge of the ion beam is applied to the secondary electron emission material film 632-1 connected thereto through the conductor film 634-1, further energy can be obtained for irradiation. If a voltage is applied to the secondary electron emission material film 632-1, the parallel plate electrodes 633 (633-1, 2) may not be present depending on the conditions. However, if parallel plate electrodes 633 (633-1, 2) are provided, it is possible to control and irradiate a predetermined place. When the ion beam 639 collides with the secondary electron emission material film 632-1, secondary electrons 640 are emitted.

A positive potential (generated secondary electrons 640) is generated from the conductor film 636-1 to the secondary electron emission material film 635-1 formed on the protruding portion 635-3-3-1 formed on the opposite side surface 631-3. Of the secondary electron emission material film 632-1, the voltage condition should be set to an optimum value while measuring). , Almost all of the secondary electrons emitted from the secondary electron emission material film 632-1 enter the secondary electron emission material film 635-1 and further emit secondary electrons. By repeating this, a large amount of the multiplied secondary electrons 640-p is emitted from the secondary electron emission material film 632-n formed on the protruding portion 631-2-3-n at the final stage, and the collector conductor is formed. Collected in membrane 638. A voltage can also be applied to the collector conductor film 638 from the outer electrode wiring 646-(n+1) through the contact 645. Is irradiated on the collector conductor film 638, and the current generated by the secondary electrons can be detected.

For example, when the incident ion 639 is positive, a negative voltage is applied to the parallel plate electrode 633-1 to bend the ion 639 to the main substrate 631-2 side, and the secondary electron emitting material film 632-1 has a negative voltage ( For example, -aV) may be applied. Further, if a voltage (for example, -a+bV) on the positive side of -aV is applied to the secondary electron emission material film 635-1 to which the secondary electron 640-1 is next applied, the secondary electron 640-1 becomes a secondary electron. This corresponds to the electron emission material film 635-1. In this way, the dynode in the next stage is applied with a little voltage (for example, a positive voltage of bV) than the diode in the previous stage, and cV is applied to the secondary electron emission material film 632-n in the final stage. (For example, c=−a+n×2b) Further, if a voltage of Cc+dV is applied to the collector 638, most of the secondary electrons 640-p emitted from the secondary electron emission material film 632-n at the final stage are collected in the collector 638. .. The values of a, b, c, and d above may be determined by actual measurement, but the ion detection chamber 637 of the present invention is extremely small, and since the LSI process is used, it can be manufactured extremely accurately. A relatively high electric field can be obtained even if the values of b, c, and d are small. For example, if the distance between the secondary electron emission material films formed on the substrate side surfaces 631-2 and 631-3 is 1 mm, then a=10V to 500V, n=10, m=9, and b=0.5V. -25V, c=0V, d=1-50V can be selected. Further, if the distance between the secondary electron emission material films formed on the substrate side surfaces 631-2 and 631-3 is increased, for example, the above value may be increased by a multiple thereof.

Although FIG. 42B is a schematic cross-sectional view of the ion detection chamber 637 in the vertical direction (direction perpendicular to the substrate surface), a part of the structure in the cross-sectional direction (direction perpendicular to the paper surface) is also shown. For example, the parallel plate electrodes 633 (633-1, 2), the contact holes 643, 645m, and the electrodes/wirings 644-0, 646-0 do not all have the same cross section, but all of them are shown so that their relationships can be understood. The structure of is described. However, transparent patterns are used for those that do not have the same cross section. Since such a relationship can be seen immediately, it is applied to other parts. Although the region of the collector 638 is depicted as having the same size as the ion detection chamber 637, the region 637-A in which the collector 638 is present can be made wider because the region in the lateral direction (vertical direction in FIG. 42A) can be made larger. The area of the collector 638 can be increased by increasing the area in the direction, and more secondary electrons 640-p can be trapped.

42(c) is a schematic cross-sectional view taken along the line A-A' in FIGS. 42(a) and 42(b), and is a view seen from the left-right direction in FIGS. 42(a) and 42(b). The line indicated by the broken line 647 indicates the boundary between the side surface 631-2 of the main substrate 631 and the protruding portion 631-2-3 serving as the dynode portion. The side surface of the main substrate in a portion where there is no protruding portion in the cavity that serves as the ion detection chamber is shown as a broken line. Similarly, a line indicated by a broken line 648 indicates a boundary between the side surface 631-3 of the main substrate 631 and the protruding portion 631-3-m serving as a dynode portion. Secondary electron emission material films 632 and 635 are laminated on the surfaces of the protrusion 631-2-3 and the protrusion 631-3-m from the lower surface of the upper substrate 641 to the upper surface of the lower substrate 642, respectively. Further, a conductor film 636 is further laminated on the surface of the secondary electron emission material film 632 on the protruding portion 631-3-m from the lower surface of the upper substrate 641 to the upper surface of the lower substrate 642. Since the conductor film 636 and the secondary electron emission material film 632 are in contact with each other in such a wide area, not only when the secondary electron emission material films 632 and 635 are conductor films but also when they are semiconductor films, A sufficient potential is applied from the conductor film 636 to the secondary electron emission material film 632. As a matter of course, the ion detection chamber is narrower than the portion without the protruding portion. As has been the case so far, it is possible to form an insulating film between the secondary electron emission material films 632 and 635 and the main substrate 631 so as not to conduct electricity. An insulating film as a protective film may be formed on the secondary electron emission material films 632 and 635. The advantage of the present invention is that since it is not necessary to form a small pattern such as a contact hole or a via in the through chamber, the accuracy of patterning in a recessed portion such as the through chamber is not required, and the manufacturing Easy to peel.

42(d) is a schematic cross-sectional view of a B-B' portion in FIGS. 42(a) and 42(b), and is a view seen from the left-right direction of FIGS. 42(a) and 42(b). Conductor films 633 (633-1, 2) for parallel plate electrodes are formed on both left and right sides of the inner surface of the central hole 630-2. These conductor films 633 (633-1, 2) extend to the upper substrate 641 or the lower substrate 642 as shown in FIGS. 42(a) and 42(b), and the outer electrode/wiring 646 is formed. Voltage can be applied from -0 or 644-0. The central hole 630 and the conductor film 633 can be formed by separating the main substrate 631 into upper and lower parts and attaching them to the upper substrate 641 and the lower substrate 642, respectively, as described above. Just stick together. The bonded (attached) portion is indicated by a broken line 649.

As shown in FIG. 42(a), the shapes of the protruding portions 631-2-3-1 to n and 631-3-3-1 to m are designed to have an inclined surface inclined in the incident direction of the ion beam 639. When formed substantially perpendicular to the thickness direction of the substrate 631, it is easy to irradiate the pattern of the secondary electron emission material film 632 with the ion beam 639 at a constant angle. Furthermore, since the incident angle of the secondary electrons is almost constant, the secondary electrons can easily be incident on the facing inclined surfaces, which simplifies the design and condition setting. The inclination angle of the protrusion 631-2-3-1, which is the dynode portion that is closest to the incident side of the ion beam 639 and is irradiated with the ion beam, is α1, and the opposite dynode portion that is irradiated with secondary electrons emitted therefrom is α1. The inclination angle of a protrusion 631-3-3-1 is β1, the inclination angle of the protrusion 631-2-3-n, which is the n-th dynode portion on the side surface 631-2 side of the main substrate 631, is αn, and the main substrate is The inclination angle of the protruding portion 631-3-3 -m, which is the m-th dynode portion on the side surface 631-3 side of 631, is βm. At this time, it is preferable that 10 degrees<α1,..., αn<45 degrees, 10 degrees<β1,..., βm<45 degrees. This makes it easy to control the irradiation angle of the ion beam, the emission rate of secondary electrons, and the irradiation angle. It should be noted that if the tilt angle is small, the ion detection chamber needs to be long, and if the tilt angle is large, the ion detection chamber can be shortened. (When the number of dynodes is the same)

The surface shape of the protruding portions 631-2-3-1 to n and 631-3-3-1 to m may be curved. For example, when the main substrate is divided into upper and lower parts and the protruding portions 631-2-3-1 to n and 631-3-3-1 to m are respectively formed, the horizontal etching (side etching) and the vertical etching (side etching) are performed. By using wet etching or dry etching that controls the etching rate in the thickness direction of the main substrate, the surface shape of the protruding portions 631-2-3-1 to 631-3-1-m is curved (one side). ) Or inclined surfaces are etched and they are attached at the central portion. If the surface shape of the protruding portions 631-2-3-1 to 63-n and 631-3-3-1 to m is such an inclined surface or a curved surface, a secondary electron beam or the like is projected onto the protruding portion 631-2-3. Since it is possible to concentrate on the surfaces of -1 to n and 631-3-3-1 to m, more secondary electron beams can be generated.

FIG. 43 is a diagram showing one embodiment of a method for producing the parallel plate electrode shown in FIG. 42. The difficulty of the method of manufacturing the parallel plate electrodes 633-1 and 2 is that electrodes are formed on the side surfaces of the central hole 630-2. FIG. 43 shows only the state near the parallel plate electrodes shown in FIG. In FIG. 43, the main board is divided into upper and lower halves. 43(a) to 43(e) are plan views (parallel to the surface of the main substrate), and FIGS. 43(f) to 43(k) are cross-sectional views perpendicular to the plan view. A photosensitive film pattern 653 is formed on the surface of the main substrate 651 attached to the lower substrate 652, and a portion for forming a central hole is opened (FIG. 43(a), and a concave portion to be the central hole is formed in the main substrate 651 through the opening). The depth of the central hole 654 is about half the depth of the actual central hole (central hole 630-2 in FIG. 42). A parallel plate electrode is provided on the side surface of the central hole 654. Since it is manufactured, the central hole 654 is etched as vertically as possible, and the photosensitive film pattern 653 is removed in FIG.

Next, the window of the photosensitive film 655 in the portion which will be the ion detection chamber is opened. The photosensitive film 655-2 is a pattern that forms the side wall of the substrate having the central hole 654, and the photosensitive films 655-2 and 35-2 are patterns that form the side surfaces of the substrate 651 that will be the ion detection chamber. Is the part that becomes the ion detection chamber. (FIG. 43B) By using these photosensitive film patterns as a mask, the portion of the main substrate 651 which will be the ion detection chamber is etched. These etchings may be vertical etchings or taper etchings. It is sufficient if the upper surface is of a controlled size when it is laminated and laminated in the future. FIG. 43C shows the state after the photosensitive film 655 is removed by etching the main substrate 651 in the portion to be the ion detection chamber, and the main substrate 651-2 to be the side surface of the ion detection chamber, 3 and a substrate side wall 651-1 having a central hole 654-1, and a lower substrate 652 which is the lower surface of the ion detection chamber. It is preferable that the longitudinal direction of the recess 654 shown in FIG. 43(b) (the ion beam advancing direction of the central hole) be larger than the actual central hole 654-1 in consideration of mask shift, etching variation and the like.

Next, an insulating film is formed on the main substrate 651, and a conductor film 656 (which is not shown when the main substrate is an insulator and may be omitted) is laminated to form an electrode for forming a parallel plate. The photosensitive film pattern 657-1 and the photosensitive patterns 657-2 and 3 for forming wiring are formed. Since these photosensitive film patterns are formed on the steps, they are formed by using a photosensitive sheet film, an electrodeposition resist film, an exposure method with a large depth of focus, an oblique exposure method, a rotary exposure method, or the like. (FIG. 43D) The conductor film 656 is etched by using the photosensitive film pattern as a mask to form conductor film patterns 656 (656-1, 2, 3). FIG. 43(e) is a plan view after removing the photosensitive film 657. The conductor film pattern 656-1 becomes electrodes formed on the left and right side surfaces of the central hole 654-1, and the conductor film pattern 656-2, Reference numeral 3 is a wiring pattern formed on the lower substrate 652. The cross section AA' in FIG. 43(e) is shown in FIG. 43(h), and the conductor film electrodes 656-1 are formed on the left and right side surfaces of the central hole 654 formed in the central portion of the side wall 651-1 of the main substrate 651. Are formed. 43(i) is a cross-sectional view taken along the line BB′ in FIG. 43(e), in which a conductor film electrode 656-1 is formed on the side surface of the central hole 654, and the conductor film electrode 656-1 is formed on the lower substrate 652. The formed wiring patterns 656-2, 3 are connected to the step portion of the substrate side wall 651-1. The formation of the conductor film 656 becomes thin at the step portion when first formed by the CVD method or the PVD method, but since the conductor film is thickly laminated by the plating method or the selective CVD method after that, the connection at the step portion is sufficient. To do. Further, when the main substrate 651 is etched, if the taper etching is performed, the step portion is tapered, so that the connection of the conductor film becomes more sufficient. Note that the insulating film between the conductor film 656 and the main substrate is not shown in FIG. 43(i).

By forming the same one on the upper substrate 658 side and attaching the lower substrate 652 side and the upper substrate 658 side to each other, an ion detection chamber whose side surface formed in the central hole serves as a parallel plate electrode is formed. .. In FIG. 43(k), after attaching the lower substrate 652 side and the upper substrate 658 side, contact holes 659 (659-1, 2), 660 (660-1, 2) and conductors to those contact holes are shown. A film is formed, and electrodes/wirings 661 (661-1, 2) and 662 (662-1, 2) connected to them are formed. (These contact holes and electrodes/wirings can also be formed before they are attached.) Connection between the upper and lower conductor film wirings 656-2 and 656-2 and 656-3 and 5, and the side surface of the central hole 654. The conductor films 656-1 (656-1-1, 2) formed in the above are connected by, for example, pressure bonding at the time of attachment. Alternatively, a suitable heat treatment may be performed for adhesion or fusion. When adhering with an adhesive, if the pressure is applied with an adhesive containing dispersed conductor particles, only the portion with the conductor film can be connected. Since the parallel plate electrodes are formed on the side surfaces of the central hole and the voltage can be freely applied from the outside of the ion detection chamber by the above-described simple process, the trajectory of the ion beam can be changed under desired conditions. As can be easily understood from the above description and drawings, the electrodes can be separated in the middle of the central hole, voltage can be applied to each electrode, and the parallel plate electrode in the front stage and the parallel plate electrode in the rear stage can be separated. Since the trajectories of the ions can be changed for each, more precise ion beam control can be performed. Furthermore, since parallel plate electrodes can be easily formed above and below the central hole (it is only necessary to form a photosensitive film pattern only on the top and bottom and etch away the conductor film on the side surface), so the vertical direction of the ion beam can be controlled. Can also Therefore, it is possible to control the ion beam vertically and horizontally while controlling the vertical direction and the horizontal direction, and it is possible to irradiate the desired portion of the desired dynode or channel electrode with the ion beam.

FIG. 44 is a diagram showing an embodiment in which the central hole of the present invention is applied to a channel type secondary electron multiplier. A substrate side wall 671-3 having a central hole 674-3 of length L is formed in the ion detection chamber 677. The ion detection chamber 677 is a hollow chamber in which a part or all of the main substrate between the upper substrate 672 and the lower substrate 673 is hollowed out while the upper substrate 672, the main substrate 671, and the lower substrate 673 are attached. The ion detection chamber 677 has a substrate side wall (partition wall) having a central hole 674-1 included in a substrate side wall (partition wall) 671-1 that separates the ion detection chamber 677 and the adjacent chamber by an ion beam 678 that is incident from the adjacent chamber, for example, a mass spectrometry room. 671-1, a parallel plate electrode 676-1-1, which bends the ion beam 678 and hits a predetermined inner wall of the central hole 674-3 of the channel type secondary electron multiplier 680, and a central hole 674 through which the ion beam passes. 2 having a substrate side wall 671-2, a channel type secondary electron multiplier 680, a collector electrode 676-4 irradiated by a secondary electron beam 679-n emitted from the channel type secondary electron multiplier 680, and a collector electrode. It has a substrate side wall 671-4 for supporting (attaching (stacking)) 676-4. In the present invention, the collector electrode can also be laminated in the same process as that of another conductor film. For example, a through chamber 677 is formed in the main substrate 671 attached to the upper substrate 672 or the lower substrate 673, and then the main substrate is a conductor substrate (for example, Fe-based, Cu-based, Al-based, conductive C-based) or semiconductor. In the case of a substrate (eg, Si-based, C-based, compound-based), an insulating film (eg, SiOx, SiOxNy, SiNy) is laminated, and then a conductor film (eg, Cu-based, Al-based, conductive C-based, Ti-based, W-based, silicide-based, conductive PolySi-based, Mo-based, Ni-based, Au-based, Ag-based) layers may be stacked and desired patterning may be performed. After that, the upper substrate side and the lower substrate side may be bonded together. Although the collector electrode 676-4 is drawn so as to be formed on the side surface 671-4 of the substrate side wall 671 in the direction perpendicular to the traveling direction of the ion beam 678, it is most easily trapped by the secondary electrons 679-n. It may be formed in For example, the central portion of the substrate side surface 671-4 may be recessed, and this formation method can be performed by performing isotropic etching or controlled side etching at the time of forming the substrate side surface 671-4 (half thereof divided). .. Further, it is possible to easily incline the side surface 671-4 of the substrate side wall 671 with respect to the traveling direction of the ion beam 678. Furthermore, the ion detection chamber with the collector electrode (the ion detection chamber from the place where the secondary electron multiplier tube 680 is exited) is located in the side direction of the main substrate (perpendicular to the thickness direction of the main substrate, with respect to the plane of FIG. It may be produced by expanding in a right angle direction) and expanding.

The parallel plate electrodes 676-1 (676-1-1, 2) in FIG. 44 are also electrodes formed in the central hole similarly to those shown in FIG. 43, but on the upper substrate 672 and the lower substrate 673, and on the main substrate surface. It differs from that shown in FIG. 43 in that it is parallel electrodes. (The one shown in FIG. 43 is formed in the vertical direction on the upper substrate 672, the lower substrate 673, and the surface of the main substrate.) This forming method is as described above, but the conductor film 676-1- is used. After forming 1, the bottom surface side of the central hole 674-2 is covered with a photosensitive film, the photosensitive film on the side surface side is removed, and the conductive film on the side surface side is removed by etching using those patterns as a mask. good. Alternatively, the parallel plate electrodes can be manufactured by forming the upper electrode on the lower surface of the upper substrate 672 and the lower electrode on the lower substrate 673 without using the substrate side wall. In this case, after the main substrate 671 is attached to the upper substrate 672 or the lower substrate 673, a through chamber is formed, and then an insulating film and a conductor film are formed, a photosensitive film is patterned, and an upper electrode is formed on the upper substrate 672. The lower electrode may be formed on the lower surface of the lower substrate 673 to form a parallel plate electrode structure, or the upper electrode and the lower electrode may be formed on the upper substrate 672 and the lower substrate 673, respectively. A parallel plate electrode structure can be formed by attaching a main substrate 671 having a chamber or a recess formed therein (matching the patterns of the upper electrode and the lower electrode with the penetrating chamber or the recess). (In the case of a concave portion, it is necessary to remove (etch) the main substrate so as to completely form the through chamber after adhering.) If the distance between the upper and lower electrodes of the central hole is d, the electric field E=V/ Since it is d, the trajectories of ions can be changed by changing d and V. That is, when obtaining the same amount of change in ion trajectory, the applied voltage V can be small if d is small. The maximum value of d is when there is no side wall of the main substrate 671, and then d is substantially equal to the thickness of the main substrate. (In practice, it is also necessary to consider the thickness of the insulating film and the conductor film.)

Next, the secondary electron multiplier 680 will be described in detail. By using the present invention, a channel type secondary electron multiplier can be manufactured by a simple process. That is, the substrate side wall 671-3 having the central hole 674-3 having the length L is manufactured. In this manufacturing method, the main substrate 671 is divided into two to form a recess having a depth of d/2 and a width of e, as in the conventional method. If the vertical etching method is used, a concave section having a rectangular cross section is formed, and if the side etching method is used, an inclined concave section (which may be called a substantially trapezoidal shape) can be formed. (It may have a slightly curved shape.) Next, the substrate side wall 671-3 of the main substrate 671 (this length becomes the channel length of the secondary electron multiplier) is manufactured. That is, the main substrate 671 other than the substrate side walls 671-3 and the like (including other substrate side wall patterns) is etched to form the ion detection chamber 677 which is a penetration chamber. After that, the insulating film and the secondary electron emitting material 675 are laminated on the recess 674-3, the side wall of the substrate, the through chamber, etc., and then the secondary electron emitting material 675 is formed on the recess 674-3 and the side wall of the substrate as shown in FIG. The secondary electron emission material 675 is left in the side surface portions of both ends of 671-3 (and the upper substrate 672, the lower substrate 673, and the portions required for the side surfaces of the through chamber 677 of the substrate 671), and the other portions are etched. Next, a conductor film 676 is stacked, and wirings 676-2 (676-2-1, 2) and 676-3 (676-3-1, 2) are contacted with both end portions of the secondary electron emission material 675. ) And other wirings 676-1 (676-1-1, 2), collector electrodes 676-4, etc. are formed. After that, a protective film (for example, SiOx, SiOxNy, SiNy) that protects the conductor film 676 may be formed. Then, the upper substrate side and the lower substrate side are bonded (attached).

FIG. 44B shows a cross-sectional view of AA′ in FIG. 44A after the attachment. The central hole 674-3 is surrounded by the insulating film 674-3 laminated on the main substrate 671 (671-3) and the secondary electron emitting material 675 laminated thereon. Secondary cavities 674-3 proceed while the secondary electrons are multiplied. That is, the ion beam 678 hits the vicinity of the entrance of a cavity (called a channel), and secondary electrons 679-1 are generated there. Electrodes 676-2 (676-2-1, 2) on the inlet side of the secondary electron multiplier 680 and electrodes 676-3 (676-3-1, 2) on the outlet side of the secondary electron multiplier 680. A voltage V is applied between (the voltage on the inlet side is made more negative than the outlet side. For example, when the outlet side is ₀ V, -P ₀ V (P ₀ >0) is applied to the outlet side. As the secondary electron multiplier becomes more positive, the number of emitted electrons increases while the electrons successively hit the secondary electron emitting material 675. At the outlet, the voltage of the collector 676-4 is changed to the outlet side. If it is set on the positive side of the electrode 676-3 (676-3-1, 2), the last secondary electron (for example, the outlet side is 0 V and the collector voltage is Q ₀ V (Q ₀ >0)). The collector current 679-n is collected in the collector 676-4, and the collector current can be detected.The shape of the central hole 674-3 can be variously changed at the time of etching the recess, so that the optimum shape can be selected. An electrode made of a parallel plate type secondary emission electron substance can also be formed by removing the secondary electron emission substance on the side surface or above and below the upper substrate 672, the lower substrate 673, and the side wall 671-3 of the main substrate 671. By stacking the secondary electron emission material on the side surface of the main substrate 671 (in the direction perpendicular to the paper surface of FIG. 44), the depth d is approximately the thickness of the main substrate 671 and the width e is approximately the width of the main substrate side surface. A type (parallel plate type or pipe type (with secondary electron emitting substance connected inside) type) secondary electron multiplier can also be produced.

Further, it is difficult to gradually increase the channel depth (thickness direction of the main substrate) d in the traveling direction, but gradually increase the channel width (side direction of the main substrate, that is, the direction perpendicular to the paper surface of FIG. 44) e in the traveling direction. Since it is easy to increase continuously (it can be easily made with a mask), the gradient electric field can be easily made. Therefore, the gradient electric field can be realized without making the channel length L too long. It is possible to control the orbit of the ion beam up and down (method of FIG. 44) or left and right (method of FIG. 42 and FIG. 43) by applying an electric field with the parallel plate electrodes. When the secondary electron multiplier 680 has a parallel plate type structure, its electrode structure is a vertical type because the generated secondary electrons are attracted to the electric field if they correspond to the location of the secondary electron emitting material. However, it is possible to multiply the secondary electrons without any problem even with the right or left type. Alternatively, even if there is no parallel plate electrode that changes the trajectory of the ion beam, if it is directly injected into the secondary electron multiplier 680, it is attracted to the electric field and hits the secondary electron emitting material to generate secondary electrons, After that, the secondary electrons can be multiplied by being attracted to the electric field. However, if there is a parallel plate electrode, the ion beam can be irradiated to a desired place of the secondary electron multiplier, so that the length and size (d and e) of the secondary electron multiplier can be reduced.

In the mass spectrometer of the present invention, glass substrates are attached to the upper and lower surfaces of a Si substrate (4 inch wafer or more) to form a plurality of through chambers in the Si wafer. Adjacent through chambers are partitioned by a substrate side wall plate having a central hole (a horizontal groove parallel to the substrate surface is formed in the center). There are various methods of forming the through-hole having the central hole. For example, the upper and lower sides of the central hole are divided into upper and lower parts by dividing them into upper and lower parts separately in the vicinity of the middle of the central hole. It can be made by adhering at the place. That is, it is a collective substrate type device.
FIG. 45 shows a sectional view (perpendicular to the substrate surface) of the present mass spectrometer using a Si substrate (4 inch wafer or more) having glass substrates attached to the upper and lower surfaces. FIG. 46(a) is a plan view (cross-sectional view parallel to the substrate surface) of the mass spectrometric section including the electric field section and the magnetic field section. FIG. 46B is a plan view showing another embodiment of the magnetic field section and the ion detection section. As shown in FIG. 45, this mass spectrometer is composed of a sample supply unit, an ionization unit, an extraction electrode unit, a mass analysis unit, and an ion detection unit.
The sample gas or sample liquid supplied from the sample supply unit is atomized (gas) at the outlet of the ionization unit and ionized at the ionization unit to which a high electric field is applied. The generated ions are attracted by the extraction electrode of the extraction electrode/acceleration electrode unit, accelerated or decelerated/focused, enter the mass analysis unit having the electric field chamber and the magnetic field chamber, and enter the mass-to-charge ratio m/z ( It is selected according to (m: mass, z: electric charge) and emitted to the ion detector. The ionic charge is electron-multiplied by the ionic detector, and the ionic quantity is detected as a current. The present invention can also be said to be a collective substrate type device of a mass spectrometer (GC-MS, LC-MS) combined with gas chromatography or liquid chromatography. (It can be applied to a solid sample.) An outline of each part will be described with reference to FIG.

<A. Sample supply section>
The sample supply section and the ionization section shown in FIG. 45 are obtained by applying the electrospray ionization method (ESI) to the present invention. Since a sample uses a liquid (sample solution) containing a target substance (sample), it is a kind of liquid chromatography (LC)-ESI method. A sample introduction line 17 into which the sample liquid enters is connected to the opening 14 of the upper substrate 2. A central hole (sample introducing pipe) 11-1 formed in the center (in the thickness direction) of the Si substrate is formed, and the inlet side of the central hole (sample introducing pipe) 11-1 is formed in the thickness direction. The vertical hole (sample introducing pipe) 13 is connected to the vertical hole (sample introducing pipe) 13, and the vertical hole (sample introducing pipe) 13 is connected to the opening 14 of the upper substrate 2. The outlet side of the central hole (sample introduction tube) 11-1 is connected to the ionization chamber 4-1 of the ionization section. The sample solution enters from the arrow A, and the central hole (sample introduction tube) 11-1 is a capillary (capillary tube), so it spreads when it enters the ionization chamber, and atomization (gasification) (symbol A-1 (Also referred to as spray gas).
The sizes of the opening 14 and the vertical hole (sample introduction tube) 13 of the upper substrate 2 can be relatively freely selected. The size of the central hole (sample introduction tube) 11-1 depends on the thickness of the Si substrate 11, but the thickness can be freely increased by stacking the Si substrate 11 as well. Therefore, for example, the thickness of the Si substrate 11 can be adjusted in the range of 0.5 mm to 10 mm (of course, it can be adjusted in a wider range), and the diameter of the central hole (sample introduction tube) 11-1 is 50 μm to 1 mm accurately. It can be produced and can function as a capillary tube. Since the heating conductor films 9-7 and 10-7 can also be formed in the central hole (sample introduction tube) 11-1, the sample can also be heated. Alternatively, the shape 15 is vertically provided on the upper surface of the upper substrate 2 through the contact wiring 5 formed on the upper substrate 2 through the conductor film electrode 9-1 which is recessed outside the central hole 11-1. It is also possible to raise the temperature in the central hole 11-1 by flowing a hot liquid or gas, or by forming a thin film resistor and electrically heating it.

<B. Ionization Department>
The ionization chamber 4-1 is a through chamber formed in the Si substrate 1. The upper part is an upper substrate (for example, a glass substrate or a quartz substrate) 2, the lower part is a lower substrate 3, and the left side surface (in FIG. 45) is the center. The side wall 1-1 of the substrate having the hole 11-1, the side wall plate 1-2 of the right side having the central hole 11-2, the back side surface and the front side surface are also formed by the Si substrate side wall (not shown in FIG. 45). being surrounded.
An outer electrode 7-1 formed with a conductor film electrode 9-1 is connected to a part of the lower surface of the upper substrate 2. Further, the conductor film electrode 9-1 is connected to the conductor film electrode 9-7 on the inner surface of the central hole.
A conductor film electrode 10-1 is formed on part of the upper surface of the lower substrate 3, and the conductor film electrode 10-1 is formed on the lower surface of the lower substrate 3 through the contact wiring 6 formed on the lower substrate 3. The outer electrode 8-1 is connected. Further, the conductor film electrode 10-1 is connected to the conductor film electrode 10-7 on the inner surface of the central hole.
The conductor film electrode 9-1 can be formed by being formed on the upper substrate 2 and then attached to the Si substrate 1. Alternatively, it is possible to form the through chamber 4-1 in the Si substrate 1 to which the upper substrate 2 is attached and then form the conductor film electrode 9-1. At this time, since the central hole 11-1 can also be formed, the conductor film electrode 9-7 can also be formed on the inner surface of the central hole. The same applies to the conductor film electrodes 10-1 and 10-7. Although not shown in the penetration chamber, an insulating film (laminated by a CVD method or the like, for example, a SiO2 film or a SiN film) is formed between the conductor film and the Si substrate 1. (Note that the insulating film does not describe other portions.) Further, an insulating film can be formed as a protective film on the conductor film.
The Si substrate 1u attached to the upper substrate 2 side and the Si substrate 1b attached to the lower substrate 3 side are attached on the Si side surface after forming a through chamber, a central hole, an insulating film, a conductor film, and a protective film. (Adhesive surface is indicated by the one-dot chain line M). As the attachment method, room temperature bonding, bonding using an adhesive, electrostatic anodic bonding with a glass substrate sandwiched therebetween, or the like can be used.
Therefore, a high voltage of 2000 V to 4000 V can be applied from the outer electrodes 7-1 and 8-1 to the conductor film electrodes 9-7 and 10-7 on the inner surface of the central hole 11-1 as a capillary tube. (The counter electrode is the conductor film electrode 10-2-1 on the side wall plate 1-2 of the substrate.) As a result, the sample solution passes through the central hole 11-1 which is a capillary tube and exits from the ionization chamber 4-1. The charged liquid droplets (spray gas) A-1 in 18 are discharged to the penetration chamber 4-1.
The inside of the penetration chamber 4-1 can be heated by using a part of the conductor film electrodes 9-1 and 10-1. Further, the openings 16 are provided in the upper and lower substrates 2 and 3 and connected to a pump to vaporize. It is also possible to quickly discharge the solvent. Further, since the central hole 11-1 can be heated as described above, the gasification of the sample liquid A can be assisted. As a result, the charged droplets (spray gas) are made into fine particles and dried, and the sample is ionized.
In order to prevent the temperature of the ionization chamber 4-1 from being transmitted to other parts, a recess similar to the recess 15 is provided around the ionization chamber 4-1 and around the central hole 11-1, and the recess is cooled. Gas (dry ice gas, etc.) or cooling water can also be introduced. Further, with respect to dirt in the ionization chamber or the like, a purge gas, a cleaning gas, a cleaning liquid, or the like can be introduced from the opening to keep a clean state at all times. Since the volume of the penetration chamber of the present invention is very small, it is easy to return to the original state in a short time even after cleaning.
As the ionization method, the following other ionization methods can also be manufactured with the collective substrate type of the present invention, so other ionization methods will be examined with TEG (test pattern). Also, ions generated outside can be introduced through an opening provided in the ionization chamber 4-1.

<(1) Atmospheric pressure chemical ionization (APCI), (2) Atmospheric pressure photoionization (APPI), (3) Electron ionization (EI), (4) Ionization by high frequency plasma by parallel plate electrodes>
For example, (3) electron ionization (EI) will be briefly described with reference to FIG. The ionization chamber 34-1 is a through chamber formed in the Si substrate 31 in which the upper substrate 32 and the lower substrate 31 are attached to the upper and lower surfaces, the sample gas G is introduced through the opening 42, and the opening 43 is evacuated. To low pressure. A filament 41 of a tungsten (W) film is formed on the lower substrate surface, a current flows through the outer electrodes 38-1-1 and 38-1-2, the filament 41 is heated, and thermoelectrons (e) are generated. The thermoelectrons e fly toward the electron trap electrodes 39-1-2 formed on the facing upper substrate surface. (Ionization voltage 50V to 100V) The sample gas G introduced into the ionization chamber 34-1 is ionized by thermoelectrons. (M+e ⁻ →M ⁺ +2e−) The generated ions are pushed out by the conductor film electrode (repeller electrode) 40-1-1 formed on the side surface of the substrate side wall 31-1, and the ion next to the ionization chamber 34-1. It is sent to the extraction electrode/acceleration electrode chamber 34-2. In the extraction electrode/acceleration electrode chamber 34-2, the ions are accelerated by the extraction electrode/acceleration electrodes 40-2-1 and 40-2 and enter the adjacent mass analysis chamber shown in FIG. 45 and the like. If necessary, the electrodes are further arranged to accelerate or converge.
The electromagnet coil B-3 is arranged outside the upper substrate. (Lower N pole) The electromagnet coil B-4 is arranged outside the lower substrate. (Upper N pole) By thus sandwiching the ionization chamber with the magnet, the thermoelectrons e emitted from the filament 41 travel toward the electron trap electrode 39-2-2 while drawing a spiral by the magnetic field, and the collision time with the sample gas molecule. (Opportunity) can be increased, and the ionization efficiency can be increased.
Other methods can be produced by the present invention, and the optimum method can be selected depending on the ion species.

<C. Lead electrode part>
The extraction electrode chamber 4-2 is partitioned from the ionization chamber 4-1 by a Si substrate side wall plate 1-2 having a central hole 11-2. A Si substrate side wall plate 1-3 having a central hole 11-3 is arranged close to the Si substrate side wall plate 1-2, and the conductor film electrode 10 is provided on the side surface of the Si substrate side wall plate 1-2 and the central hole 11-3. -2-2 is formed and connected to the outer electrode 8-2-2. The conductor film electrode 10-2-1 is formed on the side surface of the Si substrate side wall plate 1-2 facing the conductor film electrode 10-2-2 on the side surface of the Si substrate side wall plate 1-2. Connect to the outer electrode 8-2-1. The conductor film electrode 10-2-1 of the Si substrate side wall plate 1-2 is grounded, and the voltage of the opposite electric charge to the ions is applied to the conductor film electrode 10-2-2 of the Si substrate side wall plate 1-3. There is. Ions generated in the ionization chamber enter the extraction electrode chamber 4-2 through the central hole 11-2 of the Si substrate side wall plate 1-2, and are drawn to the conductor film electrode 10-2-2 which is the extraction electrode. It is accelerated and emitted to the adjacent chamber through the central hole 11-3 of the Si substrate side wall plate 1-3. If the voltage applied to the extraction electrode 10-2-2 is V ₁ , 1/2mv ² =zeV ₁ (i) is established. (Mass of m ions, velocity of v ions, number of z charges, elementary amount of e charges, V applied voltage)
When m=10 ⁻²⁵ kg and V ₁ =10V, the ion velocity v=4.5×10 ³ m/sec.
An opening 14 for vacuuming is formed in the extraction electrode chamber 4-2 and is maintained at a predetermined pressure. Further, the opening 14 is provided in addition to the one for evacuation, and the extraction electrode chamber 4-2 can be cleaned by introducing an inert gas such as Ar.
Furthermore, if necessary, the extraction electrode chamber 4-2 is provided with a substrate side wall plate (also forming a conductive film) having a central hole having the same structure as that of the extraction electrode so as to accelerate by applying a reverse voltage to ions, Alternatively, the same voltage as that of the ions can be applied to decelerate and focus.
<D. Mass Spectrometer>
The mass spectrometric section is a double focusing type having an electric field section and a magnetic field section. (In the case of the single convergence type, the electric field part is eliminated.)
<D-1. Electric field section>
The ions accelerated in the extraction electrode portion enter the electric field chamber 4-3 through the central hole 11-4 of the Si substrate side wall plate 1-4 (velocity v). The electric field chamber 4-3 is a fan-shaped penetration chamber, and has two facing side surfaces of the fan-shaped Si substrate 1 (see FIG. 46A). In FIG. 45, the rear Si substrate side surface and the front Si substrate side surface. ) Is formed with a conductor film electrode 10-8 (10-8-1, 10-8-2). The voltage V ₂ can be applied to the conductor film electrode 10-8 from the outer electrodes 7-3 and 8-3. When the center orbital radius of the sector type field chamber 4-3 r, conductive film electrode 10-8 (the 10-8-1,10-8-2) between the distance and _{d, zeV 2 / d = mv} 2 / r (ii). From (i) and (ii), r=2dV ₁ /V ₂ . For example, if d=10 mm, V ₁ =10 V, V ₂ =5 V, then r=40 mm. Therefore, a 4-inch wafer can be manufactured.
An energy filter chamber 4-6 is arranged between the electric field chamber 4-3 and the magnetic field chamber 4-4, and a slit serving as an energy filter (the center of the substrate side wall plate 1-5-2 has a vicinity of a converging surface converged by the electric field). The holes 11-5-2) are arranged so that only ions having a certain range of kinetic energy pass through.

<D-2. Magnetic field section>
The ions selected by the electric field pass through the central hole 11-5-3 of the side wall plate 1-5-3 of the Si substrate, enter the magnetic field chamber at a velocity v, and are orbitally bent by the fan-shaped magnetic field B, and have a radius R center. Draw a trajectory. {ZevB=mv ² /R (iii)}
In the magnetic field chamber 4-4, the magnetic field B is applied in the direction perpendicular to the substrate surface. That is, a B-1 electromagnet (coil) is arranged on the upper surface of the upper substrate 2, and a coil axis is arranged on the lower surface of the lower substrate 3 so that the coil axis is perpendicular to the substrate surface. Assuming that the ion velocity estimated from equation (i) is 10 ³ to 10 ⁵ m/sec, R=4 cm, and the thickness of the Si substrate (height of the magnetic field chamber) is 1 mm, the magnetic field H(=B/μ ₀ , μ ₀ The magnetic permeability is 10 ⁴ H (v=10 ³ m/sec), 10 ⁵ H (v=10 ⁴ m/sec), and 10 ⁶ H (v=10 ⁵ m/sec). Such a magnetic field is approximately 0.1 A (v=10 ³ m/sec), 1 A (v=10 ⁴ m/sec), 10 A (v=v) for a coil with a coil wiring diameter of 90 μm, a coil diameter of 1 mm, and a coil with 100 turns. It is obtained by passing a current of 10 ⁵ m/sec).
Such a coil can also be realized by stacking coil wiring (Cu or the like formed by the PVD method and the plating method) on the substrate. (Patent pending) Since the size of the coil formed on the substrate can be made small (coils with a diameter of 0.1 mm to 1 mm or less can be easily made), sufficient magnetic field strength can be applied to the magnetic field chamber even if the magnetic field chamber is small. it can. Further, by using the coil formed on the substrate, the coil can be arranged at a predetermined position of the magnetic field chamber very accurately (alignment error of 5 μm or less). In particular, the coils can be arranged on the surface of the substrate without any gap (at intervals of 10 μm or less), and the current of each coil can be controlled. Therefore, the magnetic field strength of the magnetic field chamber is uniform in the area where multiple coils are arranged. Can also be held at.
If the thickness of the interlayer insulating film of the coil wiring is set to 10 μm and double winding wiring is used (in the case of a substrate forming coil, multiple winding can be easily manufactured without increasing the number of processes), the coil height of the above size becomes about 5 mm. If the coil wiring is made of a superconductor (for example, Nb-based or high-temperature superconducting material), a large current can be passed, so that the magnetic field strength can be adjusted in a wide range, and the present invention can be applied to molecules with a large mass. Even if the coil area is dipped in liquid He, a small volume is required, and thus running costs are low.

<Survey and research on simultaneous detection method for multiple ions>
According to the present invention, a large number of ion detectors can be manufactured at the same time (without cost increase). Since these detection units have the same size and the same performance, there is little variation in the detection capability of each ion species, and absolute comparison is possible. An example thereof is shown in FIG.
FIG. 46B is a plan view showing a mass spectrometer in which a large number of ion detectors are provided around the magnetic field unit. Ions 24 that have advanced through the penetration electrode 22-1 which is the extraction electrode/acceleration electrode chamber or the energy filter chamber shown in FIG. 46(a) move from the central hole 27 of the Si substrate side wall plate 21-1 to the penetration chamber 22-2. Is emitted. A part of the penetration chamber 22-2 directly connected to the penetration chamber 22-1 is a magnetic field chamber B, and the ions emitted from the penetration chamber 22-1 always pass through the magnetic field chamber B. The magnetic field B is applied at 180 degrees with respect to the ion incident axis. The magnetic field chamber B is a rectangular (square, rectangular, etc.) or semicircular magnetic field, and the magnetic field B is applied perpendicularly to the substrate surface. The outer periphery of the penetration chamber 22-1 has a rectangular shape or a circular shape, and a large number of ion detection units 22-4 (22-4-1-n, 22-4-2-m, 22 are arranged along the outer periphery thereof. -4-3-p, 22-4-4-q, m, n, p, q=1, 2,...) are arranged. As can be seen from the equation (iii), under the uniform magnetic field B, the ion orbit radius R depends on the mass-to-charge ratio and the mass-to-charge ratio m/z. Enter Therefore, a large number of ion species can be identified simultaneously without sweeping the magnetic field B. Further, if the magnetic field B is swept, information on a larger number of ion species can be obtained, and from this large amount of information, it is possible to perform analysis with higher accuracy than in the past.
With conventional devices, the size of the device is extremely large, it is difficult to manufacture the device, it takes time to manufacture, it is difficult to match the performance of individual ion detectors, and the manufacturing cost becomes enormous. Therefore, it was impossible to fabricate the structure shown in FIG. 46B, but the present invention has a great merit that it can be easily fabricated.

<E. Ion detector>
The ions selected in the mass analysis chamber 4-4 enter the ion detection chamber 4-5 through the central hole 11-6 of the substrate side wall plate 1-6. The conductor film electrode 9-3 formed on the upper surface of the central hole 11-6 and the conductor film electrode 10-3 formed on the lower surface are parallel plate electrodes, and the outer electrode 7-4 connected to these electrodes. The trajectories of the ions can be changed in the vertical direction by adjusting the voltages applied to and 8-4. A substrate side wall plate 1-7 (length L) having a central hole 11-7 serving as an electron multiplier is formed in the ion detection chamber 4-5. When the electron multiplier is a parallel plate type, the secondary electron emitting material film 12 (12-1, 12-2) is formed on the bottom and side surfaces of both ends of the central hole 11-7 and a part of the upper substrate/lower substrate. ) Is formed, a secondary electron emission material film is formed on the entire inner surface of the central hole 11-7 and side surfaces at both ends, and a part of the upper substrate/lower substrate when the electron multiplier is a channel type. The secondary electron emitting substance is, for example, MgO, Mg or BeO. Conductor films 9-4, 9-5, 10-4, 10-5 are formed on both ends of the substrate side wall plate 1-7, and outer electrodes 7-5, 7-7, 8-5 are provided through the contact wirings 5, 6. , 8-6. By applying a voltage (the rear is positive with respect to the front) to both ends of the substrate side wall plate 1-7, a gradient electric field is formed in the length L direction of the secondary electron emission material films 12-1 and 12-2. It When the ions that have entered the ion detection chamber 4-5 are bent and hit the front of the secondary electron emission material film 12-1, secondary electrons e are emitted. When the secondary electron e hits the facing secondary electron emission material film 12-2, the next secondary electron e is emitted. When this secondary electron e hits the facing secondary electron emission material film 12-1, the next secondary electron e is emitted. The amount of secondary electrons emitted by repeating these processes is multiplied one after another, and the multiplied electrons come out from the central hole 11-7, which is an electron multiplier tube, and are formed on the side wall of the Si substrate behind them. An electric current flows through the contact 5 to the outer electrode 7-7, reaching the conductor film electrodes 9-6 and 10-6. That is, the selected amount of ions can be detected.

<Conceptual diagram of final product>
FIG. 48 is an image completed view of the final product (only the main body) of the present invention. That is, a sample supply part, an ionization part, an extraction electrode/acceleration electrode part, a mass spectrometric part {electric field part (1/ (4 fan shape), magnetic field part (1/4 fan shape)}, and a mass spectrometer having an ion detection part. The vacuum system is attached externally. As shown in the figure, a plurality of sample supply units can be arranged, and a liquid sample or the like is connected to the sample supply unit of the apparatus from the outside. Each functional part is connected to an electrode by a conductor film wiring and can be controlled by a control and analysis LSI. When a superconducting magnet is used in the magnetic field part, a substrate frame container can be provided in that part to cool to a cryogenic temperature. As described above, the mass spectrometer of the present invention has a size that can be accommodated in a wafer (substrate) of 4 inches to 8 inches, and a very small mass analyzer can be manufactured at extremely low cost. The resolution depends largely on the size of the electric field and magnetic field, but it is possible to process with extremely high accuracy, and there is no assembly error, so a precise device can be manufactured. It is thought that an accuracy of more than 10,000) will be obtained.

<The novelty and superiority of the present invention>
Using a substrate of 4 inches to 8 inches {diameter 100 mm to 200 mm, thickness 3 mm or less (Si substrate 2 mm, glass substrate 0.3 mm x 2), 8 inches or more} as in the present invention, a minute sample supply unit It has not been reported that an ionization chamber, an extraction electrode/acceleration chamber, an electric field chamber, a magnetic field chamber, and an ion detection chamber (these are referred to as functional units) have been produced. In addition, no idea such as a patent has been found. Furthermore, it has not been reported that they are realized on the same substrate all at once, and it has novelty, inventive step and superiority.
This mass spectrometer is ultra-compact {main body: size 6 inch wafer (50 cm ³ ) or less, weight 130 g or less} and it is a batch manufacturing, so the manufacturing cost is 100,000 yen or less {main body: size 6 inch wafer} it can. With the same performance, the conventional products are 50 cm x 50 cm x 50 cm or more and 20 kg or more, so the size (volume) is 1/2500 or less, the weight is 1/100 or less, and the price is 1/20 or less. There is enough advantage.
Since each functional part can be manufactured collectively and with high accuracy (1 μm or less), it can be manufactured much more accurately than other parts assembling methods, so that detection accuracy can be expected to be about the same as or higher than conventional ones.
Since the present invention is ultra-compact and lightweight, it can be carried, so that in-situ observation is possible. However, in-situ observation is extremely difficult because conventional products can hardly be carried, and this is also a great advantage.
Further, in this mass spectrometer, a coil for making a substrate is used in the magnetic field chamber. Since the coils are arranged by aligning between the substrates, the arrangement accuracy is 10 μm or less, which is very good. Moreover, the size of the coil is as small as 1 mm to 10 mm, so the overall size does not increase. A magnetic field chamber using such a substrate coil is highly novel and innovative. The price and size are small and the accuracy is high, so it has a significant advantage over conventional products. The coil is also used in the electron ionization method. This is also highly novel and inventive.

<Details of social contribution expected from development results>
From the results obtained by the present invention, it is found that the mass spectrometry layer can be produced in a substrate type, which increases the possibility of developing an apparatus (mass production machine).
Even if the price including the vacuum system is less than 200,000 yen, you can have one mass spectrometer for each home. Therefore, the quality of water and food can be inspected at home, and the awareness of food safety is dramatically improved.
The size is about the size of a small attache case (30 cm × 20 cm × 5 cm) including the vacuum system, so you can easily carry it. Therefore, radioactive cesium (137Cs), which is a problem in Fukushima nuclear pollution, can be analyzed on the spot, and human safety can be improved by not approaching dangerous areas.
Since the substance can be directly analyzed even at the crime scene, it can assist in the quick investigation of the cause and the identification of the offender, and as a result, it also serves as a deterrent to the crime.
In addition, archaeologists and environmental scientists can make precise in-situ observations in the field, which greatly enhances the development of science and technology. Also, since it is cheap and small, it can be purchased in large quantities and a large number of analyzes can be performed quickly.
As described above, the mass spectrometer can be made familiar to individuals and contribute to the realization of a safe and secure society.
Further, the present invention is applicable to other types of mass spectrometers such as quadrupole type, ion trap type, tandem type, time-of-flight type, FT-ICR (Fourier transform ion cyclotron resonance). A wide range of applications can be expected by making various selections according to the requirements.
Furthermore, it can also be applied to ion implantation equipment, and the equipment price can be reduced from the current approximately 100 million yen to the million yen range. It can greatly contribute to cost reduction of semiconductor price.
Further, since the structure of this mass spectrometer can be applied to an accelerator (linear accelerator, synchrotron, microtron, etc.), the conventional super-large accelerator can be made ultra-compact.
For example, a synchrotron with a diameter of 100 m may be downsized to a diameter of 10 m, and a lineartron (ILC) with a length of 30 km may be downsized to 1 km or less.
The manufacturing cost will be drastically reduced, and there is a possibility of achieving less than 1 million yen/unit for medical use, and cancers of all cancer patients can be treated cheaply.
Furthermore, since the system can be formed in a lump by using the substrate, a small and precise product can be manufactured at a low cost, so that it can be applied to various products. At one time, it was hoped that the era of lightness, thinness, shortness, and smallness would arrive, but it did not materialize. With the present invention as an opportunity, the age of lightness, thinness, shortness and smallness can be realized by using semiconductor/MEMS technology as a weapon.

FIG. 50 is a diagram showing a method or apparatus for forming a pattern on a side wall of a substrate through hole or a substrate recess. A case where a through hole (or a recess) 1009 is formed in the main substrate 1011 and a conductor pattern such as an electrode or wiring is formed on the side wall of the through hole 1009 will be described. An insulating film 1012 is laminated on the side surface of the through hole 1009 of the substrate 1011. As the substrate 1011, a substrate suitable for the purpose of use is used. In the case of a mass spectrometer, an accelerator, etc., the substrate is various semiconductor substrates such as silicon (Si), SiC, GaN, InP, C, etc., insulating substrates such as glass, quartz, sapphire, various plastics, various ceramics or semi-insulating substrates, A conductor substrate such as a metal such as Al, Cu or Fe or an alloy can be used. The insulating film 1012 is, for example, a silicon oxide film, a silicon oxynitride film, or a silicon nitride film. In the case of a silicon oxide film, it can be formed by an oxidation method, a CVD method, a PVD method, a coating method, or the like. When the substrate 1011 is an insulating substrate, the insulating film 1012 is not always necessary, but it is better to stack the insulating film 1012 in order to improve the adhesiveness with the adhesive layer 1013 laminated thereon. An adhesion layer 1013 is stacked on the insulating film 1012. The adhesion layer 1013 is for improving the adhesion to the conductor film 1014 laminated thereon and for preventing diffusion (barrier). When the conductor film 1014 is a plated layer, it also serves as a seed layer. The adhesion layer 1013 is a conductor film, for example, Ti, TiN, TiO, Ta, TaN, or the like. When the conductor film 1014 is plated with copper (Cu), for example, a Cu film is preferably laminated. These adhesion layers 1013 can be laminated by a CVD method or a PVD method.

A conductor film 1014 is laminated on the adhesion layer 1013. The conductor film 1014 is, for example, a metal film of Cu, Zn, Ni, Al, Au, Ag, W, Mo, Fe or the like, or various metal films. It may be a conductive carbon nanotube or a superconductor. These conductor films 1014 can be stacked by a CVD method, a PVD method, a coating method, or a plating method. In the case of the plating method, the adhesion layer and the seed layer 1013 can be used to energize and perform electroplating. In the case of plating film, various solder plating can be used.

A photosensitive film 1015 is laminated on the conductor film 1014 in order to form electrodes and wirings on the sidewalls of the through holes 1009. The photosensitive film 1015 is a photoresist film, a photosensitive resin, or the like. The photosensitive film 1015 is formed by a coating method, a dipping method, a spray method, an electrodeposition method, or the like. Since it is also necessary to stack the layers inside the through hole 1009, it is easy to set conditions for the dipping method or the electrodeposition method. Since the aspect ratio of the through hole 1009 is not so high (about 0.5 to 2), the photosensitive film 1015 can be formed inside the through hole 1009. After forming the photosensitive film 1015, pre-baking before exposure is performed if necessary.

Next, exposure is performed, but as described above, it is possible to perform exposure by the oblique exposure method. When the aspect ratio is 1, when the deepest bottom of the substrate 1011 is exposed, oblique exposure may be performed at an angle of about 45 degrees in order to make the photosensitive film pattern as vertical as possible. When the photosensitive film pattern is faithful to the exposure angle, the photosensitive film shape is an inverse taper shape of about 45 degrees. When exposing from the front and back to half the thickness of the substrate 1011, the photosensitive film shape has an inverse taper of about 27 degrees. Even if the thickness of the photosensitive film is 2 μm, the pattern shift (difference between the upper and lower portions of the pattern) of the photosensitive film pattern is 1 μm to 2 μm, which is about 1% compared with the electrode area (width) and the wiring pattern area (width). The pattern shift is hardly a problem. Therefore, if the oblique exposure method is used, the photosensitive film pattern in the through hole 1009 can be formed.

Here, an exposure method of the present invention by another method will be described. FIG. 50 shows an exposure method apparatus 1020 using a light emitting body formed on a substrate. A light-emitting body 1022 is formed on both surfaces of the substrate 1021, and the substrate on which the light-emitting body 1022 is formed is sandwiched between transparent substrates 1024 to be used as an exposure device. A portion 1026 through which light from the light emitting body 1022 passes and a portion 1025 through which light does not pass are formed on the transparent substrate 1024. The pattern of this portion 1026 corresponds to the pattern on the side surface of the through hole 1009. Although a space 1023 exists between the light emitter substrate 1021 and the transparent substrate 1024, the space 1023 is formed when the light emitter substrate 1021 is set in the transparent substrate 1024 container. The exposure method apparatus 1020 can also be formed by a method similar to that of the mass spectrometer and the accelerator of the present invention. That is, the through hole 1023 is formed in the substrate 1028, and the light emitting substrate 1021 is attached to one side. A region where the light emitting body 1022 is provided is arranged in the through hole 1023. A transparent substrate 1024 is attached to the other side of the substrate 1028. Here, the through hole 1023 becomes a space. When the light emitters 1022 are formed on both sides of the light emitter substrate 1021, the substrate 1028 and the transparent substrate 1024 may be attached to both sides.

The light emitting body 1022 is, for example, an LED element. The LED element may be directly formed on the substrate 1021, or the LED chip may be mounted on the substrate 1021. The substrate on which the LED element can be directly formed is a compound semiconductor substrate made of GaN, GaAs, InP, or the like, a substrate having various compound semiconductor layers epitaxially formed, or a bonded substrate. The substrate on which the LED chip is mounted is a COB substrate, a ceramic substrate, or the like. A wiring layer is formed on any of the substrates, and the LED element and the LED chip can be turned on. The light emitting body 1022 is also an organic EL (electroluminescence) element. The organic EL element may be directly formed on the substrate, or the organic EL element may be mounted on the substrate. The portion 1025 that does not transmit light from the light-emitting body 1022 can be formed by forming a metal film layer (Al film or the like) on the transparent substrate 1024 and patterning it by an exposure method. It is also possible to obtain a portion 1025 that does not transmit light by mixing a light absorbing material such as carbon with the photosensitive film, patterning the same by an exposure method, and then performing heat treatment. These patterns serve as masks for patterns formed on the side surface of the through hole 1009 on the substrate side.

The exposure apparatus 1020 manufactured as described above is inserted into the through hole 1009, and after alignment, the light emitting body 1022 is turned on and light 1027 is emitted from the portion 1026 through which light passes. This light 1027 selects the light emitter so that it has a wavelength at which the photosensitive film 1015 is exposed. As a result, as shown in FIG. 50B, the photosensitive film patterns 1015-1 and 1015-2 are formed on the substrate sidewall of the through hole 1009. Although the photosensitive film shown in FIG. 50 is positive, a negative photosensitive film can also be used. Since the distance between the exposure device 1020 and the side wall of the substrate of the through hole 1009 is short, the light beam 1027 emitted from the exposure device 1020 is a light beam which is substantially perpendicular to the side wall of the substrate of the through hole 1009. Since the patterns 1015-1 and 1015-2 are substantially vertical patterns, there is almost no pattern deviation. The photosensitive film patterns 1015-3 and 1015-4 can be formed on the upper surface and the lower surface of the substrate 1011 by using a normal exposure method.

Although the depth side (the front surface or the rear surface in the direction perpendicular to the paper surface) is not shown in FIG. 50, the front surface or the rear surface can be exposed by arranging a substrate on which LED elements are similarly formed on the front surface or the rear surface. In this case, the LED is not required on one surface, so when irradiating light on the front surface, the substrate on which the LED elements are arranged is arranged on the front surface. When irradiating the rear surface with light, the substrate on which the LED elements are arranged is arranged on the rear surface. FIG. 53 is a diagram showing an exposure apparatus in which light emitting bodies are arranged on the front surface and the rear surface. The substrate 1061 having the LED elements 1063 arranged on one side thereof is arranged on the side surface (end face, which may be considered to be the end surface) side of the substrate 1021 having the LED elements 1022 arranged on both sides of the exposure apparatus 1020 shown in FIG. Similarly, a substrate 1062 having LED elements arranged on one side is arranged on the side surface (end face, which may be considered as an end surface) side of the substrate 1021. A front side surface 1024 (1024-S3) of a transparent substrate 1024 is arranged on the LED element mounting surface (front surface) side of the substrate 1061 with a space 1023 interposed therebetween, and this transparent substrate 1024 (1024-S3) is also provided. A mask pattern, which is a portion that does not pass light, is formed, and the light of the LED element 1063 mounted on the substrate 1061 also forms a photosensitive film pattern matching the mask pattern on the front side of the through chamber 1009.

Similarly, a rear side surface 1024 (1024-S4) of the transparent substrate 1024 is arranged on the LED element mounting surface (rear surface) side of the substrate 1061 with a space 1023 interposed therebetween. This transparent substrate 1024 (1024-S4). ), a mask pattern, which is a portion that does not pass light, is formed, and a light sensitive film pattern matching the mask pattern is also formed on the rear side of the through chamber 1009 by the light of the LED element mounted on the substrate 1062. It The transparent substrates facing the LED element mounting surface on the side surface of the substrate 1021 are 1024 (1024-S1) and 1024 (1024-S2). The upper surface 1024 (1024-T) of the transparent substrate 1024 is attached to the upper surface of the substrate 1021, and the lower surface 1024 (1024-B) of the transparent substrate 1024 is attached to the lower surface of the substrate 1021. 1021 is supported. The substrates 1061 and 1062 may also be attached to the upper surface 1024 (1024-T) and the lower surface 1024 (1024-B) of the transparent substrate 1024. The substrates 1061 and 1062 may or may not be attached to the end faces (front face, rear face) of the substrate 1021. When not attached, the upper end surfaces and/or the lower end surfaces of the substrates 1061 and 1062 are attached to and supported by the upper surface 1024 (1024-T) and the lower surface 1024 (1024-B) of the transparent substrate 1024. The upper surface 1024 (1024-T) and the lower surface 1024 (1024-B) of the transparent substrate 1024 need not be transparent because they do not need to transmit light. 50, the upper surface 1024 (1024-T) and the lower surface 1024 (1024-B) of the transparent substrate 1024 may be separate substrates 1028 (upper substrate) and 1029 (lower substrate). In that case, the transparent substrate 1024 (1024-S1 to S4) is attached to the separate substrates 1028 and 1029. Photosensitive patterns can be formed on the four sidewalls of the substrate of the through chamber 1009 by the above-described four side exposure apparatus 1020. Even in the state of the art, if the width of the through chamber is 2 mm or more, the substrates 1061 and 1062 can be arranged on the end surface of the substrate 1021 as shown in FIG.

By using these photosensitive film patterns 1015-1 to 101-4 as a mask, the underlying conductive film 1014 and the adhesion layer 1013 can be removed by etching. The etching can be performed by wet etching or dry etching. In the case of wet etching, the through hole 1009 can be filled with an etching solution by dipping to perform etching. In spray etching or irradiation etching, etching can be performed by oblique spray or oblique irradiation. In the case of dry etching, etching gas can be circulated into the through hole 1009 for etching. In directional dry etching (for example, RIE), etching can be performed by oblique irradiation. In the case of these etchings, the side etching amount is about the thickness of the conductor film 1014 to the thickness×2 to 3 or so. When the thickness of the conductor film 1014 is 100 μm, the side etching amount is MAX 300 μm, but if the entire electrode size is about 5 mm, this is not a particularly problematic amount.

FIG. 51 is a diagram showing a through hole side wall etching apparatus 1030. Through holes (chambers) 1032 are formed in the substrate 1031 and substrates 1033 and 1034 are attached to both sides thereof. These manufacturing methods are the same as those described above. An etching solution or etching gas introduction hole 1035 is formed in the central portion or a part of the substrate 1034. The etching gas (liquid) introduction hole 1035 can be formed by bonding the substrates. Alternatively, the etching gas introduction hole 1035 can be formed in the substrate 1033 and/or 1034. A large number of holes 1036 for ejecting etching gas or etching solution are formed in the substrates 1033 and 1034 corresponding to the depth of the through holes 1009. The through hole side wall etching apparatus 1030 is inserted into the through hole 1009, and the etching gas or etching solution injection hole 1036 is arranged in a region corresponding to the side wall of the through hole 1009. The etching gas (liquid) 1037 is introduced from the etching gas (liquid) introducing hole 1035, and the etching gas (liquid) 1038 is further ejected from the etching gas (liquid) ejecting hole 1036 to the side wall of the substrate of the through hole 1009 to form a conductor film. 1014 and the adhesion layer 1013 are etched. As a result, the pattern of the conductor film 104 can be formed on the side wall of the through hole 1009. The jetting etching gas (liquid) 1038 is jetted toward the substrates 1033 and 1034 at an angle close to vertical. Since the distance between the through hole side wall etching apparatus 1030 and the side wall of the substrate of the through hole 1009 is small, the shape of the conductor film 1014 and the like can be obtained close to vertical. Further, since the speed and angle of the etching gas (liquid) 1038 can be adjusted by changing the pressure of the introduced etching gas (liquid) 1037, the etching speed and shape of the conductor film 1014 and the like can be controlled. Dry etching is also possible by generating an electric field between the side of the substrate 1011 to be etched and the conductive substrates 1033 and 1034 using the substrates 1033 and 1034 as conductive substrates, and the etching rate and shape of the conductive film 1014 or the like can be used. Can also be controlled.

Although FIG. 51 shows a substrate side wall surface etching apparatus for the through chamber 1009, the front side and the rear side are not shown, but the front side and the rear side have the same structure. Can be etched. In order to etch the four substrate sidewall surfaces as uniformly as possible, it is better to make the distances between the etching device 1030 and the four substrate sidewall surfaces as equal as possible. Therefore, the etching device 1030 is manufactured according to the size of the through chamber 1009. Good to do. The atmosphere in which the substrate or the like is placed is a low temperature to room temperature to a high temperature at which etching is possible, and is maintained at a low pressure to atmospheric pressure to a high pressure at which etching is possible.

Since the aspect ratio of the through hole 1009 (ratio of the diameter (width) of the through hole to the thickness of the substrate 1011) used in the invention of the present invention is not so large, a film (CVD, PVD, plating, etc.) laminated on the side surface of the through hole. The step coverage (ratio of the thickness of the film on the side surface of the through hole to the flat portion) does not become so small. For example, when the thickness (through hole depth) of the substrate 1011 is 5 mm to 20 mm, the through hole width is also about the same, so the aspect ratio is 1 and the step coverage is about 30 to 80%. Improvements in CVD, PVD, plating and other technologies will improve this step coverage. When the width of the through hole is 5 mm and the width of the substrate side wall exposure device 1020 and the substrate side wall etching device 1030 of the present invention is 4 mm or less, the substrate side wall exposure device 1020 and the substrate side wall etching device 1030 can be inserted without contacting the substrate side walls on both sides. In the case of the substrate sidewall exposure apparatus 1020, the thickness of the light emitter mounting substrate is 0.5 mm, the thickness of the light emitter is 0.2 mm, the thickness of the (main) substrate 1021 is 2 mm, and the thickness of the transparent substrates 1024 on both sides is 0.5 mm. If the thickness of the mask portion 1025 is 0.1 mm, the width of the substrate side wall exposure device 1020 is about 3.2 mm. In the case of the substrate sidewall etching apparatus 1030, if the (main) substrate 1021 has a thickness of 2 mm and the substrates 1033 and 1034 on both sides have a width of 0.5 mm, the substrate sidewall etching apparatus 1030 has a width of about 3 mm. Note that the substrate 1011 has a thickness of 5 mm to 20 mm, the insulating film 1012 has a thickness of 100 nm to 10000 nm, the adhesive layer 1013 has a thickness of 100 nm to 100000 nm, the conductive film 1014 has a thickness of 1 μm to 500 μm, and the photosensitive film 1015 has a thickness of It is also possible to select 1 μm to 500 μm. However, the optimum size can be selected regardless of these sizes.

FIG. 52 is a diagram showing a method of producing a through chamber of an accelerator or a mass spectrometer of the present invention using a mold. FIG. 51 shows a case where the mass spectrometer shown in FIG. 47 is manufactured. As shown in FIG. 52A, a mold 1040 having a sample supply unit/ionization unit 1041, extraction electrode unit 1042, electric field unit 1043, magnetic field unit 1044, and ion detection unit 1045 is produced. As for this mold, a mold may be prepared in advance and a mold may be prepared according to the mold, or it may be assembled and manufactured. As an assembled production, for example, it can be produced using a 3D printer device. The optimum mold material is selected according to the material of the substrate 1046 that covers the mold material. For example, when the material of the substrate 1046 is Si (PolySi, or amorphous Si, or single crystal Si), a material having a melting point and a reaction temperature with the material higher than its formation temperature is selected. For example, there are many materials such as carbon (C), WC, quartz, sapphire and zirconia (ZrO2). These materials can also be powdered and sintered to be molded. The shape of the mold is the same as that of a planar shape (in this case, a mass spectrometer), and is a columnar body having that shape.

A substrate material is crystal-grown around the mold 1040, a molten material is poured to produce an ingot of the substrate material, or a powder material of the substrate material surrounds the periphery of the mold and is sintered to produce an ingot. .. Powder sintering has the advantage that it can be sintered at a temperature lower than the melting point of the powder body. Thus, as shown in FIG. 52B, an ingot 1048 having the mold body 1040 inside is formed. With the mold body 1040 removed, the same cavity as the mold body is formed in the ingot 1048. If this ingot 1048 is cut to the same thickness as the mass spectrometer, a substrate (wafer) having a through chamber can be produced. For example, if the thickness of the substrate is 5 mm, the length of T=1000 mm is 200 substrates. Can be produced. In this way, a large number of substrates having through chambers can be produced at the same time when the substrates are produced without etching the through chambers in the substrate. Substrate cutting from the ingot 1048 includes cutting with a wire saw and cutting using dicing, and after the cutting, necessary polishing, chemical polishing, or CMP is performed to bring the substrate surface and the substrate sidewall surface of the through chamber to a predetermined surface state. Can also The ingot 1048 can be cut while the mold body 1040 is still contained, and the mold body 1040 can be removed after cutting. When the substrate material is Si and the molding material is quartz, sapphire, or the like, the molding material can be removed by performing HF treatment to melt (a part or all of) the molding material. When the substrate material is Si and the molding material is carbon, the carbon material can be changed to CO2 with oxygen to remove the molding material.

When the substrate is plastic, the molding material can be made of metal such as Al, glass, or the like. After the ingot is made, the plastic is not soluble, but the metal can be treated with a soluble solution. When the substrate is a metal or an alloy, the mold material is preferably a material having a higher melting point than the metal or alloy and hardly reacting with each other up to a temperature near the melting point temperature. For example, when the substrate is a solder alloy, the melting point of the solder alloy (Sn-Pb, Sn-Cu, Sn-Ag-Cu, Sn-Zn-Bi, Sn-Zn-Al, etc.) is 150°C to 400°C. Therefore, a heat-resistant polymer material such as polyimide, glass, Si or the like can be used as the molding material. Regarding the coefficient of thermal expansion of the substrate and the molding material, it is preferable that the coefficient of thermal expansion of the molding material is larger than that of the substrate. For example, after the mold is filled with the melted substrate material to form a substrate ingot and then solidified, the mold shrinks more than the substrate when the temperature is lowered, so the molding material can be naturally removed from the substrate ingot. .. The size of the mold is selected in consideration of the size of the cavity (through hole) at the operating temperature (for example, room temperature, when using a superconductor). Also, if a low melting point metal such as solder metal or a low melting point alloy is used as the mold material and the substrate material is composed of a polymer material having a lower melting point such as plastic or cellulose nanofiber (CNF), the production of the substrate ingot is easy. Is.

It is also possible to form an electrode/wiring film on the side surface of the molded body 1040, enclose it with a substrate material, and then transfer the electrode/wiring film to the inner surface of the ingot 1048. For example, the electrode/wiring film is attached to the entire side surface of the molded body 1040, and the electrode/wiring film is transferred to the entire inner surface of the ingot 1048. After the ingot 1048 is cut into a substrate body, the electrode/wiring film formed on the inner surface of the formed penetration chamber is patterned to form an electrode/wiring layer. Alternatively, as shown in FIG. 52A, the electrode/wiring films 1051 and 1052 are partially formed on the side surface of the molded body 1040. The electrode/wiring film 1051 is an electrode/wiring film that is continuous in the depth direction of the ingot 1048, and may be patterned only in the depth direction of the penetration chamber after being cut into a substrate body. Since the electrode/wiring film 1052 is a pattern formed according to the pattern formed on the inner surface of the through-hole of the substrate, patterning of the electrode/wiring film 19052 after cutting into a substrate body is unnecessary. However, it is necessary to accurately form the electrode/wiring film pattern 1052 formed on the side surface of the mold body 1040 at the position of the substrate penetration chamber after cutting. In order to form an electrode/wiring film on the side surface of such a molded body 1040, a CVD method, a PVD method (including an ion plating method), a coating method, a dipping method, or the like may be used. When forming, there is also a method of forming an electrode/wiring film on the mold and transferring the film. Alternatively, the electrode/wiring film can be formed using a 3D printer.

The shape of the ingot 1048 can be various shapes such as a cylindrical shape, a rectangular cross section, a square shape, a triangular shape, various polygonal prisms, and an elliptic cylinder in cross section. The crystal form of the ingot can also be composed of a single crystal, a polycrystal, an amorphous material, a solidified powder body, a resin state, a plastic body, a rubber-like body, or a combination thereof. If the depth of the penetration chamber is large, for example, if it is 10 cm or more, the thickness of the ingot may be the same as the thickness of the penetration chamber, and at that time, only one main substrate can be taken from one ingot. Become. Furthermore, in some cases, the ingot can take only half the thickness of the substrate, and in that case, it is necessary to stack the substrates (by bonding or the like) to form the through chamber. It is also possible to manufacture a flat substrate without inserting a mold and punch the substrate with a mold to manufacture the through chamber. Especially when the substrate is metal, it is easy to punch. Further, the through chamber and the recess can be formed by laser cutting.

Although the central hole is not shown in FIG. 52, FIG. 54 is a diagram showing a method of forming the central hole. There is a mold 1073 forming a central hole between the molds 1071 and 1072 forming the through chamber. FIG. 54A is a perspective view of the mold 1070, which is a perspective view. Central hole molds 1073 connecting between the rectangular parallelepiped molds 1071 and 1072 are arranged at equal intervals. FIG. 54B is a cross-sectional view (height direction) of the mold 1070. The dashed-dotted line 1074 shows a cross section. The mold may be removed after forming a substrate around the molds 1070 fitted with the molds 1071 and 1072 and the central hole mold 1073 and producing a substrate ingot. The mold may be removed after cutting the substrate ingot to produce the (main) substrate. Since the central hole mold 1073 has a smaller size than the molds 1071 and 1072, after separating the molds 1071 and 1072 from the substrate boundary surface, if a light shock is applied, the central hole mold 1073 and the molds 1071 and 1072 can be easily connected. The molds 1071 and 1072 can be folded and separated from the substrate ingot or the substrate after the substrate ingot is cut. When the central hole mold 1073 and the molds 1071 and 1072 are made of the same material, if the central hole mold 1073 and the molds 1071 and 1072 are weakly attached, they can be separated with a lower impact force.

For example, the mold is made of sapphire (aluminum oxide, melting point: about 2070° C.), and the substrate ingot is made of silicon (melting point: 1410° C.). A liquid or gas that etches sapphire rather than silicon is used to etch the boundary between silicon (ingot, substrate) and sapphire (mold) to separate a gap. When the mold is made of quartz (melting point about 1700° C.), the substrate ingot is made of silicon (melting point 1410° C.). The boundary between silicon (ingot, substrate) and quartz is etched by a liquid or gas that etches quartz rather than silicon, and a gap is formed to separate the boundary. An HF solution is used as an etching solution for quartz. The mold is made of Fe (melting point 1540° C.), and the substrate ingot is made of glass (melting point 600° C. to 700° C.). A liquid or gas that etches Fe rather than glass is used to etch the boundary between the glass (ingot, substrate) and Fe (mold) to separate a gap. Hydrochloric acid and sulfuric acid are used as an etching solution for Fe.

The penetrating chamber can also be manufactured by a method in which the mold 1070 is divided into a number of blocks and manufactured by a split mold, and the split mold is removed after the ingot is formed. Even at that time, if it is difficult to remove the central hole mold 1073 from the ingot, the central hole mold 1073 is dissolved with a wet etching solution or an isotropic dry etching gas. Alternatively, as shown in FIG. 54( b ), the central hole mold 1073 can be exposed and removed by cutting at a surface (shown by a broken line) 1075 that passes through a substantially central portion of the central hole. Also in this case, the boundary between the central hole mold and the substrate can be easily etched by using a solution or dry etching gas capable of etching the central hole mold 1073. After separating the mold by cutting along the plane (shown by the broken line) 1075 that passes through substantially the center of the central hole, attach the necessary upper and lower substrates to the through chamber and central hole, and then attach the separated upper and lower substrates at the cutting surface 1075. Then, a substrate having a normal central hole can be manufactured. It is also possible to attach a necessary film around the mold 1070, transfer the film to a substrate (ingot), and form an insulating film, a conductor film, or a pattern thereof on the inner surface of the through chamber or the central hole.

When the central hole mold 1073 is not used, it is necessary to make a central hole for connecting the through chamber to the substrate having the through chamber. First, the substrate ingot is cut along a cutting line (plane) 1076 which is a position approximately half the height of the central hole in the portion where the cutting surface 1074 and the central hole are formed. FIG. 55 is a diagram showing a method of forming a central hole in a substrate cut at a position approximately half the height of the central hole in the portion where the central hole is formed. FIG. 55(a) is a plan view of the substrate before forming the central hole. A plan view of the substrate 1080 on which the through chambers 1076 (1076-1, 2) and the through chambers 1077 (1077-1, 2) are formed is a cut surface 1075 indicated by a broken line in FIG. 54. The penetration chamber 1077 (1077-1, 2) is a penetration chamber of the accelerator or the mass analyzer next to the accelerator or the mass analyzer having the penetration chamber 1076 (1076-1, 2). The central hole has not yet been formed. 1079 is a substrate surface or a substrate. FIG. 55(d) is a sectional view of FIG. 55(a). As shown in FIG. 55B, a photosensitive film 1081 is formed on the substrate surface 1079 and patterned to open a central hole formation region 1082 (1082-1, 1082-1). FIG. 55(e) is a sectional view of FIG. 55(b). Next, as shown in FIG. 55F, the substrate 1079 is etched using the photosensitive film pattern 1081 as a mask to form a central hole 1083. This etching may be formed using a laser or the like. Alternatively, it can be prepared by a polishing method. For example, a cylindrical polishing jig adapted to the size of the central hole is rotated to polish half of the central hole (a semicircular column on the lateral side). At the time of polishing, a polishing agent and water are applied, and a lighter etching solution is mixed to perform polishing. FIG. 55(g) shows a polishing method using a cylindrical polishing jig 1084. The substrate 1079 is polished by applying the cylindrical polishing jig 1084 to the region where the central hole is formed while rotating. The cylindrical polishing jig 1084 is attached to a support base that can move up and down with respect to the substrate 1079, and the support base is gradually lowered, and when the substrate 1079 has been shaved to a predetermined depth, the support base is stopped from descending and raised. As a result, half of the central hole can be formed in the substrate 1079. The photosensitive film pattern 1081 is not necessary when using a cylindrical polishing jig.

A mold can be produced even if the mold is hollow. Enclose the mold with a thin film or plate to make a hollow inside. (It is referred to as a mold frame.) Nitrogen, oxygen, air, an inert gas such as He, Ar, etc. may be introduced into the cavity of the mold frame to apply an appropriate internal pressure. When the temperature is raised when manufacturing the substrate ingot, the gas in the cavity expands, so the internal pressure increases, so the strength of the mold frame is adjusted so as not to deform due to the internal pressure. Alternatively, even if the mold frame is deformed, the strength of the mold frame and the internal pressure in the cavity may be adjusted so that the substrate ingot becomes an accurate mold when being manufactured. Naturally, the mold frame material must be formed of a material that does not deform or melt during the production of the ingot. This is as described above. When the mold die is removed, the gas inside the cavity is released to reduce the internal pressure, so that the mold frame shrinks, so that the mold die (mold frame) can be easily removed. After the ingot is manufactured, the temperature is lower than that at the time of manufacturing the ingot, and the internal pressure in the cavity is lowered. At that time, the mold frame is contracted, so that the mold frame can be removed naturally.

Even if the mold frame does not come off from the ingot substrate, the pressure inside the cavity drops, so the pressing force of the mold frame also lowers the ingot substrate, so etching liquid or etching gas (including plasma etching) that etches the mold material It becomes easy to enter between the mold frame and the ingot substrate, and the mold frame facing the interface between the mold frame and the ingot substrate is etched. As a result, the mold frame can be separated from the ingot substrate. Further, an etching liquid or etching gas (including plasma etching) can be put in the cavity, and the thickness of the mold frame is thin, so that the mold frame can be dissolved from the inside and the outside. As a result, the mold frame can be removed from the ingot substrate. As the central hole mold, a mold having a hollow inside can be used.

FIG. 56 is a diagram ((b), (c)) for explaining a method ((a)) for polishing the inner wall of the through-hole to form a smooth and smooth surface and a method for transferring a pattern to the inner wall of the through-hole. .. FIG. 56( a) is a diagram showing a method of polishing the inner wall (inner surface) of the through chamber 1086 of the ingot substrate having the through chamber 1086 after removing the mold for forming the through chamber. A cylindrical polishing rod 1087 is inserted into the through chamber 1086, and the inner surface of the through chamber 1086 is traced while rotating the polishing rod 1087. Since the inner surface of the through chamber 1086 may be rough due to the removal of the mold, the rotation of the polishing rod 1087 can remove the unevenness of the inner surface of the through chamber 1086 and smooth the surface. An abrasive is adhered to or coated on the cylindrical surface of the polishing rod 1086, and/or a liquid containing an abrasive is sprayed, and the polishing rod 1086 is rotated in the liquid. If the ingot substrate is used, a large number of substrates can be processed together, and if the substrates are cut into individual substrates, more precise polishing is possible. Since the polishing rod 1086 has a cylindrical shape, it is difficult to polish the corner portion when the through chamber 1085 has a rectangular parallelepiped shape, but the corner portion can be sufficiently polished by using the cylindrical polishing rod having a smaller radius. You may choose to use the corners and others. Further, a polishing rod having a rectangular parallelepiped shape instead of a cylindrical shape can also be used. The rectangular parallelepiped polishing rod can reciprocate to polish the inner surface of the through chamber.

FIG. 56(b) is a diagram showing a method of transferring a pattern onto the inner surface of the through chamber using a cylindrical transfer bar. The transfer pattern 1089 is attached to the cylindrical transfer rod 1088, the cylindrical transfer rod 1088 is inserted into the through chamber 1086, and the transfer pattern 1089 attached to the cylindrical transfer rod 1088 is brought into contact with the inner surface of the through chamber 1086, The transfer pattern 1089 is attached to the inner surface of the through chamber 1086 and transferred. The transfer pattern 1089 is formed by adhering to the periphery of the cylindrical transfer rod 1088, and thus the pattern is transferred by rotating while pressing the surface of the cylindrical transfer rod 1088 against the inner surface of the through chamber 1086. The transfer pattern 1089 is, for example, a conductor electrode/wiring pattern. A conductor film is laminated on a cylindrical surface, a conductor film pattern is formed by using a photolithography method, and the cylindrical surface is applied to the inner surface of the penetrating interior. At this time, the conductor film is adhered to the surface of the through chamber by processing under conditions (for example, heat treatment) in which the surface of the through chamber and the conductive film adhere to each other with good adhesion. At the same time, if the degree of adhesion between the cylindrical surface and the conductor film is lower than the degree of adhesion between the through chamber surface and the conductor film, the conductor film pattern on the cylindrical surface can be transferred to the through chamber surface. By rotating the cylindrical shape, it can be transferred one after another. Alternatively, a conductor film pattern is attached to the transfer sheet, and the transfer sheet is wound around a cylindrical transfer rod. At this time, when the conductor film pattern is placed outside, the conductor film pattern attached to the transfer sheet is transferred to the surface of the through chamber while the cylindrical transfer rod is pressed against the surface of the through chamber and rotated. Alternatively, if the conductor sheet pattern is on the inside and the transfer sheet is on the outside, and the transfer sheet is attached to the surface of the through chamber while pressing the cylindrical transfer rod against the surface of the through chamber and rotating it, the transfer sheet will be attached. A conductive film pattern can also be attached to the surface of the through chamber. It can be transferred to the through chamber in the ingot substrate or can be transferred to the through chamber of the substrate after cutting. If the penetrating chambers have the same shape (for example, penetrating chambers 1076 and 1077 in FIG. 55), it is possible to attach a plurality of transfer rods to the support and insert the transfer rods into the respective penetrating chambers at the same time to perform transfer at the same time. it can.

FIG. 56(c) is a diagram showing a method of forming conductor film electrode/wiring patterns 1092 and 1093 on the same rectangular parallelepiped transfer plate as the through chamber and transferring these patterns to the inside of the through chamber. The transfer plate 1091 having the conductor film patterns 1092 and 1093 attached thereto or the transfer plate 1091 having the transfer sheet having the conductor film patterns 1092 and 1093 attached thereto is inserted into the through chamber 1086 and transferred by being pressed against the inner surface of the through chamber 1086. .. When using a transfer sheet, form electrodes and wiring of aluminum, Cu, Au, etc. on a high heat resistant sheet such as polyimide, attach a high heat resistant thermosetting adhesive to the opposite surface, and penetrate this adhesive surface It is possible to form a conductor film pattern on the inner surface of the penetrating inner surface by sandwiching the polyimide sheet on the inner surface of the penetrating inner surface by applying a transfer sheet to the inner surface of the penetrating sheet and heat-treating it. After the transfer, if necessary, a protective film may be laminated by a CVD method or the like, or a protective film (good for heat resistance) tape may be attached by a transfer method. As a result, a penetration chamber having heat resistance of about 300°C to 500°C can be manufactured. Further, it can be transferred to the through chamber in the ingot substrate or can be transferred to the through chamber of the substrate after cutting. If the through chambers have the same shape (for example, the through chambers 1076 and 1077 in FIG. 55), it is possible to attach a plurality of transfer rods to the support and insert the transfer plates into the respective through chambers at the same time to perform simultaneous transfer. it can.

The apparatus shown in FIG. 51 can also be used as a film forming apparatus (CVD apparatus). A film forming gas is introduced instead of the etching gases 1037 and 1038. For example, when growing polycrystalline Si on the side wall of the through chamber, SiH4 gas is introduced from the inlet 1035 and ejected from the ejection hole 1036 to the side wall of the through chamber. If the substrate 1011 is heated at a predetermined temperature (for example, 350° C. to 500° C.), a polycrystalline Si film can be grown on the sidewall of the through chamber. The device 1030 may be cooled in order to prevent film formation on the device 1030. By applying an electric field between the substrate 1011 and the device 1030, film formation can be performed at a lower temperature and high-speed film formation is also possible. To grow the W film, for example, to grow the WF6 gas and the WSi film, a mixed gas of WF6 gas and SiH4 gas may be introduced and ejected from the ejection holes. In that case (when reacting by gas mixing), in order to prevent the mixed gas from reacting in the device, the through holes 1032 are separated, and the introduction port and the ejection hole to these through holes (chambers) are also separated. Alternatively, the gas may be mixed in the vicinity of the side wall of the through chamber (of the substrate 1011) by ejecting from the ejection port. In the case of a SiO film, it can be formed using SiH4 gas and O2 gas. In the case of a SiN film, SiH2Cl2 gas and NH3 film can be formed. Other metal films (a variety of Al, Cu, Ni, Cr, Ti, etc.), alloy films and various films can be formed. Further, various carrier gases such as N2, H2 and He may be mixed. These film forming devices are CVD devices. The atmosphere in which the substrate and the like are arranged is a temperature at which the film can be formed from a low temperature to a room temperature to a high temperature, and is maintained at a low film pressure to a normal pressure to a high film forming pressure.

The apparatus shown in FIG. 51 can also be used for growing a plated film. Instead of the etching gases 1037 and 1038, a plating solution is introduced and ejected. For example, in the case of Cu plating, an electric field is applied to the substrate 1011 (minus application), a plating solution copper sulfate (CuSO4) solution is introduced from the inlet 1035, and ejected from the ejection hole 1036 to the side wall of the through chamber. High-speed plating is possible because a new plating solution can be supplied. In this case, the plating device is used. In the case of plating film lamination, if a place where the plating film is not desired to be grown is masked with a photosensitive film (resist film) or the like as in the case of normal plating, it is possible to plate only the portion without the mask.

A target substrate (for example, an insulator such as Al, Cu, Ti, Cr, TiN, Ni, Au, Si, W, Mo, or SiO) is inserted into the through chamber instead of the device shown in FIG. When a high frequency electric field is applied to the target and a sputtering gas (for example, Ar or N2) is introduced under a low pressure, the target material is sputtered from the target and the target material can adhere to the side wall of the through chamber. Since the distance between the target material and the side wall of the through chamber is very short, the sputtered film can be deposited at high speed. In this case, the device is a sputter device. Further, a device containing a photosensitive film liquid such as a resist liquid may be inserted into the penetration chamber or the like and jetted or sprayed to form a photosensitive film on the penetration chamber, the side surface or the bottom surface of the recess. If a device equipped with a heating element (resistor, infrared lamp, etc.) is inserted into the penetration chamber or the like, the photosensitive film can be prebaked. After the exposure, a device containing a developing solution can be inserted into the penetration chamber or the like, and jetted or sprayed to pattern the photosensitive film on the penetration chamber, the side surface or the bottom surface of the recess. CVD (plasma) of the photosensitive film is also possible with the insertion CVD device. A large number of the above-described devices are mounted on different substrates and inserted into a large number of through chambers in the substrate to perform patterning, film formation and heat treatment (coating/adhesion/formation of photosensitive film, photosensitive film Exposure, photosensitive film development, various film etching, various film CVD, various film PVD (sputtering, vapor deposition), various heat treatments, etc.) can be simultaneously processed.

According to the present invention, a penetration chamber penetrating from the substrate upper surface to the substrate lower surface is formed in a substrate, an insulating film and a conductor film are laminated in the penetration chamber, a conductor film electrode having a desired shape is formed, and the penetration chamber is passed. This is an ion implantation device in which the trajectories of ions are controlled. The embodiment shown in FIG. 57 is an application of a synchrotron type accelerator using a high frequency power source as an acceleration source to a substrate type ion implantation system, and FIG. 57 shows a substrate of the synchrotron type substrate type ion implantation device of the present invention. It is the top view seen parallel to the surface. Ions are generated in the ionization chamber 2112, and the ions are accelerated to a predetermined speed in the extraction electrode/acceleration chamber 2113. The accelerated ions are sorted into desired ions in the mass separation chamber 2114, and the sorted ions are sent to a connection chamber 2115 which connects the synchroton system acceleration chamber 2117 and the mass separation chamber 2114. A substrate partition having a central hole 2116 is arranged between the connection chamber 2115 and the synchrotron acceleration chamber 117, and ions advancing through the connection chamber 2115 pass through the central hole 2116 and form a linear shape in the synchrotron acceleration chamber 2117. Enter the high-frequency acceleration chamber 211-18, which is a penetration chamber.

The synchrotron type acceleration chamber 2117 has penetrating chambers connected in an annular shape, and ions orbit in an annular passage 2118 which is an annular penetrating chamber while accelerating. The annular passage 2118 is composed of two linear acceleration chambers 2118-1, 3 and a circular acceleration chamber 2118-2, 4 having an arc (semi-circular) shape connecting these two linear acceleration chambers 2118-1, 3. .. A high frequency voltage is applied to the linear acceleration chambers 2118-1 and 2118 to accelerate the ions. Conductor film electrodes 2121 and 2122 are formed on the sidewalls of the two facing penetration chambers of the semicircular circular acceleration chamber 2118-2. The conductor film electrodes 2121 and 2122 formed on the two facing sidewalls of the through chamber of the circular acceleration chamber 2118-2 are parallel to each other. (So-called parallel plate electrodes, inter-electrode distance r1) Further, conductor film electrodes 2123 and 2124 are formed on the two facing sidewalls of the semi-circular circular acceleration chamber 2118-4. The conductor film electrodes 2123 and 2124 formed on the two facing penetration chamber side walls of the circular acceleration chamber 2118-4 are parallel to each other. (So-called parallel plate electrodes, distance r1 between electrodes)

The ions circulate in the circular passage 2118, and are accelerated to the left side in FIG. 57 by the high-frequency voltage application in the linear acceleration chamber 2118-1, and proceed to the circular acceleration chamber 2118-2. Radius R1), and then the ions are accelerated to the right side in FIG. 57 by applying a high frequency voltage in the linear acceleration chamber 118-3 and proceed to the circular acceleration chamber 2118-4, where they are subjected to a constant electric field force and a circular orbit (center). Take the orbital radius R1) and enter the linear acceleration chamber 2118-1. When these are repeated and the ions are accelerated each time they orbit to reach a predetermined velocity (predetermined energy), the central hole 2125 provided in the substrate partition wall arranged in the direction of the ion orbit that advances in the linear acceleration chamber 2118-1 and goes straight ahead. And enters the exit passage (penetration chamber) 2126 and exits from the ion exit 2127. A scanner portion 2128 is provided in the outlet passage (penetration chamber) 2126 of the ion outlet 2127, and conductor film electrodes 2129-1 and 2129-2 are formed on the two facing substrate side walls, and these two conductor film electrodes 2129-1 are formed. The ions are oscillated (scanned) to the left and right (in the direction parallel to the substrate surface) by the electric field between the two and emitted. Although not shown in FIG. 57, two conductor film electrodes are also formed in a direction parallel to the substrate surface, and ions are oscillated up and down (in a direction perpendicular to the substrate surface) by the electric field between these electrodes ( Emit (scanned). Ions oscillated vertically (left and right) (scanned) are implanted into a wafer 2130 arranged in an end station or the like arranged on the ion emission side. It should be noted that the communication chamber 2115 and the outlet passage 2127 can be accelerated in the same manner as in the acceleration chamber. Further, since a magnetic field can be formed in the scanner unit 2128, the ion trajectory can be scanned vertically and horizontally with the magnetic field. For example, ions can be scanned left and right (lateral direction) by arranging coils and electromagnets above and below and changing the magnetic field, and ions can be scanned up and down by arranging coils and electromagnets on the side surface of the main substrate.

The through-hole chamber formed in the main substrate 2111 is provided with a substrate side wall plate having a central hole as needed, and partitions each through-hole (however, it is connected by the central hole) or a conductor film electrode. There is also a portion formed and to which an electric field is applied. Conductor film electrodes are also formed on the side surface of the side wall plate of the substrate having a central hole, and high-frequency voltage, electrostatic field, etc. are applied to these conductor film electrodes to accelerate, decelerate, or converge ions. can do. The main substrate 2111 is a conductor substrate (for example, metals such as Al, Cu, Fe, Ni, Zn, Ti and Cr or alloys containing these, conductive plastics, conductive carbon (conductive graphene, conductive carbon nanotubes are also included. ), conductive semiconductors (for example, low resistance Si containing high-concentration impurity elements), conductive ceramics), semiconductor substrates (for example, Si, Ge, C, compound semiconductors (for example, GaAs, InP, GaN, etc.). Original semiconductors, various multi-component semiconductors), insulator substrates (for example, glass, quartz, AlN, alumina, various plastics, various ceramics, various polymer substrates), and composite substrates thereof. In the case where a conductor film is formed on the conductor substrate or the semiconductor substrate and the substrate and the conductor film are not electrically connected to each other, an insulating film is interposed therebetween. A first upper substrate is attached to the upper surface of the main substrate 2111 and a first lower substrate is attached to the lower surface. Therefore, the through chamber formed in the main substrate 2111 is surrounded by the first upper substrate at the upper portion, the first lower substrate at the lower portion, and the side wall of the main substrate 111 at the side surface. Ions travel in a penetration chamber surrounded by these substrates. The penetration chamber formed in the main substrate 2111 is maintained at a predetermined pressure or lower by evacuating from the openings provided in the first upper substrate and the first lower substrate. Further, a gas or liquid for cleaning or purging the through chamber can be flown from another opening (which can also be used for vacuuming).

For the mass separation chamber 2114, various methods such as the magnetic field type, the electric field type or a combination thereof described above, a quadrupole type, an ICR type, or an ion trap type may be used. As the ionization chamber 2113, the ionization chamber described above can be used. Alternatively, externally ionized ions may be introduced. As the acceleration chambers 2113, 2115, 2118-1, 2118-3, the linear acceleration chambers described so far can be used. The circular acceleration chambers 2118-2, 4 have electrodes on both sides, but if the electrodes are divided in the traveling direction or the vertical direction so that a voltage can be applied individually to each of them, the electric field of the circular acceleration chambers is increased. Can be changed to control the ion trajectory. This circular accelerating chamber can also control the ion trajectory by using a magnetic field. That is, if coils and electromagnets are arranged above and below the main substrate, the ion trajectory can be controlled by the Lorentz force. Furthermore, by using both electric and magnetic fields, it is possible to control more precise ion trajectories.

Similar to the one shown in FIG. 16, if the ring-shaped orbits surrounding the ring-shaped orbit shown in FIG. 57 are connected in the lateral direction, it is possible to easily generate high-concentration ions at high speed. FIG. 58 is a diagram (plan view) showing a synchrotron type ion implanter having two orbits. The first-stage annular orbit 2140 is the same as the synchrotron type ion implanter shown in FIG. 57 and also has an ionization chamber and the like, but the ion emission line 243 is part of the first-stage annular orbit 2140 (so as to exit from the circular orbit). To the opening (the opening having the central hole is good) 2144, which exits from the opening (the opening having the central hole is good) 2142 provided in the second stage annular raceway 2145. Connecting. Ions that have entered the second-stage annular orbit merge with ions that are already rotating and accelerate while rotating, and go through a linear acceleration chamber and go straight ahead. And enters the exit passage (penetration chamber) 2147 and exits from the ion exit 2150. A scanner unit 2148 is provided in the exit passage (penetration chamber) 2147 of the ion exit 2150, and conductor film electrodes 2149-1 and 2149-2 are formed on the two facing substrate side walls, and these two conductor film electrodes 2149-1 are formed. The ions are oscillated (scanned) to the left and right (in the direction parallel to the substrate surface) by the electric field between the two and emitted. Although not shown in FIG. 58, two conductor film electrodes are also formed in a direction parallel to the substrate surface, and ions are oscillated vertically (in a direction perpendicular to the substrate surface) by the electric field between these electrodes ( Emit (scanned). Ions oscillated vertically (left and right) (scanned) are implanted into a wafer 2151 arranged at an end station or the like arranged on the ion emission side. The exit passage 2147 can be accelerated in the same manner as in the acceleration chamber. Further, since a magnetic field can be formed in the scanner unit 2148, the ion trajectory can be scanned vertically and horizontally with the magnetic field. For example, ions can be scanned left and right (lateral direction) by arranging coils and electromagnets above and below and changing the magnetic field, and ions can be scanned up and down by arranging coils and electromagnets on the side surface of the main substrate. Further, the third step, the fourth step,... And the multi-step annular track can be simultaneously formed in the present invention. Ions of higher speed and higher current can be created by using a multi-stage circular orbit. In addition, since the wiring layer can be formed in the present invention, the voltage or current applied to each electrode or coil can be controlled by mounting the LSI chip on the substrate 2111, so that the ion trajectory can be controlled extremely precisely.

FIG. 59 is an enlarged view of a state of a connection region between the ion emission line 2143 and the second-stage annular orbit 2145 (a plan view parallel to the substrate). The ion emission line 243 is connected to the cavity 2159 of the second-stage annular orbit 2145 by the connection opening 2144. Electrodes 2153 (2153-1, 2) and 2154 (2154-1, 2) are formed on the inner surfaces of the through-holes on both side surfaces (substrate side walls) 2152 (2152-1, 2) of the ion emission line 243. These electrodes 2153-1, 2154-1 and 2154-1, 2 are parallel electrodes. The ions 2160 travel straight along the ion emission line 243, but when they come near the exit 2144 of the ion emission line 2143, the orbits are bent by the electric field generated by these electrodes, and the cavities 2159 of the second-stage annular orbit 2145 are generated. The ions 2151 advancing in a direction as parallel as possible to join. The electrodes 2153 and 2154 provided in the vicinity of the outlet 2144 of the ion emission line 243 are divided into several parts (in FIG. 59, they are divided into two parts, but can be divided into more parts), and different electric fields can be applied to each of them. The trajectory of 2160 can be changed smoothly as desired. Therefore, the voltage to these divided electrodes can be merged with the ions 2161 as much as possible by adjusting the (electric field). Electrodes 2156 (2156-1, 2156-1, 2156, 2156, 2156-1, 2) near the exit (opening) 2144 of the ion emission line 2143 of the substrate side surface (sidewall) 2155-1, 2157 of the cavity 2159 of the second-stage annular orbit 2145. ) And 2158 (2158-1, 2) are formed. By applying a voltage also to these parallel plate electrodes 2156 (2156-1, 2) and 2158 (2158-1, 2), the trajectory of the ions 2160 emitted from the outlet (opening) 2144 of the ion emission line 2143 can be changed. The trajectory of the ion 2160 can be adjusted so that the ion 2160 can join with the ion 2161 passing through the cavity 2159. Ion trajectories can be precisely adjusted by applying different voltages to the parallel plate electrodes 2156 (2156-1, 2) and 2158 (2158-1, 2). Further, the parallel plate electrodes 2156 and 2158 can be divided into more parts to control the ion trajectory more accurately. Further, the electrodes 2153, 2154 and 2156, 2158 can be divided also in the substrate thickness direction, and the ion trajectory can be adjusted vertically and horizontally. Further, by disposing coils and electromagnets above and below the main substrate, a magnetic field can be generated in the thickness direction of the substrate, so that the ion orbit can be adjusted also by these magnetic fields. Therefore, the ion orbit can be further accurately adjusted by using the electric field and the magnetic field.

The substrate type ion implantation apparatus of the present invention may be stacked on top of each other to form a multi-stage ion implantation apparatus. Higher-speed (high-energy) ions can be obtained by using multiple stages, and since ions can be accumulated in each stage, high-dose ion implantation can be performed. FIG. 60 is a view showing a cross section of the track connecting portion of the ion implantation apparatus stacked in two stages. The first-stage annular orbit 2170 has a main substrate attached on a lower substrate 2171 and an upper substrate 2172 attached thereon. The first-stage circular orbit 2170 has a cavity 2175 in which ions 2176 are rotating. Similarly, in the second-stage annular track 2180, the main substrate is attached on the lower substrate 2182, and the upper substrate 2181 is attached thereon. The second-stage annular orbit 2180 has a cavity 2185 in which ions 2186 are rotating. The first-stage annular orbit 2170 and the second-stage annular orbit 2180 are stacked, but the upper substrate opening 2177 of the first-stage annular orbit 2170 and the lower substrate opening 2187 of the second-stage annular orbit 2180 are stacked. The cavities 2175 of the first-stage annular orbit 2170 and the cavities 2185 of the second-stage annular orbit 2180 are connected to each other. An electrode 2173 is formed on the upper surface of the lower substrate 2171 and an electrode 2174 is formed on the lower surface of the upper substrate 2172 behind the opening 2177 of the opening 2177 of the first-stage annular orbit 2170. These electrodes 2173 and 2174 are parallel plate electrodes, and an electric field is generated between them to change the trajectory of ions advancing through the ion trajectory 2176 upward to form an ion trajectory 2179 passing through the openings 2177 and 2187. An electrode 2184 is formed on the upper surface of the lower substrate 2182 and an electrode 2183 is formed on the lower surface of the upper substrate 2181 in front of the opening 2187 of the second orbit 2180 in the ion traveling direction. These electrodes 2183 and 2184 are parallel plate electrodes and generate an electric field therebetween. The ions that have proceeded along the ion orbit 2179 passing through the openings 2177 and 2187 enter between the parallel plate electrodes, and the orbit is changed by the force of the electric field, so that the ions pass through the cavity 2185 of the second-stage annular orbit 2180. Enter orbit 2186 and orbit. Alternatively, by disposing a coil or an electromagnet in the opening in a direction perpendicular to the substrate, a magnetic field can be applied in a direction parallel to the substrate (a direction perpendicular to the paper surface) to change the ion trajectory upward. Ion trajectories can be controlled more accurately by arranging a number of small coils and controlling each magnetic field individually. These controls can be performed using an LSI. By repeating this, a large number of annular orbits can be stacked above and below, so that a multi-stage ion implantation apparatus is obtained. When stacking in multiple stages, vacuuming and supply of electrical wiring to the middle annular orbit may be performed by opening the gap (region where there is nothing such as the orbit) in each stage and starting from that portion. Further, the trajectory may be controlled by using an LSI chip that controls the voltage and current to each electrode. Further, if various sensors such as a vacuum gauge, a thermometer, and an ammeter are installed at various places, the state of the annular orbit at each stage can be grasped and controlled.

FIG. 61 is a diagram showing an example of an RFQ (Radio Frequency Quadrouple) type linear accelerator. A conductive cylindrical body 2193 having a cavity 2194 inside and open at both ends is arranged in a cavity (penetration chamber) 2191 formed in the substrate. A quadrupole electrode 2197 is arranged in the cavity 2194 of the cylindrical body 2193. The quadrupole electrodes 2197 and 2198 are, for example, four electrodes (Vane electrodes) having a corrugated end in the lengthwise direction, four rod electrodes, or electrodes having other shapes. The four quadrupole electrodes 2197, 2197 and 2198, 2198 are arranged so as to be orthogonal to each other along the ion beam (acceleration axis) passing through the space surrounded by the electrodes 2197, 2198, and the electrodes facing each other are Each of the quadrupole electrodes 2197, 2197, and 2198, 2198, which are adjacent to each other and are facing each other at 90 degrees apart from each other, are arranged so that the peaks and the valleys are alternately adjacent to each other. Has been done. One of the pair of electrodes 2197, 2197 facing each other is electrically short-circuited to the cylindrical body 2193, and the pair of electrodes 2198, 2198 facing the other of the stem 2118 and/or 2189 surrounding the cavity (penetrating chamber) 2191 is a stem. It is supported by 2196 and/or the support pedestal 2195 to form a cavity resonator. High frequency power is applied to the pair of electrodes 2197 and 2197 and the pair of electrodes 2198 and 2198 facing each other by a high frequency introduction line 2199 connected to a predetermined position of the substrate surrounding the cavity 2191 so that their signs are different from each other. The RFQ linear accelerator configured as described above uses the conductor 2193 as an inner conductor and the substrate around the first coaxial line having the pair of electrodes 2197, 2197 as the inner conductor and the tubular body 2193 as the outer conductor. The second coaxial line having 2188 and/or 2189 as an outer conductor has a structure in which the second coaxial line is coupled so as to be folded back.

FIG. 62 is a diagram showing a method of manufacturing the RFQ linear accelerator shown in FIG. The figure on the left side is a schematic sectional view in the longitudinal direction (parallel to the ion advancing direction), and the figure on the right side is a schematic sectional view in the direction perpendicular thereto. A conductor substrate 3002 is attached on the conductor substrate 3001. (FIG. 62(a)) The material of these conductor substrates is, for example, a metal or alloy such as Al, Cu, Ni, or Ti, or a low-resistance semiconductor (for example, Si) doped with an impurity element at a high concentration. Is. As the adhesion method, various bonding methods such as a room temperature bonding method, a high temperature bonding method, a direct bonding method such as a diffusion bonding method, or a bonding method in which a low melting point alloy such as a conductive adhesive or solder is interposed can be used. The conductor substrate 3001 and the conductor substrate 3002 may be made of different materials or the same material. Next, an unnecessary portion of the conductor substrate 3002 is removed by using a photolithography method or the like to form a through hole (penetration chamber) 3003 (3003-1, 2, 3). This removal method includes etching (WET or dry), laser etching, and punching. In the etching method, the thickness of the photosensitive film or the like is selected in consideration of the etching selection ratio between the photosensitive film or the like formed by the photolithography method and the conductor substrate 3002 which is an etching material. Side etching may be performed, but vertical etching is preferable in order to form a mask pattern. Further, it is desirable to perform the etching under the etching conditions such that the conductor substrate 3001 which is the base material is hardly etched. In the case of laser etching or punching, a maskless method such as a photolithography method which does not use a mask can be used. The penetrating chamber 3003-1 is a portion that becomes a cavity 2194 inside the cylindrical body 2193 shown in FIG. 61. The conductor substrate 3002 can be patterned before being attached to the conductor substrate 3001, but the portions 3002 (3002-1, 2, 3) to be left are the side surface portions of the cylindrical body 2193 shown in FIG. When all the removed portions 3003-2 are removed, the portions 3002 (3002-1, 2, 3) to be left are also removed, so some of them must be left. However, since the punching method and the mold ingot method can be used, there is an advantage that the process is simplified. (FIG. 62(b)) Alternatively, the conductor substrate 3001 and the conductor substrate 3002 may be made into one conductor substrate and etched so that the cross-sectional shape becomes a U-shape. That is, in this case, a recess is formed without forming a through hole (chamber).

Next, the substrate 3004 is attached to the conductor substrate 3001. When the substrate 3004 and the conductive substrate 3001 are electrically connected to each other, the substrate 3004 may be a conductive substrate. In this case, a semiconductor substrate or an insulator substrate can be used, but after the substrate 3004 is etched, a conductor film is formed over the pattern 3004-1 (shown in FIG. 62D) to form a conductor. Conduction is established between the substrate 3001 and the conductor substrate 3007 attached to the substrate 3004. When the substrate 3004 and the conductor substrate 3001 are not electrically connected to each other, the substrate 3004 is preferably an insulator substrate. In this case, when a semiconductor substrate or a conductor substrate is used as the substrate 3004, an insulating film is stacked over the conductor substrate 3001 or the substrate 3004 is etched, and then the pattern 3004-1 (see FIG. An insulating film is formed on the conductive substrate 3001 and the conductive substrate 3007 attached to the substrate 3004 so that they are not electrically connected to each other. Next, in order to separate the cylindrical portion 3001-1 of the conductive substrate 3001, the conductive substrate 3001 around the side surface portion 3002 (3002-1, 2, 3) of the cylindrical body 2193 is removed, and a through hole (penetration hole) is formed. A chamber 3005 (3005-1, 2, 3, 4) is formed, which separates the periphery 3001-2 of the conductor substrate 3001 from the cylindrical portion 3001-1. The substrate 3004 supports the cylindrical body 2193. A stem 2196 for manufacturing is formed and a substrate surrounding the cavity 2191. Therefore, an unnecessary portion is removed by etching the substrate 3004 using a photolithography method or the like to remove the through chamber 3006 (3006-1, 2, 6-1, 3, 4). These penetrating chambers 3006 (3006-1, 2, 3, 4) become cavities 2191. The part 3004-1 that is not removed becomes the stem 2196, and penetrating chambers 3006 (3006-1, 2). The part 3004-2 surrounding 3, 4) serves as a substrate surrounding the cavity 2191. The adhesion method can be selected from the methods described above. If no adhesive is used, an insulating adhesive is used if an adhesive is used. Good. The through chamber 3006 (3006-1, 2, 3, 4) is a cavity 2191 surrounding the cylindrical body 2103. The through chamber 3006 (3006-1, 2, 3, 4) is a through hole (through chamber 3005 (3005). -1, 2, 3, 4).

A conductor substrate 3007 is attached on the substrate 3004. The attachment method can be performed by the method described above. The conductor substrate 3007 becomes the outer conductor of the second coaxial line. Since the conductor substrate 3007 only needs to cover the accelerator portion, unnecessary portions are removed by etching or the like. The conductor substrate 3007 from which unnecessary portions have been removed in advance may be attached to the substrate 3004. (FIG. 62E) As a result, the upper half or the lower half of the RF linear accelerator was manufactured. The conductor substrate 3001-1 to be a cylinder and the side faces 3002-1 to 3002-1 are supported by the stem 3004-1, and the stem 3004-1 is connected to the conductor substrate 3007. Since the upper and lower sides of the RF linear accelerator are almost symmetrical, the same one as shown in FIG. 62(e) was manufactured, and a quadrupole was used in the ion implantation acceleration chamber, the accelerator acceleration chamber, the mass spectrometer acceleration chamber, etc. After the electrode 3009 is set, the outer side of the conductor substrate 3001 is attached to the upper and lower surfaces of the upper and lower substrates 3010 and 3011 in the acceleration chamber while the electrodes shown in FIG. At this time, the entire size is adjusted so that the end faces 3008 of the cylindrical body 3002 can be simultaneously attached to each other. The method described so far can also be used for these attachments. Electrical contact between the quadrupole electrode 3009 and the cylindrical body or the outer conductor substrate 3007 can be made by forming a contact hole or a wiring layer through the acceleration chamber substrates 3010 and 3011 by the method described above, or These can be obtained by directly contacting them or providing a contact or a wiring layer for direct connection, or through a stem or a support pedestal, or by providing a wiring layer using the stem support pedestal. The quadrupole electrode 3008 can be mounted by the method described so far. (For example, the diagram and the description of FIG. 26) Ions 3014 that have exited from the penetration chamber 3012 on the left side of the acceleration chamber into the cavity 3013 of the RF linear accelerator enter the cylindrical cavity 3015 and are converged and accelerated to penetrate the right side of the acceleration chamber. Sent to chamber 3016. Two stems 3004 for supporting the cylindrical body are shown above and below, but one may be the support pedestal 2195 shown in FIG. 61, or only one if it can be supported. As a result, an RF linear accelerator can be manufactured with the substrate type of the present invention extremely easily and accurately. The support pedestal 2195 can be manufactured by a method similar to the method of forming the stem. Regarding a substrate manufactured using a conductor substrate, it is also possible to secure conductivity by laminating a conductor film on the surface of an insulator substrate or a semiconductor substrate (in this case, the inner surface of the cavity in particular). ..

FIG. 63 is a diagram showing another acceleration method (IH (Interdigital H) type) of a linear accelerator (including APF (Alternating Phase Focus)). FIG. 63(a) is a diagram showing the configuration. An accelerator having a large number of cylindrical electrodes (also referred to as a drift tube and formed of a conductor) 3020, wherein the thickness of the i-th cylindrical electrode 3020-i from the ion entrance direction is Mi, and the i-th cylindrical electrode 3020-i. And the i+1-th cylindrical electrode 3020-i+1-th distance is Li. The cylindrical electrode 3020 has a central hole 3023 in the central portion, through which the ion beam 3025 passes. The cylindrical electrode 3020 is connected to a substrate surrounding the cavity by a support stem 3024 inside the cavity. The cylindrical electrode 3020 is separately prepared in two parts (3021.3022) at the upper and lower sides, and is attached at its end face 3026. The cylindrical electrode is arranged substantially perpendicular to the ion beam. A high-frequency voltage is applied to each cylindrical electrode through the stem, and ions passing therethrough can be accelerated. The distance Li+Mi/2 between the cylindrical electrodes is predetermined and arranged so as to be synchronized with the high frequency. Therefore, the ions circulated by the synchrotron type ion implanter are accelerated by the accelerator each time. The linear accelerator shown in FIG. 63 can be easily manufactured by almost the same method as that shown in FIGS. 61 and 62. The size of the central hole, the size of the cylindrical electrode, Mi, Li, and the size of the cavity can be appropriately determined according to the acceleration voltage of the ion beam, the current, the applied high-frequency characteristics, and the like. FIG. 63( b) is a diagram showing a part of the method for manufacturing the structure shown in FIG. 62. FIG. 63(b) corresponds to FIG. 62(e). Since the process is almost the same as the method shown in FIG. 62, the same reference numerals are given and different points will be mainly described. The conductor substrates 3001 and 3002 forming the half 3021 (or 3022) of the drift tube 3020 are manufactured by the same method, and these can be made as one substrate or made of the same material. A large number of drift tubes 3021 are arranged. In the case where the substrate 3007 is an insulator, the stem substrate 3004 and the insulator substrate 3007 are bonded to each other by using an adhesive, a metal that can be adhered, or various bonding methods. Next, a contact hole 3031 for connection to the stem 3004 is formed in the insulator substrate 3007, a conductor film 3032 is stacked in the contact hole, and conduction is established with the stem 3004. Further, the electrode 3033 connected to the contact hole is patterned. When the adhesive is a non-conductive adhesive, the adhesive exposed at the time of forming the contact hole is removed. Further, the contact hole 3031 and the conductor film 3032 may be formed on the insulator substrate 3007 before being attached to the stem substrate 3004. In this case, the insulator substrate 3007 and the stem substrate 3004 are attached so that the stems are connected in accordance with the contact holes 3031. If an adhesive is used at this time, it is a conductive adhesive. The same thing as this is manufactured, and the other half of the drift tube 3020 is attached with a main substrate or the like interposed therebetween as shown in FIG. 62(f). That is, the end surface 3026 of 3021 and the end surface 3026 of 3022 are attached together. A high frequency wave of the same phase is applied to every other electrode (for example, 3033-i and 3033-i+2), and another high frequency is applied to every other electrode (for example, 3033-i-1 and 3033-i+1). A high frequency of phase is applied to accelerate the ions passing through the drift tube 3020. Alternatively, it is possible to accelerate the ions passing through the drift tube 3020 by sequentially applying high frequencies having gradually changing phases to the adjacent electrodes. Particularly, in the IH accelerator of the present invention, since electrodes are formed on the upper and lower sides of each drift tube, it is possible to apply a high frequency optimum for ion acceleration. When the substrate 3007 is a conductive substrate, the stem 3004 of the drift tube (for example, 3033-i-1 and 3033-i+1) which does not want to have conductivity with the conductive substrate 3007 and the conductive substrate 3007 can be bonded. Use an insulating adhesive. However, the adhesive on the opposite side to which it adheres should be electrically conductive. By doing so, it is possible to arrange the drift tubes connected to the conductor substrate 3007 arranged on the upper side and the drift tubes connected to the conductor substrate 3007 arranged on the lower side so as to be alternately conductive in the vertical direction. Further, a ridge substrate may be arranged between the conductor substrate and the stem 3004 to uniformly generate an accelerating electric field over the entire cavity.

FIG. 64 is a diagram showing an acceleration method in another linear acceleration chamber. When the ions advancing from the connection chamber 2115 or the circular acceleration chamber 2118-2 shown in FIG. 57 enter the linear acceleration chambers 2118-1 and 3, central holes 2139 (2139-1, 2,...) Are provided, .. in the substrate side wall 2136 (2136-1, 213-1,...) In which the conductor film 2132 is formed in the central hole 2139, ions are accelerated by the high frequency electric field or electrostatic field applied thereto, Enter the circular acceleration chambers 2118-2,4. By repeating this, the ions orbit while accelerating, and are ejected when a predetermined speed (accelerating voltage) is reached. There are also substrate side walls 2135 (2135-1, 2) between the penetration chambers, and ions and the like out of the orbit collide with the substrate side walls and cannot enter the adjacent chamber. Further, the substrate side wall 2135 (2135-1) is not attracted to the side surface of the substrate side wall electrode 2136-1 and goes through the central hole. It is also possible to form a conductor film on this 2135 (2135-1) and apply the same voltage as that of the ions to focus the ions. The conductor film formed on the substrate side wall 2136 formed in the linear acceleration chambers 2118-1 and 2118 is connected to the electrode/wiring 2134 on the substrate through the contact electrodes/wiring 2133 formed on the upper and lower substrates 2108 and 2109. An electrode/wiring 2134 on the substrate is formed on each of the substrate side wall electrodes 2136 (2136-1, 2,...) And a voltage can be applied individually. For example, a voltage (|V|) opposite to that of the ions is applied to the substrate sidewall electrode 2136-1 to accelerate the ions. A voltage (│V│+Δv1) slightly higher than this is applied to the substrate side wall electrode 2136-2 adjacent to the substrate side wall electrode 2136-2 to further accelerate the voltage. Ions are accelerated more and more by applying a larger voltage (|V|+Δv1+Δv2) next to them. When the ions diverge, a substrate side wall voltage applied with a voltage having the same charge as the ions is provided to converge. This is repeated to accelerate the ions to a predetermined speed. Ion diffusion may be prevented by providing a substrate side wall without a conductor film (with a central hole) or a substrate side wall with a conductor film to which no voltage is applied (with a central hole) between the substrate side wall electrodes. Moreover, since electrodes and wirings can be formed on the upper and lower substrates, the degree of freedom in applying voltage is increased. As described above, the ions can be accelerated by using the electrostatic field.

Ions can also be accelerated using a high frequency electric field. For example, ions can be accelerated by applying the same high frequency voltage to every other electrode and applying the same high frequency voltage with a different phase to every other electrode to synchronize with the ion velocity. Ions can also be accelerated by applying the same high-frequency voltage to every two electrodes or every m electrodes and applying a high-frequency voltage to the electrodes between them so that the phase gradually changes. Since the substrate side wall electrode of the present invention has the electrodes and wirings 2134 on the upper and lower sides individually, the way of applying the high frequency voltage can be changed according to the ion velocity, and the ions can be efficiently accelerated. it can. Moreover, since the LSI chip can be placed in the immediate vicinity, these controls can be performed quickly and automatically. Further, since the side wall of the substrate (with the central hole) with or without the conductor film to which high frequency is not applied can be arranged, it is easy to prevent interference due to high frequency leakage. The upper and lower substrates 2108 and 2109 can be provided with openings 2137 to evacuate the through chamber, or cleaning and purging can be performed. FIG. 64B is an A1-A2 cross section (perpendicular to the ion trajectory G), in which a conductor film 2132 is laminated on the side surface of the central hole 2139. The periphery of the central hole 2139 is the main substrate 2111, and the boundary of the through chamber is indicated by 2141 (2141-1, 2). Since the substrate side wall electrode interval can be freely selected, it has a structure that facilitates high frequency synchronization. FIG. 64C is also a cross section taken along line A1-A2 (perpendicular to the ion trajectory G), but showing a different side wall of the substrate. The gaps 2142-1, 2 are formed between the substrate side wall 2136 and the through chamber side surface 2111 (2111-1, 2) of the main substrate 2111. Further, conductor films 2143-1 and 2143-1 are formed on the outer side surface of the substrate side wall 2136. These conductor films 2143-1 and 214-3 are connected to the central hole conductor film 2132. When a high frequency voltage is applied to the conductor film 2132, the gap 2142 makes the synchronization of the high frequency electric field smoother. That is, the efficiency is improved. Since the substrate side wall electrode interval can be freely selected, it has a structure that facilitates high frequency synchronization. The above description can be applied to all things described in this specification such as the accelerator and the mass spectrometer.

It should be noted that the fact that the contents can be applied to other parts where the contents described and described in each part of the specification are not described without contradiction can be applied to the other parts. Further, it goes without saying that the above embodiment is an example, and various modifications can be made without departing from the scope of the invention, and the scope of rights of the present invention is not limited to the above embodiment.

INDUSTRIAL APPLICABILITY The present invention can be applied not only to the accelerator and the mass spectrometer, but also to the individual elements and mechanisms constituting them. Further, it can be used for all devices using an acceleration mechanism, for example, an ion implantation device.

11... Charged particle generator, 13... Linear (type) accelerator, 15, 17, 19, 21, 22, 23, 26, 28, 29, 31, 32, 35, 36... Various electromagnets, 25, 30, 34, 37... Bending electromagnet, 12, 14, 16, 18, 20, 24, 27, 33, 38, 40... Cavity through which charged particles pass, 39... Linear accelerator, 21 ...Inflector,

Claims (69)

A mass spectrometer comprising a plurality of substrates including a first main substrate, a first upper substrate attached to an upper surface of the first main substrate, and a first lower substrate attached to a lower surface of the first main substrate. The analysis chamber is a through chamber formed in the first main substrate and penetrating from the upper surface of the first main substrate to the lower surface of the first main substrate, and the direction perpendicular to the substrate surface (Z direction) is the upper substrate and the lower substrate. Both sides of the direction perpendicular to the Z direction and in the traveling direction of the charged particles (X direction) are surrounded by the first main substrate side plate, and both sides of the Z direction and the direction orthogonal to the X direction (Y direction) are surrounded by the first main substrate. The first main substrate side plate on which the charged particles are incident has a central hole, and the charged particles are incident on the mass analysis chamber through the central hole formed on the first main substrate side plate. Analysis equipment. The mass spectrometer according to claim 1, wherein the first main substrate is an insulator substrate, a semiconductor substrate, a conductor substrate, or a laminated substrate thereof. The upper substrate and the lower substrate are glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates thereof, according to claim 1 or 2. Mass spectrometer. When the main substrate is an insulating substrate, a glass substrate, a quartz substrate, a plastic substrate, an alumina substrate, an AlN substrate, a ceramic substrate, a polymer substrate, or a laminated substrate of these,
When the main substrate is a semiconductor substrate, it may be a Si substrate, a SiC substrate, a C substrate, a GaAs substrate, an InP substrate, a GaN substrate, a CdS substrate, a binary compound semiconductor, a ternary compound semiconductor, or a laminated substrate thereof. Characterized by
When the main substrate is a semiconductor substrate, and when it is a conductor substrate, it is Cu, Al, Ti, Zn, Fe, an alloy containing these metals, or a laminated substrate thereof. Item 4. The mass spectrometer according to any one of items 1 to 3. The mass spectrometer is a quadrupole mass spectrometer, and in the mass spectrometer,
Two quadrupole electrodes attached or formed on the lower surface of the upper substrate and two quadrupole electrodes attached or formed on the upper surface of the lower substrate;
A contact wiring (upper substrate contact wiring) formed on the upper substrate connected to the two quadrupole electrodes arranged on the lower surface of the upper substrate, and an electrode formed on the upper surface of the upper substrate connected to the upper substrate contact wiring. Wiring (upper substrate upper surface electrode/wiring), contact wiring (lower substrate contact wiring) formed on the lower substrate connected to two quadrupole electrodes arranged on the upper surface of the lower substrate, and the lower substrate contact wiring Has electrodes/wirings (lower board lower surface electrodes/wirings) formed on the lower board lower surface to be connected,
A mass spectrometer, wherein a high-frequency voltage and/or a DC voltage is applied from the upper electrode/wiring and the lower electrode/wiring. Of the two quadrupole electrodes arranged on the lower surface of the upper substrate and the two quadrupole electrodes arranged on the upper surface of the lower substrate, two quadrupole electrodes which are not adjacent to each other have substantially the same distance. The mass spectrometer according to claim 5, characterized in that the midpoints between them are substantially the same. Of the two quadrupole electrodes arranged on the lower surface of the upper substrate and the two quadrupole electrodes arranged on the upper surface of the lower substrate, the distances between two adjacent quadrupole electrodes are substantially the same. The mass spectrometer according to claim 4 or 5, characterized in that. The second main substrate is attached on or above the upper substrate (first upper substrate), and the second upper substrate (second upper substrate) is further attached on the second main substrate. ), a through chamber (second through chamber) penetrating from the second upper substrate to the first upper substrate is formed in the second main substrate, and the first upper substrate between the first through chamber and the second through chamber is formed. An opening is provided in a part of the opening, and the opening is formed between two quadrupole electrodes arranged on the lower surface of the first upper substrate,
The electrode/wiring formed on the first upper substrate connected to the quadrupole electrode arranged on the lower surface of the first upper substrate is connected to the wiring (second wiring) formed on the side surface of the second penetration chamber, The second wiring is connected to an electrode/wiring formed on the lower surface of the second upper substrate, and the electrode/wiring formed on the lower surface of the second upper substrate is a contact wiring (second upper substrate contact) formed on the second upper substrate. Wiring, and the second upper substrate contact wiring is connected to an electrode/wiring (second upper electrode/wiring) formed on the second upper substrate,
A third main substrate is attached to or below the lower surface of the lower substrate (first lower substrate), and a second lower substrate (second lower substrate) is attached to the lower surface of the third main substrate, and the through chamber (first (1st penetration chamber), a penetration chamber (third penetration chamber) penetrating from the second lower substrate to the first lower substrate is formed in the third main substrate, and a first penetration chamber between the first penetration chamber and the third penetration chamber is formed. 1. An opening is provided in a part of the lower substrate, and the opening is formed between two quadrupole electrodes arranged on the upper surface of the first lower substrate,
The electrode/wiring formed on the lower surface of the first lower substrate connected to the quadrupole electrode arranged on the upper surface of the first lower substrate is connected to the wiring (third wiring) formed on the side surface of the third penetration chamber. , The third wiring is connected to an electrode/wiring formed on the upper surface of the second lower substrate, and the electrode/wiring formed on the upper surface of the second lower substrate is a contact wiring (second lower substrate). Contact wiring), and the second lower substrate contact wiring is connected to an electrode/wiring (second lower electrode/wiring) formed on the lower surface of the second upper substrate,
A mass spectrometer, wherein a high-frequency voltage and/or a DC voltage is applied from the second upper electrode/wiring and the second lower electrode/wiring. The second upper substrate and the second lower substrate are glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates thereof, according to claim 8. The mass spectrometer described. When the second main substrate and the third main substrate are insulator substrates, they may be glass substrates, quartz substrates, plastic substrates, alumina substrates, AlN substrates, ceramic substrates, polymer substrates, or laminated substrates thereof. Characteristic,
When the second main substrate and the third main substrate are semiconductor substrates, Si substrate, SiC substrate, C substrate, GaAs substrate, InP substrate, GaN substrate, CdS substrate, binary compound semiconductor, ternary compound semiconductor, or Characterized by being a laminated substrate of these,
When the second main substrate and the third main substrate are semiconductor substrates, and when they are conductor substrates, they are Cu, Al, Ti, Zn, Fe, alloys containing these metals, or laminated substrates thereof. The mass spectrometer according to claim 8 or 9, characterized in that. The mass spectrometry chamber is a quadrupole mass spectrometry chamber, one quadrupole electrode is arranged on the upper surface of the upper substrate attached to the upper portion of the mass spectrometry chamber, and on the lower surface of the lower substrate attached to the lower portion of the mass spectrometry chamber. One quadrupole electrode is arranged, and one quadrupole electrode is arranged in each of the left and right penetration chambers formed in the main substrate provided next to the mass spectrometry chamber, The mass spectrometer according to any one of claims 8 to 10. The mass spectroscope according to claim 11, wherein the left and right through chambers formed on the main substrate next to the mass spectrometric chamber have substrate side walls between the mass spectrometric chamber and the through chamber. 13. The quadrupole electrode is a rod, and the rod is attached to predetermined positions of the upper substrate, the lower substrate, and the main substrate, and the quadrupole electrode is characterized in that: The mass spectrometer according to. The quadrupole electrode is laminated on the upper substrate or the lower substrate by a CVD method, a PVD method, a plating method, an electroforming method, a screen printing method, a squeegee method, a spin coating method, a dispensing method, or a combination thereof to form a predetermined shape. The mass spectrometer according to any one of claims 8 to 13, which is a processed conductor film electrode. The mass spectrometry chamber is a quadrupole mass spectrometry chamber, and two quadrupole electrodes attached or formed on the lower surface of the upper substrate attached to the upper portion of the mass spectrometry chamber and on the surface on the mass spectrometry chamber side are arranged. A mass spectrometer, wherein two quadrupole electrodes attached to the upper surface of a lower substrate attached to or formed on the lower portion of the mass analysis chamber and attached to the surface on the mass analysis chamber side are arranged. A through chamber (second through chamber) is further formed above the upper substrate (first upper substrate) having two quadrupole electrodes attached or formed thereon, and the second upper substrate is attached above the second through chamber. A part of the first upper substrate between the mass analysis chamber (first penetration chamber) and the second penetration chamber is removed, and the pressures of the first penetration chamber and the second penetration chamber are substantially the same. Characterized by
A penetration chamber (third penetration chamber) is further formed below the lower substrate (first lower substrate) having the two quadrupole electrodes attached or formed thereon, and the second lower substrate is adhered to the lower portion of the third penetration chamber. A part of the first lower substrate between the mass analysis chamber (first penetration chamber) and the third penetration chamber is removed, and the pressures of the first penetration chamber and the third penetration chamber are substantially the same. The mass spectrometer according to claim 15, wherein The mass spectrometry chamber has one quadrupole electrode (first quadrupole electrode) attached or formed on the lower surface of the upper substrate and one quadrupole electrode (second quadrupole electrode) attached or formed on the upper surface of the lower substrate. Part of the substrate on one side of the mass analysis chamber extends in the Y direction inside the mass analysis chamber, and one quadrupole electrode attached or formed on the upper or lower surface of the substrate on the extended side ( A third quadrupole electrode) and a part of the substrate on the other side of the mass analysis chamber extends in the Y direction in the mass analysis chamber, and one of the four attached or formed on the upper or lower surface of the substrate on the extended side. The mass spectrometer according to claim 16, further comprising a quadrupole electrode (fourth quadrupole electrode). The upper substrate has a contact wiring (first upper substrate contact wiring) connected to the first quadrupole electrode and an electrode/wiring (first upper substrate electrode/wiring) connected to the first contact wiring on the upper surface thereof. ,
The lower substrate has a contact wiring (first lower substrate contact wiring) connected to the second quadrupole electrode and an electrode/wiring (first lower substrate electrode/wiring) connected to the second contact wiring on the lower surface thereof. ,
The side substrate on which the third quadrupole electrode is attached or formed has a wiring for connecting to the third quadrupole electrode, and the wiring is connected to the wiring formed on the side surface of the main substrate and further formed on the side surface. The formed wiring is connected to the wiring formed on the upper substrate or the lower substrate, and the wiring is further connected to the contact wiring (the second upper substrate contact wiring or the second lower substrate contact wiring) formed on the upper substrate or the lower substrate. In addition, the second upper substrate contact wiring or the second lower substrate contact wiring is an electrode/wiring (second upper substrate electrode/wiring or second lower substrate electrode/wiring) formed on the upper surface of the upper substrate or the lower surface of the lower substrate. ) Is connected to the mass spectrometer according to any one of claims 15 to 17. A penetration chamber (second penetration chamber) is further formed above the upper substrate (first upper substrate), a second upper substrate is attached to an upper portion of the second penetration chamber, and the mass spectrometry chamber (first penetration chamber) is formed. A part of the first upper substrate between the second through chamber and the second through chamber is removed, and the pressures of the first through chamber and the second through chamber are substantially the same,
A through chamber (third through chamber) is further formed below the lower substrate (first lower substrate), a second lower substrate is attached to a lower portion of the third through chamber, and the mass spectrometry chamber (first through chamber) is formed. 19. A part of the first lower substrate between the first and third through chambers is removed so that the pressures of the first and third through chambers are substantially the same. The mass spectrometer according to any one of 1. The mass spectrometer is a quadrupole mass spectrometer, and in the mass spectrometer,
A quadrupole electrode (first quadrupole electrode) attached or formed on the lower surface of the upper substrate, and a quadrupole electrode (third quadrupole electrode) attached or formed on the upper surface of the lower substrate,
Contact wiring (upper substrate contact wiring) formed on the upper substrate connected to the quadrupole electrode (first quadrupole electrode) arranged on the lower surface of the upper substrate and an upper substrate upper surface connected to the upper substrate contact wiring The formed electrodes/wirings (upper substrate upper surface electrodes/wirings) and contact wirings (lower substrate) formed on the lower substrate connected to the quadrupole electrode (third quadrupole electrode) arranged on the upper surface of the lower substrate. Contact wiring) and electrodes/wirings (lower substrate lower surface electrodes/wirings) formed on the lower substrate lower surface connected to the lower substrate contact wiring,
A quadrupole electrode (second quadrupole electrode and fourth quadrupole electrode) formed on two side surfaces of the main substrate in the Y direction,
The second quadrupole electrode and the fourth quadrupole electrode are the contact wiring formed on the upper substrate and/or the lower substrate, and the electrode/wiring formed on the upper surface of the upper substrate and/or the lower surface of the lower substrate ( Upper substrate upper surface electrode/wiring and/or lower substrate lower surface electrode/wiring)),
20. The mass spectrometer according to claim 15, wherein a high frequency voltage and/or a DC voltage is applied from the upper substrate upper surface electrode/wiring and the lower substrate lower surface electrode/wiring. The second quadrupole electrode and the fourth quadrupole electrode are conductor films stacked in a through chamber formed in the main substrate, and a part of the conductor film is a plating film. The mass spectrometer according to any one of claims 15 to 20. The mass spectrometric chamber is of a magnetic field application type and has one or more coils arranged above the upper substrate attached to the upper part of the main substrate forming the mass spectrometric chamber and/or of the main substrate forming the mass spectrometric chamber. It was used that the orbit of charged particles was changed by generating a magnetic field in the direction perpendicular to the substrate surface of the main substrate by one or more coils arranged on the lower side of the lower substrate attached to the lower portion. The mass spectrometer according to any one of claims 1 to 4, characterized in that The mass spectrometric chamber is of a magnetic field application type and includes an electromagnet disposed above the upper substrate attached to the upper part of the main substrate forming the mass spectrometric chamber and/or below the lower substrate attached to the lower part of the main substrate. The mass according to any one of claims 1 to 4, wherein the orbit of the charged particles is changed by generating a magnetic field in a direction perpendicular to the substrate surface of the main substrate. Analysis equipment. Mass spectrometer. 24. The one or more coils arranged on the upper side of the upper substrate and/or the lower side of the lower substrate are formed on the second main substrate by lamination, and are characterized in that: Mass spectrometer. Charged particles are emitted from the charged particle extraction chamber or charged particle acceleration chamber to the mass analysis chamber, and a substrate side wall plate (front substrate) having a central hole between the charged particle extraction chamber or charged particle acceleration chamber and the mass analysis chamber. 25. A mass spectrometer according to any one of claims 22 to 24, characterized in that a side wall plate) is arranged and charged particles are emitted to the mass analysis chamber through the central hole of the front substrate side wall plate. .. The charged particles that have left the mass analysis chamber are subjected to ion detection in the ion detection chamber, and the ion detection chamber is a penetration chamber formed in the main substrate, and has a central hole between the mass spectrometry chamber and the ion detection chamber. 26. The substrate side wall plate (rear substrate side wall plate) is arranged, and the charged particles are emitted to the ion detection chamber side through a central hole of the rear substrate side wall plate. The mass spectrometer according to the item. 27. The charged particle is bent in a direction of 360 degrees by a magnetic field, and a plurality of ion detection chambers are arranged in a region of 360 degrees. 27. Mass spectrometer. The mass spectrometric chamber is a double-focusing type in which an electric field application type is further added, and a region of the electric field application type through which charged particles pass is formed on the main substrate, and the upper surface (Z direction) is on the upper substrate and the lower surface (Z direction). Direction) is a penetration chamber (electric-field-applied penetration chamber) including a fan-shaped penetration chamber (fan-shaped region penetration chamber) whose side surface (Y direction) is surrounded by the side surface (Y direction) of the main substrate. The chamber is surrounded by a substrate side wall plate having a central hole in the X direction, charged particles enter through the central hole of one of the substrate side wall plates, and the orbit of the charged particle is bent in the electric field application type penetrating chamber, so that the other It is characterized in that it is emitted from the central hole of the side wall plate of the substrate. In the electric field application type penetration chamber, electrodes are formed on both sides of the main substrate facing each other with a central orbit of radius R0, a central angle α, and a constant distance d0 from the central orbit. 28. The mass spectrometer according to claim 22, wherein the charged particles are bent by an electric field generated by a voltage applied to electrodes formed on both side surfaces. The side electrode in the electric field application type penetration chamber is characterized in that a plating film is further laminated on a conductor film laminated by a CVD method or a PVD method,
The contact wiring connected to the side surface electrode is formed on the upper substrate attached to the upper surface of the electric field type penetration chamber, connected to the electrode/wiring formed on the upper surface of the upper substrate, and/or the lower surface of the electric field type penetration chamber. 29. The mass spectrometer according to claim 28, which is formed on a lower substrate attached to the substrate and is connected to an electrode/wiring formed on a lower surface of the lower substrate. The through chamber (ICR chamber) in which charged particles enter and perform cyclotron motion is provided in a substrate side wall plate (substrate side wall plate for extraction electrode) having a central hole which is an entrance of charged particles from an ion source, and in a traveling direction of charged particles. Yes, the substrate side wall facing the extraction electrode substrate side wall, the side wall of the substrate on which the cyclotron-moved charged particles collide (trap electrode substrate side wall), the upper substrate attached to the upper part of the ICR chamber, and the lower substrate attached to the lower part of the ICR chamber. , Is surrounded by two substrate side walls (receiver electrode substrate side walls) substantially parallel to the charged particles, and the surface of the extraction electrode substrate side wall plate serves as an extraction electrode for drawing the charged particles from the central hole to the ICR chamber. A conductor film electrode is formed, a conductor film electrode to which a voltage for trapping the charged particles is applied is formed on the surface of the side wall of the trap electrode substrate, and the upper substrate and the lower substrate excite the charged particles. Characterized in that a conductor film electrode to which a voltage is applied is formed,
The mass spectrometer according to any one of claims 1 to 4, characterized in that a magnetic field parallel to the direction from the extraction electrode to the trap electrode, which is the traveling direction of the charged particles, is applied in the ICR chamber. .. The coil wiring for generating the magnetic field is formed in close contact with the upper substrate and the lower substrate and further formed in close contact with the outer side surface of the main substrate, or formed inside the main substrate, the upper substrate and the lower substrate. 31. The mass spectrometer according to claim 30, wherein The support substrate is attached on the upper substrate, the second upper substrate is further attached on the support substrate, the support substrate is attached on the lower substrate, and the second lower substrate is further attached on the support substrate. The coil wiring for generating the magnetic field is formed in close contact with the upper substrate and the lower substrate, and further formed in close contact with the outer side surface of the main substrate,
Further, the electrode wirings connected to the extraction electrode, the trap electrode, the two opposing ion excitation electrodes, and the two opposing receiver electrodes in the ICR chamber are formed on the upper substrate and/or the lower substrate, and the upper substrate and the pillar It exists in the space surrounded by the substrate and the second upper substrate, and/or it exists in the space surrounded by the lower substrate, the pillar substrate, and the second lower substrate, and their electrode wiring is 2 the electrode wiring formed on the upper substrate and/or the second lower substrate, and the electrode connected to the coil is the electrode wiring formed on the second upper substrate and/or the second lower substrate. 32. The mass spectrometer according to claim 30, wherein the mass spectrometer is connected. The charged particle generating chamber for generating charged particles includes two through chambers (charged particle generating chambers 1 and 2) formed on a main substrate having an upper portion on an upper substrate and a lower portion on a lower substrate. 1 and the charged particle generation chamber 2 are adjacent chambers separated by a substrate side wall plate (first substrate side wall plate) having a central hole, and the sample plate inserted from the opening formed in the upper substrate is a charged particle generation chamber. 1, the laser beam is applied to the sample attached to the sample plate from the opening formed in the upper substrate, and the sample is decomposed into particles, and the decomposed particles (decomposed particles) are the side walls of the substrate. The ionization beam selected from laser light, electron beam, synchrotron radiation, and X-rays passes through the central hole of the plate and enters the charged particle generation chamber 2 from the outside of the upper substrate or the lower substrate. Characterized in that charged particles are generated by irradiating the decomposed particles present in the inside,
Next to the charged particle generation chamber 2, there is an extraction electrode/acceleration chamber separated by a substrate side wall plate having a central hole (second substrate side wall plate),
The extraction electrode/acceleration chamber is a penetration chamber formed on the upper substrate on the upper side and on the lower substrate on the lower side.
In the inner surface of the charged particle generation chamber 2, the upper substrate and the lower substrate, and/or the side surface of the first substrate side wall plate, and/or the side surface of the second substrate side wall plate, and/or the side surface of the other two substrate side walls are electrically conductive. Body membrane electrodes are formed,
The conductor film electrode is connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is connected to a conductor film electrode/wiring formed on the outer surface of the upper substrate and/or the lower substrate. Characterized by
The charged particles having the same sign as the voltage applied to the conductor film electrode are attracted to the extraction electrode/acceleration chamber through the central hole of the second substrate side wall plate by the extraction electrode arranged in the extraction electrode/acceleration chamber. Characterized by
33. The mass spectrometer according to claim 1, wherein the charged particles that have entered the extraction electrode/acceleration chamber exit the extraction electrode/acceleration chamber and enter the mass analysis chamber. In the charged particle generating chamber 1, the back surface of the sample plate is arranged in close contact with the side surface of the substrate side wall, the substrate side wall is provided with a central hole, and the central hole is connected to the opening of the upper substrate or the lower substrate. 34. The mass spectrometer according to claim 33, wherein cavities in the thickness direction of the main substrate are connected to each other, and the sample plate is sucked to the side surface of the side wall of the substrate by being evacuated from the opening of the upper substrate or the lower substrate. .. The charged particle generation chamber for generating charged particles includes two through chambers (charged particle generation chambers 1 and 2) formed in an upper substrate at an upper portion and a lower substrate attached to a lower substrate. 1 and the charged particle generation chamber 2 are adjacent chambers separated by a substrate side wall plate having a central hole (first substrate side wall plate),
The sample plate inserted from the opening formed in the upper substrate is arranged in the charged particle generation chamber 1,
In the charged particle generating chamber 1, the back surface of the sample plate is arranged in close contact with the side surface of the substrate side wall, the substrate side wall is provided with a central hole, and the central hole is connected to the opening of the upper substrate or the lower substrate. The cavities in the thickness direction of the main substrate are connected, and the sample plate is sucked to the side surface of the substrate side wall by being evacuated from the opening of the upper substrate or the lower substrate.
A conductive film is formed on the side surface of the side wall of the substrate, and the conductive film formed on the side surface of the side wall of the substrate is connected to the conductive film formed on the surface of the upper substrate and/or the lower substrate on the charged particle generation chamber 1 side. , The conductor film is further connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is further connected to a conductor film electrode wiring formed on the outer surface of the upper substrate and/or the lower substrate. Then
A voltage is applied to the sample plate, which is a conductor, from the conductor film electrode wiring,
By irradiating the sample attached to the sample plate with a laser beam from the opening formed in the upper substrate, the sample is decomposed into particles and charged particles are generated,
Charged particles with the same sign as the charge of the sample plate jump out of the sample plate,
A substrate side wall plate (third substrate side wall plate) having a central hole in a direction facing the sample plate is arranged, a conductor film is formed on the surface of the third substrate side wall plate, and is formed on the surface of the third substrate side wall plate. The formed conductor film is connected to the conductor film formed on the surface of the upper substrate and/or the lower substrate on the charged particle generation chamber 1 side, and the conductor film is further formed on the upper substrate and/or the lower substrate. Connecting to a contact wiring, and the contact wiring is further connected to a conductor film electrode wiring formed on the outer surface of the upper substrate and/or the lower substrate,
A voltage opposite to the voltage applied to the sample plate is applied to the conductor film formed on the surface conductor of the third side wall plate from the conductor film electrode wiring, and the charged particles jumping out of the sample plate are extracted,
The charged particles pass through the central hole formed in the side wall plate of the third substrate and further enter the charged particle generating chamber 2 through the central hole of the side wall plate of the first substrate.
On the inner surface of the charged particle generating chamber 2, the upper substrate and the lower substrate, and/or the side surface of the first substrate side wall plate, and/or the side surface of the second substrate side wall plate, and/or the side surface of the other two substrate side wall plates, and / Or a conductor film electrode is formed on the inner surface of the central hole of the first substrate side wall plate,
The conductor film electrode is connected to a contact wiring formed on the upper substrate and/or the lower substrate, and the contact wiring is connected to a conductor film electrode/wiring formed on the outer surface of the upper substrate and/or the lower substrate. Characterized by
The voltage applied to the conductor film electrode has the same sign as that of the charged particles, and by adjusting the voltage, the charged particles are converged and the side wall plate of the substrate (second part) separating the charged particle generation chamber 2 from the adjacent chamber is formed. Incident on the adjacent chamber through a central hole of the substrate side wall plate),
33. The mass spectrometer according to claim 1, wherein the charged particles that have passed through the central hole of the second substrate side wall plate enter the mass spectrometry chamber. An upper substrate is attached to the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, the through chamber formed in the main substrate is used as an ionization chamber, and a central hole connecting to the ionization chamber is provided. Connect to the vertical hole (vertical direction to the substrate surface) formed in the main substrate that connects to the opening (opening for sample introduction) in the lower substrate,
A conductor film (second conductor film) is formed on the inner surface of the central hole, a conductor film (first conductor film) is formed on the inner surface of the ionization chamber, and the first conductor film and the second conductor film are formed in the ionization chamber. The first conductor film is connected by a conductor film formed on the side surface of the main substrate, and the first conductor film is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Characterized by
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the ionization chamber as a spray gas at the outlet to the ionization chamber,
By applying a voltage from the outer electrode formed on the upper substrate and/or the lower substrate, a voltage is applied to the conductor film formed on the inner surface of the central hole, whereby the gas (spray gas) ejected at the outlet of the ionization chamber ) Is an ionization method characterized by being ionized. An upper substrate is attached to the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, the through chamber formed in the main substrate is used as an ionization chamber, and a central hole connecting to the ionization chamber is provided. Connect to the vertical hole (vertical direction to the substrate surface) formed in the main substrate that connects to the opening (opening for sample introduction) in the lower substrate,
Parallel plate conductor film electrodes were formed on the upper and lower sides of the inner surface of the central hole, or parallel plate conductor film electrodes were formed on two side surfaces of the inner surface of the central hole, and each parallel plate conductor film electrode was formed on the inner surface of the ionization chamber. The conductor film is connected to the conductor films formed on the upper substrate and the lower substrate in the ionization chamber, and the outer side is formed on the upper substrate and/or the lower substrate through the contact wiring formed on the upper substrate and/or the lower substrate. Characterized by connecting to electrodes,
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the ionization chamber as a spray gas at the outlet to the ionization chamber,
By applying a high-frequency voltage from the outer electrode formed on the upper substrate and/or the lower substrate, a high-frequency voltage is applied to the conductor film formed on the inner surface of the central hole, so that the gas ejected at the outlet of the ionization chamber ( Spray gas) is an ionization method characterized by being ionized. A recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and/or the central hole. 38. The mass spectrometer according to claim 36 or 37, characterized in that it is cooled or heated. 39. The mass spectrometer according to claim 36, wherein the ionization chamber is heated by using a part of the conductor film formed on the upper substrate and/or the lower substrate. 39. The mass spectrometer according to claim 36, wherein the ionization chamber is heated by using a part of the conductor film formed in the central hole. A conductive film electrode is provided on a substrate side wall plate or a substrate side wall facing the extraction electrode chamber, and a voltage having the same sign as the ion is applied to the conductive film electrode to push out the ions into the extraction electrode chamber. The mass spectrometer according to any one of claims 36 to 40. An upper substrate is attached to the upper surface of the main substrate, a lower substrate is attached to the lower surface of the main substrate, and one penetration chamber formed in the main substrate is used as an ionization chamber. Whether the ionization chamber and the heating chamber are partitioned by a substrate side wall plate having a central hole (second central hole), or the ionization chamber and the heating chamber are the same penetration chamber and there is no substrate side wall plate for partitioning. ,
There is a central hole (first central hole) connected to the heating chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
A conductor film (second conductor film) is formed on the inner surface of the central hole, a conductor film (first conductor film) is formed on the inner surface of the heating chamber, and the first conductor film and the second conductor film are formed in the heating chamber. The first conductor film is connected by a conductor film formed on the side surface of the main substrate, and the first conductor film is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Characterized by
Sample liquid or sample gas is introduced from the sample introduction opening, through the vertical hole and the central hole, is introduced into the heating chamber as a spray gas at the outlet to the heating chamber,
A heating chamber is heated by applying a voltage from an outer electrode formed on the upper substrate and/or the lower substrate and flowing a current to the first conductive film to heat the first conductive film.
In the ionization chamber, a steeple electrode is arranged on the upper substrate and/or the lower substrate, and the steeple electrode is connected to an outer electrode formed on the upper substrate and/or the lower substrate through a contact wiring formed on the upper substrate and/or the lower substrate. Then, by applying a voltage to the outer electrode, the spray gas heated by causing discharge at the steeple electrode is ionized. A recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and/or the central hole. 43. The mass spectrometer according to claim 42, wherein the mass spectrometer is cooled or heated. The mass spectrometer according to claim 42 or 43, wherein the ionization chamber is heated by using a part of the conductor film formed on the upper substrate and/or the lower substrate. 45. The mass spectrometer according to claim 42, wherein the ionization chamber is heated by using a part of the conductor film formed in the central hole. A conductive film electrode is provided on a substrate side wall plate or a substrate side wall facing the extraction electrode chamber, and a voltage having the same sign as the ion is applied to the conductive film electrode to push out the ions into the extraction electrode chamber. 46. The mass spectrometer according to any one of claims 42 to 45. The upper substrate is attached to the upper surface of the main substrate, the lower substrate is attached to the lower surface of the main substrate, and the penetration chamber formed in the main substrate is used as the ionization chamber,
There is a central hole (first central hole) connected to the ion chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
The sample solution is introduced through the sample introduction opening, the matrix is formed at the outlet to the ionization chamber through the vertical hole and the central hole, and the laser is applied from the outside through the opening formed in the upper substrate or the lower substrate to the matrix. An ionization method characterized by irradiating a fast atom beam, which results in the molecules in the matrix being ionized. The upper substrate is attached to the upper surface of the main substrate, the lower substrate is attached to the lower surface of the main substrate, and the penetration chamber formed in the main substrate is used as the ionization chamber,
There is a central hole (first central hole) connected to the ion chamber, and the first central hole is a vertical hole (substrate) formed in the main substrate connected to the opening (sample introduction opening) of the upper substrate or the lower substrate. (In the direction perpendicular to the plane),
The sample solution is introduced through the sample introduction opening, passes through the vertical hole and the central hole, and a matrix is formed at the outlet to the ionization chamber,
Ionization, characterized in that a laser or fast atom beam chamber is placed next to the ionization chamber, the laser or fast atom beam chamber irradiates the laser or fast atom beam chamber onto the matrix, which results in the molecules in the matrix being ionized. Law. The penetrating chamber formed in the main substrate adjacent to the ionization chamber is the extraction electrode chamber, and the extraction electrode chamber and the ionization chamber are partitioned by the substrate side wall plate having the central hole (second central hole). A conductor film electrode is formed on the side surface of the facing substrate side wall, a voltage having the same sign as that of the ions is applied to the conductor film, and the generated ions are pushed out by the conductor film electrode to form the second central hole of the substrate side wall plate. 49. The ionization method according to claim 47 or 48, characterized in that the ionization method is carried out through the extraction electrode chamber. A recess and an opening that surround a part of the periphery of the ionization chamber are formed in the main substrate and the upper substrate and/or the lower substrate, and a cooling or heating medium is passed through the recess to form the ionization chamber and/or the central hole. 50. The ionization method according to any one of claims 47 to 49, wherein the ionization method is performed by cooling or heating. The conductor film is formed on the inner surface of the central hole and/or the inner surface of the penetration chamber, and an electric current is passed through the conductor film to generate heat to heat the central hole and/or the penetration chamber. 50. The ionization method according to any one of 50. The upper substrate is attached to the upper surface of the main substrate, and the lower substrate is attached to the lower surface of the main substrate.A ring electrode is formed on the main substrate.The penetration chamber formed in the center of the ring electrode is the ion trap chamber. An upper electrode (ion trap upper electrode) formed on the upper substrate is arranged on the upper portion, and a lower electrode (ion trap lower electrode) formed on the lower substrate is arranged on the lower portion of the ion trap chamber.
The ring electrode forms a conductor film (ring conductor film electrode) in a ring shape of the main substrate, and the ring conductor film electrode passes through the contact wiring formed on the upper substrate and/or the lower substrate to the upper substrate and/or the lower substrate. Connect to the outer electrode formed on the lower substrate,
The ion trap upper electrode and the ion trap lower electrode are connected to the outer electrodes formed on the upper substrate and the lower substrate through the contact wirings formed on the upper substrate and the lower substrate, and the ring electrode is a main substrate having a central hole. , One of the penetration chambers adjacent to the ion trap chamber is the ionization chamber or between the extraction electrode/accelerating electrode chamber and the ion trap chamber, and the other penetration chamber adjacent to the ion trap chamber. Located between an ion detection chamber and an ion trap chamber, one central hole connects from the ionization chamber to the ion trap chamber, the other central hole connects from the ion trap chamber to the ion detection chamber,
By applying a predetermined voltage to the ring conductor film electrode, the ion trap upper electrode, and the ion trap lower electrode, the ion trap chamber is passed through the central hole connected to the ion trap chamber from the ionization chamber or the extraction electrode/acceleration electrode chamber. The ion that entered is trapped in the ion trap chamber, and the trapped ion is emitted from the ion trap chamber through the central hole connected to the ion detection chamber to the ion detection chamber and is detected. , Ion trap mass spectrometer. The upper substrate is attached to the upper surface of the main substrate, and the lower substrate is attached to the lower surface of the main substrate.A ring electrode is formed on the main substrate.The penetration chamber formed in the center of the ring electrode is the ion trap chamber. An upper electrode (ion trap upper electrode) formed on the upper substrate is arranged on the upper portion, and a lower electrode (ion trap lower electrode) formed on the lower substrate is arranged on the lower portion of the ion trap chamber.
The ring electrode forms a conductor film (ring conductor film electrode) in a ring shape of the main substrate, and the ring conductor film electrode passes through the contact wiring formed on the upper substrate and/or the lower substrate to the upper substrate and/or the lower substrate. Connect to the outer electrode formed on the lower substrate,
The ion trap upper electrode and the ion trap lower electrode are connected to the outer electrodes formed on the upper substrate and the lower substrate through the contact wirings formed on the upper substrate and the lower substrate, and the ring electrode is a main substrate having a central hole. ,
One of the penetration chambers located above the ion trap chamber is the ionization chamber or between the extraction electrode/acceleration electrode chamber and the ion trap chamber, and the other penetration chamber adjacent to the ion trap chamber. It is arranged between the ion detection chamber and the ion trap chamber, one central hole is connected from the ionization chamber to the ion trap chamber, the other central hole is connected from the ion trap chamber to the ion detection chamber,
By applying a predetermined voltage to the ring conductor film electrode, the ion trap upper electrode, and the ion trap lower electrode, the ion trap chamber is passed through the central hole connected to the ion trap chamber from the ionization chamber or the extraction electrode/acceleration electrode chamber. The ion that entered is trapped in the ion trap chamber, and the trapped ion is emitted from the ion trap chamber through the central hole connected to the ion detection chamber to the ion detection chamber and is detected. , Ion trap mass spectrometer. An accelerator including a main substrate having a plurality of through-holes penetrating from the upper surface to the lower surface, an upper substrate attached to the upper surface of the main substrate, a lower substrate attached to the lower surface of the main substrate, and a substrate sidewall plate having a central hole partitioning the through-hole. Wherein the charged particles pass through the through chamber and the central hole of the substrate side wall plate. 55. The accelerator according to claim 54, wherein the accelerator includes a charged particle generation mechanism and a linear acceleration mechanism, and the charged particle generation mechanism and the linear acceleration mechanism are formed in the through chamber. The electrodes and wirings formed in the penetrating chamber are conductor films laminated by one or more methods selected from a CVD method, a PVD method, a plating method, and an electroforming method, and the upper substrate and/or the lower substrate. 56. The accelerating device according to claim 53 or 55, wherein the accelerating device is connected to the outer electrode formed on the upper substrate and/or the lower substrate through the contact wiring formed on the substrate. The linear acceleration mechanism is configured by arranging a plurality of electrodes (substrate side wall plate electrodes) having a conductor film formed on a substrate side wall plate having a central hole, and applying a static voltage or a high frequency voltage to the substrate side wall plate electrodes. The acceleration device according to any one of claims 54 to 56, wherein the charged particles are accelerated or decelerated (focused). The accelerating device further has a deceleration (focusing) mechanism, and the deceleration (focusing) mechanism is configured by arranging a plurality of electrodes (substrate sidewall plate electrodes) having a conductor film formed on a substrate sidewall plate having a central hole. The acceleration device according to any one of claims 54 to 57, wherein the charged particles are decelerated (focused) by applying a reverse voltage to the charged particles to the substrate sidewall plate electrode. .. The acceleration device according to any one of claims 54 to 58, wherein the acceleration device further has a deceleration (focusing) mechanism, and the deceleration (focusing) mechanism is performed by a quadrupole magnet. .. A quadrupole magnet has electromagnets arranged vertically in the vertical direction (perpendicular to the substrate surface) from the outside of a substrate having a through chamber formed in the substrate which is a passage for charged particles, and a substrate which is a passage for charged particles. 60. The accelerator according to claim 59, wherein electromagnets are arranged on both sides in a lateral direction (a direction perpendicular to the vertical direction) from the outside of the substrate having the through chamber formed therein. 61. The accelerator according to claim 60, wherein, when the electromagnets are arranged in the lateral direction, the substrate region at the place where the electromagnets are arranged is cut and the electromagnets are arranged in the openings. The accelerating apparatus according to claim 61, wherein the cutting method is laser dicing or high pressure liquid jet dicing. 61. The accelerator according to claim 60, wherein the coils are arranged in the main substrate on both sides of the through chamber. For the coil, a conductor film (through hole wiring) is formed in the through holes penetrating the upper and lower substrates and the main substrate, and wiring for connecting the through hole wiring is formed on the upper and lower substrates to form the coil wiring. 64. The accelerator according to claim 63, wherein the electrodes are formed on the upper substrate and/or the lower substrate. A through chamber (through chamber for coil placement) is formed on both sides of the through chamber (through chamber for charged particle focusing), and a coil is inserted into the through chamber for coil placement and coils are placed on both sides of the through chamber for focusing charged particles. 64. Accelerator according to claim 63, characterized in that 66. The accelerator according to claim 65, wherein the coil is arranged by inserting the coil attached to the support substrate into the coil arrangement through chamber. 67. The accelerator according to any one of claims 59 to 66, wherein the coils are arranged in an upper portion and a lower portion of the coil arrangement through chamber. 69. The accelerator according to claim 67, wherein the coil is disposed in close contact with or close to the upper substrate and the lower substrate. 69. The accelerator according to claim 68, wherein the coil-formed substrate (coil-formed substrate) is attached to the upper substrate and the lower substrate to dispose the coil.