WO2011081188A1 - Spectromètre de masse quadripolaire - Google Patents

Spectromètre de masse quadripolaire Download PDF

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Publication number
WO2011081188A1
WO2011081188A1 PCT/JP2010/073736 JP2010073736W WO2011081188A1 WO 2011081188 A1 WO2011081188 A1 WO 2011081188A1 JP 2010073736 W JP2010073736 W JP 2010073736W WO 2011081188 A1 WO2011081188 A1 WO 2011081188A1
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Prior art keywords
quadrupole
electrodes
mass spectrometer
annular
electrode
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PCT/JP2010/073736
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English (en)
Japanese (ja)
Inventor
善郎 塩川
恵 中村
強 彭
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キヤノンアネルバ株式会社
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Publication of WO2011081188A1 publication Critical patent/WO2011081188A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/421—Mass filters, i.e. deviating unwanted ions without trapping
    • H01J49/4215—Quadrupole mass filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/068—Mounting, supporting, spacing, or insulating electrodes

Definitions

  • the present invention relates to a quadrupole mass spectrometer that performs mass separation of ions passing through four electrodes.
  • FIG. 1A is a configuration diagram of a conventional quadrupole analyzer, where reference numeral 1 is an ion source, reference numeral 2 is a mass analyzer, and reference numeral 3 is a detector.
  • the mass analyzer 2 has four cylindrical electrodes 4, and ions 5 emitted from the ion source 1 pass between the four cylindrical electrodes 4 and enter the detector 3.
  • the opposing electrodes (facing each other with the central axis of the mass analyzer in between) are electrically coupled (conducted), and a direct-current voltage (DC) and a high-frequency voltage (RF) is applied to form a quadrupole electric field (“U-quadrupole electric field” to be described later) 7, and only ions having a mass number corresponding to each voltage, frequency, etc. It is made to pass in the longitudinal direction of the electrode 4.
  • DC direct-current voltage
  • RF high-frequency voltage
  • vacuum ultraviolet rays may be incident on the detector 3 from the ion source 1 as described above. This is because vacuum ultraviolet light (light with high energy) is generated in the ion source 1. Further, when the ions 5 collide with the cylindrical electrode 4, soft X-rays (light having higher energy) may be generated and enter the detector 3. Such high-energy light that has entered the detector 3 due to vacuum ultraviolet rays, soft X-rays, or other factors will be collectively referred to as “stray light”. That is, the stray light 6 may enter the mass analyzer 2 together with the ions 5.
  • a high-frequency voltage and a DC voltage are applied to four parallel electrodes.
  • a rectangular frame-shaped insulating support 14 having an inner dimensional accuracy is used, and each of the four cylindrical electrodes 11a to 11d is brought into close contact with the inner surface of the insulating support 14 by tightening screws 13. ing.
  • This method has a problem that the accuracy (internal dimensional accuracy) of the insulating support 14 is difficult to obtain and is high in cost, and that the screw tightening force must be within a range.
  • a metal film formed on the surface of an insulator processed into an arc shape is used instead of a metal cylinder as a cylinder electrode (see Patent Document 1). That is, the metal films 16a to 16d are formed on the surfaces of the insulating supports 15a to 15d, respectively.
  • various methods can be used for the structure of the four insulating supports 15a to 15d, it is general that the outer sides of the insulating supports 15a to 15d are pressed together with the fixtures 17a to 17d. In this method, there are many places where the accuracy of the insulating support is required, and it is also difficult to arrange the metal films 16a to 16d in parallel with each other, and the cost is high.
  • two metal films are formed on one insulator (see Patent Document 2). That is, two protrusions 19a and 19b are formed on the insulating support 18a, and metal films 20a and 20b are formed on the protrusions 19a and 19b. Similarly, two protrusions 19c and 19d are formed on the insulating support 18b, and metal films 20c and 20d are formed on the protrusions 19c and 19d.
  • Various methods can be used for positioning and assembling the two insulating supports 18a and 18b, but it is general that the spacers are pressed with a thickness accuracy between them. In this method, the number of parts is reduced, but it is difficult to obtain the accuracy of the insulating support so that the four protrusions 19a to 19d are parallel to each other, and the problem of high cost is not improved so much.
  • the insulating support 21 is a hollow insulating support 21 having four regions recessed in a hyperbola inward along the longitudinal direction, and inside the four recessed regions of the insulating support 21.
  • Metal films 22a to 22d are formed. This method is excellent in that the number of parts is extremely small and assembly is not required, but the insulating support 21 when forming the hyperbolic depressions so that the formed metal films 22a to 22d are parallel to each other. It is difficult to ensure the accuracy of the system, and the cost problem is increasing.
  • the ions 5 to be signals are emitted from the ion source 1, but unavoidably high energy such as vacuum ultraviolet light or soft X-rays (that is, the ionization process) , Stray light 6) is emitted. Since the stray light 6 has no electric charge, it is incident on the detector 3 without being separated by the mass analyzer 2 and is detected as a false signal by the detector 3 because of its high energy. Since this is not an original signal, it becomes a background (noise) and deteriorates the performance of sensitivity (S / N). In particular, the conventional quadrupole mass spectrometer has a problem of stray light because the electrodes are straight (the detector can be expected from the ion source).
  • FIG. 2A there is an example in which the stray light 6 from the ion source 1 is difficult to enter the detector 3 by installing a curved ion guide 1 in front of the mass analyzer 2.
  • a bent ion guide 30 is provided between the ion source 1 and the mass analyzer 2.
  • the ion guide 30 has four curved cylindrical electrodes (metal cylinders) 31, and the ion 5 passes between the four cylindrical electrodes 31.
  • a quadrupole electric field (“U-less quadrupole electric field” described later) 32 is formed between the cylindrical electrodes 31. .
  • the ions 5 travel while bending along the curve of the cylindrical electrode 31 (curve of the ion guide).
  • the ions 5 pass between the cylindrical electrodes 31 or at the cylindrical electrode 31. It will be absorbed and reflected. Therefore, the stray light 6 incident on the detector 3 can be reduced.
  • the stray light 6 is reflected on the surface of the cylindrical electrode 31 with a reflectivity of about several tens of percent, some of the reflected stray light is reflected to the detector 3 side. Therefore, the stray light problem has not been significantly improved.
  • the ion guide allows all ions to pass through without mass separation, and the quadrupole mass analyzer has the same mechanical structure and coupling (conduction) state, but only high-frequency voltage. Is applied and no DC voltage is applied. The high frequency voltage is customarily called the V voltage and the DC voltage is called the U voltage.
  • a quadrupole electric field having a mass analysis function as a mass analyzer is referred to as “a quadrupole electric field with U”, an ion guide.
  • a quadrupole electric field having no mass spectrometric function is referred to as “U-less quadrupole electric field”.
  • the ion guide does not perform mass fractionation, the accuracy of the electrodes (particularly, the accuracy with which the four electrodes are arranged in parallel) is not as required as the mass analyzer. Therefore, although the conventional ion guide uses an electrode having a curvature, the fixing method is basically the same as the method of the mass analyzer (FIGS. 1B to 1E).
  • FIG. 2B to 2E are cross-sectional views showing how a conventional ion guide is fixed.
  • the cylindrical electrodes 33a to 33d of the ion guide are fixed by screws 34 inside the insulating support 35 having a hollow structure.
  • FIG. 2B is a cross-sectional view of FIG.
  • FIG. 2D also shows a structure in which the metal parts 39a to 39d are fixed to the insulating support 38 by screws 34 (see Patent Document 6).
  • the insulating support 38 has a very complicated shape, and the cost problem is counterproductive even if the number of parts is reduced. Note that not only the structure shown in FIG. 2D but also in FIGS. 2A and 2B, the influence of “bending” is strong, and it is difficult to achieve accuracy throughout. Therefore, in this state, the structure shown in FIGS. 2A to 2D can be used as an ion guide, but cannot be used as a mass analyzer.
  • Patent Document 5 discloses an ion filter in which a curved ion guide and a curved quadrupole mass spectrometer are arranged between an ion source and a detector.
  • 2E is a perspective view of the curved quadrupole mass spectrometer disclosed in Patent Document 5, and FIG. 2F illustrates how to assemble the curved quadrupole mass spectrometer shown in FIG. 2E. It is a figure for doing.
  • the curved quadrupole mass spectrometer 40 includes an insulating support 41 and metal parts 43 to 46 fixed to the insulating support 41 with screws 42. These metal parts 43 to 46 function as quadrupole electrodes and have hyperbolic surfaces 43c to 46c. In this way, the surfaces 43c to 46c are arranged so as to face each other, thereby forming a quadrupole electric field.
  • a plurality of through holes 49 are provided in the first surface 47 of the insulating support 41 and the second surface 48 facing the first surface 47. It has been.
  • Each of the metal parts 43 to 46 functions as a quadrupole electrode and is curved.
  • the metal part 43 has a hyperbolic surface 43c and a plurality of support spokes 43a, and a through hole 43b is formed in each of the support spokes 43a.
  • the metal part 44 has a hyperbolic surface 44c and a plurality of support spokes 44a, and through holes (not shown) are formed in each of the support spokes 44a.
  • the metal parts 45 and 46 have hyperbolic surfaces 45c and 46c and a plurality of support spokes 45a and 46a, respectively, and through holes 45b and 46b are formed in the support spokes 45a and 46a, respectively. ing.
  • each of the support spokes 43a is provided on the first surface 47 side of the insulating support 41 by passing the screws 42 through the through holes 43b, the through holes 49, and the through holes formed in the support spokes 44a.
  • the support spokes 44 a are fixed to the second surface 48 side of the insulating support 41.
  • each of the support spokes 45a is fixed to the first surface 47 side of the insulating support body 41 by passing the screw 42 through the through hole 45b, the through hole 49, and the through hole 46b.
  • the support spoke 46a is fixed to the second surface 48 side.
  • each of the four metal parts 43 to 46 to be arranged in parallel has a plurality of support spokes and through holes formed in the support spokes so that the surfaces 43c to 46c are parallel to each other.
  • each of the many through holes must be formed accurately. That is, each of the metal parts 43 to 46 has three objects to be adjusted so as to establish a parallel relationship so that the surfaces 43c to 46c are parallel to each other.
  • the metal part 43 establishes the positional relationship with the metal part 44 so that the surface 43c and the surface 44c are parallel, and the positional relation with the metal part 45 so that the surface 43c and the surface 45c become parallel.
  • positioning must be performed while aligning with the through holes of other metal parts positioned in this manner.
  • each through hole formed in the support spokes is positioned, there are a plurality of support spokes that should form the through holes, so each through hole must be accurately formed in the support spoke. Very high strictness is required for through-hole forming processing. Furthermore, since each support spoke is fixed to the insulating support body 41 through a plurality of through holes 49, the above through holes 49 are also required to be processed very strictly.
  • Patent Document 5 there are many reference points (such as through holes formed in the support spokes and through holes formed in the insulating support 41) as factors that determine the parallelism of the surfaces 43c to 46c. There will be a separate reference point. Therefore, unless the through holes, each of the metal parts having the support spokes, and the insulating support 41 are made precisely, the parallelism of the surfaces 43c to 46c cannot be expected. Further, as described above, since there are many factors that determine the parallelism, the process of adjusting them is complicated and takes a lot of time and effort.
  • Patent Document 5 the metal parts 43 to 46 have a very complicated shape, which increases costs.
  • each of the metal parts 43 to 46 serving as the quadrupole electrodes has support spokes, so there is a limit to downsizing the quadrupole mass spectrometer 40.
  • the support spoke has a complicated structure and is difficult to manufacture. Therefore, when the support spoke is further reduced, it becomes more difficult to produce the support spoke.
  • the support spoke must be formed with a through hole for fixing the support spoke to the insulating support 41, and in order to stably fix the support spoke to the insulating support 41 while forming the through hole. The support spokes need to secure a certain length.
  • the present invention has been made in view of such problems, and the object of the present invention is to reduce the incidence of stray light from the ion source on the detector and to increase the sensitivity (S / N). It is an object of the present invention to provide a quadrupole mass spectrometer that can be miniaturized.
  • Another object of the present invention is to reduce the incidence of stray light from the ion source to the detector while improving the accuracy of the parallelism of the quadrupole electrode and increasing the resolution. It is an object of the present invention to provide a quadrupole mass spectrometer that can be configured.
  • one embodiment of the present invention is a quadrupole mass spectrometer that includes an ion source that ionizes neutral molecules and emits ions, and four non-linear electrodes.
  • a quadripole in a region surrounded by the four electrodes by applying a voltage in which a DC voltage and a high-frequency voltage are superimposed between two opposing electrode sets of the four electrodes.
  • a mass separation region for performing mass fractionation of the ions passing through the quadrupole field by forming an electric field; a detector for detecting the ions that have passed through the mass separation region as signals; and a concentric fit
  • the mass separation region is configured, and the four electrodes are at least a part of four concentric annular electrodes, and each of the four annular electrodes is formed on a part of the insulating support.
  • the conductive film is assembled by a circularly symmetrical fitting between the insulating supports by the fitting portion.
  • Another aspect of the present invention is a quadrupole mass spectrometer, a mass fractionation region having an ion source that ionizes neutral molecules and emits ions, and four non-linear electrodes, A quadrupole electric field is formed in a region surrounded by the four electrodes by applying a voltage in which a DC voltage and a high-frequency voltage are superimposed between two opposing electrode sets among the four electrodes, and the quadrupole electric field is formed.
  • the mass fractionation region is non-linear.
  • the mass fractionation region is configured such that the non-linear mass fractionation region prevents the detector from being viewed from the ion source through the mass fractionation region, and the four electrodes are concentric four annular rings. Less of electrode Also part, the four annular electrodes, characterized in that it is assembled by fitting the plate-like insulating support having a concentric fitting portion.
  • the detector is configured such that the detector cannot be expected through a portion surrounded by four electrodes for forming a quadrupole electric field having a U necessary for mass spectrometry from the ion source. Incident stray light can be reduced. Furthermore, by forming the four electrodes in a concentric ring shape, the four electrodes can be arranged with high parallelism.
  • FIG. 2E It is a block diagram of the conventional quadrupole-type mass spectrometer provided with the ion guide to which a DC voltage is not applied. It is sectional drawing which shows a mode that the conventional ion guide is fixed. It is sectional drawing which shows a mode that the conventional ion guide is fixed. It is sectional drawing which shows a mode that the conventional ion guide is fixed. It is a perspective view of the conventional curved quadrupole mass spectrometer. It is a figure for demonstrating how to assemble the curved quadrupole-type mass spectrometer shown by FIG. 2E. It is a figure which shows the structure of the quadrupole-type mass spectrometer which concerns on one Embodiment of this invention. FIG.
  • FIG. 3B is a cross-sectional view of the quadrupole mass spectrometer shown in FIG. 3A.
  • FIG. 3B is a circuit diagram of the quadrupole mass spectrometer shown in FIG. 3A. It is a figure which shows the structure of the quadrupole-type mass spectrometer which concerns on one Embodiment of this invention. It is a figure explaining the mode of fitting of the circularly symmetric thing of the quadrupole-type mass spectrometer shown to FIG. 3D, Comprising: The mode of fitting with an annular electrode and an annular
  • FIG. 3D It is a figure explaining the mode of fitting of the circularly symmetric thing of the quadrupole-type mass spectrometer shown to FIG. 3D, Comprising: The mode of fitting with an annular electrode and an annular
  • FIG. 3A It is sectional drawing of the orthogonal
  • FIG. 3A it is a figure for demonstrating the form which provides a spacer in the fitting part of a cylindrical electrode and an insulation support body. It is a figure which shows the mode of the fitting of the electrode which concerns on one Embodiment of this invention, and an insulation support body, and the fitting of insulation support bodies. It is a figure which shows the example which attaches the quadrupole-type mass spectrometer which concerns on one Embodiment of this invention to a sputtering device.
  • the four electrodes (quadrupole electrode) provided in the quadrupole mass spectrometer are configured so that the cross section of the quadrupole electrode satisfies a specific relationship regarding the curvature and position of the electrode in each cross section.
  • the longitudinal direction is concentric "annular" so that stray light from the ion source does not enter the detector or reduces the incidence of the stray light, and these quadrupole electrodes are fitted to each other so ] To improve the accuracy of the parallelism of the electrodes.
  • the quadrupole electrode is bent so as to reduce stray light incidence.
  • the quadrupole mass spectrometer having the above structure can be easily downsized.
  • a support spoke and an insulating support for fixing the support spoke are required.
  • the support spokes that are difficult to reduce in size are not required by adopting the fitting structure. Therefore, it is easy to reduce the size of the quadrupole mass spectrometer.
  • the merit of miniaturization of the apparatus according to the present invention relating to a quadrupole mass spectrometer has the intrinsic value of expanding the upper limit of the atmospheric pressure that can be measured, in addition to saving space and reducing weight.
  • the upper limit of the pressure that can be measured is the pressure at which the mean free path of the atmosphere is approximately the same as or longer than the orbital distance (movement distance) of ions.
  • the orbital distance movement distance
  • Sputtering equipment is frequently used in advanced industries such as semiconductors, but the operating pressure of the sputtering equipment is about 0.3 Pa, and the mean free path at that time is about 10 to 20 mm. That is, a small quadrupole mass spectrometer with an orbital distance of ions of about 10 to 20 mm is required.
  • the conventional quadrupole mass spectrometer has an orbital distance of about 100 to 200 mm, downsizing of 1/10 is required.
  • the quadrupole mass spectrometer is used. Can be reduced in size, so that the orbital distance of ions can be shortened. More importantly, in one embodiment of the present invention, even if the quadrupole electrodes are bent so as to reduce stray light incidence on the detector, the parallelism between the quadrupole electrodes is improved, The downsizing can be realized.
  • the quadrupole mass spectrometer 100 includes an ion source 101, a quadrupole mass analyzer 102, and a detector 103.
  • the ion source 101 and the detector 103 are surrounded by cases 108a and 108b with openings, respectively.
  • the component to be measured (neutral molecule) becomes an ion 105 in the ion source 101, and only specific ions that meet the set conditions pass through the quadrupole mass analyzer 102 and reach the detector 103 as a signal. Detected.
  • the ion source 101 can be the most common electron impact (EI) type ion
  • the detector 103 can be a microchannel type electron multiplier plate (MCP).
  • EI electron impact
  • MCP microchannel type electron multiplier plate
  • the quadrupole mass analyzer 102 of the present embodiment basically has four electrodes 104a to 104d (in this specification, electrodes 104a to 104d) that are, for example, metal cylinders.
  • a high-frequency voltage (RF) and a direct-current voltage (DC) are applied to the electrode 104 (also generally referred to as an electrode 104).
  • the opposing electrodes 104a and 104d (facing each other with the central axis of the mass analyzer in between) and electrodes 104b and 104c are coupled (conducted), respectively, and a DC voltage is generated between the two electrode sets.
  • a quadrupole electric field 107 is formed in a region U (region where ions 105 fly) surrounded by the electrodes 104a to 104d.
  • the center voltage of the DC voltage and the high-frequency voltage determines the axial velocity of the ions, and is determined by other requirements.
  • the curvature of each electrode and each position satisfy a specific relationship known in the art, while the longitudinal direction of the electrode is a concentric “circular ring”. (3/4 laps).
  • the four electrodes 104 are non-linear and are annular, so the quadrupole mass analyzer 102 is also a linear ring. Therefore, the present embodiment is configured such that the detector 103 cannot be expected from the ion source 101 by the non-linear quadrupole mass analyzer 102.
  • Each of the four electrodes 104 is a concentric annular electrode, and two of the four electrodes 104 (reference numerals 104a and 104c in FIG. 3B) have the same first radius, and the remaining 2 Two electrodes (reference numerals 104b and 104d in FIG. 3B) are larger than the first radius and have the same second radius. Therefore, as shown in FIG. 3B, the parallelism between the annular electrodes 104a and 104b can be improved by arranging the annular electrodes 104a and 104b to be concentric. Similarly, by arranging the annular electrodes 104c and 104d to be concentric, the parallelism between the annular electrodes 104c and 104d can be improved.
  • annular electrode 104a (104b) and the annular electrode 104c (104d) are arranged.
  • the degree of parallelism with 104c (104d) can be improved, and as a result, the four annular electrodes 104a to 104d can be arranged in parallel with each other or with the degree of parallelism improved.
  • the electrodes 104a to 104a are arranged such that the annular surface of the electrode 104a (104c) having the first radius coincides with the annular surface of the electrode 104b (104d) having the second radius. 104d are arranged concentrically. Therefore, the electrodes 104a to 104d can be arranged with high parallelism.
  • the metal cylinder used as the cylinder electrode 104 is made of stainless steel (SUS) or molybdenum (Mo). In any cross section, the curvature of each electrode and the position of each electrode maintain a system of several microns (micrometers) or less. Therefore, ions exiting the ion source 101 enter the detector 103 with a 270 ° curve.
  • SUS stainless steel
  • Mo molybdenum
  • the ions 105 are converged while vibrating with a high frequency voltage of several hundreds V or more and about several MHz in the cross-sectional direction, but proceed with a voltage difference of only about several V in the longitudinal direction. . Therefore, the centrifugal force generated in the ions due to the curve in the traveling direction is almost canceled by the high potential in the cross-sectional direction, so the adverse effect due to the curve is very slight. Therefore, the ion incident from the ion source 101 is detected by detecting the ion 105 to be detected by traveling in the quadrupole electric field 107 with U and being separated by mass while the annular electrode 104 is curved. Incident on the vessel 103.
  • the ion source 101 and the detector 103 are installed in cases 108a and 108b that are closed except for the surface on the quadrupole mass spectrometer 102 side, the stray light 106 from the ion source 101 is quadruple. There is a possibility of being incident on the detector 103 only by reflection inside the polar mass analyzer 102. However, since the quadrupole mass spectrometer 102 is curved as much as 270 °, the incident light to the detector 103 is limited to only one reflected several times.
  • the quadrupole mass analyzer 102 that can perform mass analysis by applying both a DC voltage and a high-frequency voltage is non-linear, and the non-linear quadrupole.
  • the ion source 101 and the detector are prevented from being detected by the polar mass analyzer 102 through the portion surrounded by the four electrodes 104 that are components of the quadrupole mass analyzer 102 from the ion source 101.
  • 103 and the quadrupole mass analyzer 102 are configured.
  • the ions 105 and the stray light 106 are on the left side of the ion source 101 in FIG. 3A. Since the cases 108a and 108b are obstructed, a configuration in which the detector 103 cannot be expected from the ion source 101 is realized. Further, on the right side of the ion source 101 in FIG. 3A, the quadrupole mass analyzer 102 is formed in a non-linear annular shape, so that a configuration in which the detector 103 cannot be expected from the ion source 101 is realized. ing.
  • the ions 105 that are desired to be detected can reach the detector 103, and the amount of stray light 106 that is not desired to be detected can be reduced. Therefore, detection of noise in the detector 103 can be reduced, and sensitivity (S / N ratio) can be increased.
  • the quadrupole mass analyzer 102 By bending the quadrupole mass analyzer 102 itself, through the portion surrounded by the four electrodes 104a to 10d (bent electrodes) of the quadrupole mass analyzer 102 from the ion source 101. This is preferable because the detector can be prevented from being expected and the incidence of the stray light 106 on the detector 103 can be reduced.
  • the quadrupole mass analyzer 102 considering that the quadrupole mass analyzer 102 operates well, it is more preferable to arrange the four bent electrodes with high parallelism. In order to achieve this, it is required to arrange at least the electrodes 104a to 104d with the parallelism required for the user to perform a desired measurement.
  • the electrode is bent in order to reduce the incidence of stray light on the detector, but the configuration of bending this electrode is to form a U-less quadrupole field. It is an ion guide, not a mass analyzer with a U-containing quadrupole field. That is, conventionally, in order to reduce the incidence of the stray light 6 on the detector 3, it is necessary to provide an ion guide 30 that is curved separately from the mass analyzer 2. This is because even if the cylindrical electrode 4 of the mass analyzer 2 is bent, it is still required to arrange the four electrodes necessary for the mass analysis in parallel as much as possible, and the four bent electrodes are highly parallel to each other. Arranging at a degree is associated with considerable difficulty.
  • annular electrodes 104a and 104c two annular electrodes having a first radius and two annular electrodes having a second radius larger than the first radius are used.
  • a quadrupole mass spectrometer 102 is formed using electrodes (electrodes 104b and 104d). Therefore, by arranging the four electrodes concentrically, the electrodes can be arranged with high parallelism simply and at low cost. This is because a technique for processing an annular object with high accuracy has been established, and by using this technique, concentric annular electrodes having a uniform radius (a pair of electrodes 104a and 104c, and electrodes 104b and 104d). Since the electrodes are annular, when the four electrodes 104a to 104d are arranged, the reference points for the arrangement of the respective electrodes can be set at the same point. is there.
  • annular electrodes 104a and 104c inner electrodes arranged on the inside
  • two annular electrodes 104b and 104d outer electrodes having a larger diameter than the inner electrodes.
  • annular electrodes with the arranged outer electrode are prepared, and two pairs are arranged in which the inner electrode is arranged concentrically inside the outer electrode (first pair (electrode 104a and electrode 104b) and second pair Pair (electrode 104c and electrode 104d), and these pairs are spaced apart in the left-right direction (the in-plane vertical direction of the annular electrode, the left-right direction in FIG. 3D). Since the inner electrode and the outer electrode are annular, the parallelism between the outer electrode and the inner electrode can be improved by arranging them concentrically.
  • the first pair of inner electrodes and the second pair of inner electrodes face each other (facing each other with the central axis of the mass analyzer in between), and the first pair of outer electrodes and the second pair Of the first pair of inner electrodes and the second pair of inner electrodes, and between the first pair of outer electrodes and the second pair of outer electrodes.
  • a spacer having the same thickness for example, insulating supports 111a and 111b described later
  • the electrodes 104a and 104d are electrically coupled, and the electrodes 104b and 104c are electrically coupled, and a high frequency voltage (RF) and a direct current are connected between these two electrode sets.
  • RF high frequency voltage
  • DC voltage superimposed with a voltage
  • a quadrupole electric field 107 with U is formed, and mass spectrometry can be performed. That is, each electrode is arranged concentrically using an annular electrode 104, and further, a high frequency voltage and a direct current voltage are applied to the annular electrode 104, so that the quadrupole mass analyzer 102 has a stray light reduction function. And a mass spectrometric function.
  • the present embodiment by arranging the four annular electrodes concentrically, the portions surrounded by the four electrodes 104a to 104d from the ion source 101 while arranging each electrode with high parallelism.
  • the detector 103 cannot be expected.
  • by incorporating a stray light reduction function into the mass analyzer it is possible to suppress the incidence of stray light to the detector without providing an ion guide separately as in the prior art.
  • FIG. 3D is a diagram illustrating a configuration for arranging the annular electrodes 104 provided in the quadrupole mass spectrometer according to the present embodiment with high parallelism.
  • the left figure of FIG. 3D is a cross-sectional view perpendicular to the flight direction of the ions 105 (3 ⁇ cross-section of the right figure of FIG. 3D), and the right figure of FIG. (3 ⁇ cross section in the left figure of 3D).
  • an insulating support that determines the position while insulating them is important.
  • the insulating support include machinable ceramics (ceramics that can be machined, such as Macor, Photovale, Macerite, etc.) in view of electrical insulation and workability.
  • the insulating supports 111a, 111b, 112a, and 112b are formed of such materials.
  • the insulating supports 112a and 112b are formed in the same concentric annular shape as the annular electrode 104, and their cross sections have this character shape.
  • the position of the electrode having a large ring diameter is determined by the surface facing the center direction on the outside of the character, and the position of the electrode having a small ring diameter is determined by the surface facing the outside direction on the inside.
  • the position of the electrode 104a having a small diameter is determined by the surface 113a facing the outer direction inside the character, and the diameter is determined by the surface 113b facing the center direction outside the character.
  • the position of the large electrode 104b is determined.
  • the position of the electrode 104c having a small diameter is determined by the surface 113c facing the outer direction inside the character, and the surface 113d facing the central direction outside the character.
  • the position of the electrode 104d having a large diameter is determined.
  • the positioning of the ring in the axial direction is not a fit but a method similar to the conventional method. That is, the axial positioning is performed using an annular insulating support 111a and an annular insulating support 111b having a diameter smaller than that of the insulating support 111a as spacers.
  • 3E and 3F show details of an assembling method by fitting circularly symmetric objects of the quadrupole mass spectrometer shown in FIG. 3D.
  • the electrodes 104a to 104d are positioned by the respective surfaces of the corresponding insulating supports 112a and 112b. Furthermore, the insulating supports 112a and 112b are also positioned by fitting circularly symmetrical objects. Therefore, each of the electrodes 104a to 104d has a structure that provides accuracy with reference to a common center point (concentric point).
  • the insulating support 112a is provided along the circumferential direction of the annular electrode 104b.
  • a fitting portion is formed between the surface 113b of the body 112a and the electrode 104b.
  • the electrode 104b is fitted by the presence of the surface 113b by producing the electrode 104b and the insulating support 112a so that the outer wall surface (surface 113b) of this character in the cross section of the insulating support 112a is fitted.
  • the insulating support 112a is fixed in place.
  • each of the insulating support 112a and the electrode 104b and the insulating support 112a and the electrode 104a, which are fittings of circularly symmetrical objects, are positioned with reference to a common center point (concentric point). Therefore, as a result, the electrodes 104a and 104b are also positioned with respect to a common center point (concentric point). Therefore, the electrode 104a and the electrode 104b can be arranged with high parallelism.
  • the description is omitted here, the same applies to ⁇ electrode 104cvs insulating support 112b> and ⁇ electrode 104dvs insulating support 112b> in FIG. 3F.
  • the electrode 104a and the electrode 104c, and the electrode 104b and the electrode 104d can be arranged with high parallelism, and as a result, the electrodes 104a to 104d can be arranged with high parallelism with each other.
  • Patent Document 5 when forming a curved quadrupole mass spectrometer, a reference for arranging four quadrupole electrodes in parallel with each other Since there are a plurality of points, the parallelism of the quadrupole electrode cannot be improved unless each of the plurality of reference points is formed with high accuracy. Therefore, it is necessary to accurately position the plurality of reference points.
  • the through holes formed in the support spokes 43a to 46a and the insulating support 41 for fixing the support spokes are used as reference points. It is necessary to precisely process the through hole.
  • each of the annular electrodes 104a to 104d included in the quadrupole mass spectrometer 100 is fitted to one of the annular insulating supports 112a and 112b, and The insulating supports 112a and 112b are fitted together. Since the fitting is a fitting of a circularly symmetric object, as a result, each of the annular electrodes 104a to 104d and the annular insulating supports 112a and 112b is based on the same reference point (concentric point). Thus, the electrodes 104a to 104d can be arranged with a high degree of parallelism.
  • the electrodes 104a to 104d are fixed by the fitting structure as described above, a support spoke that extends inward and is difficult to be miniaturized is required as in Patent Document 5. do not do.
  • the curved electrodes 104a to 104d (quadrupole electrodes) can be fixed with high parallelism without using support spokes that are rate-limiting for downsizing. Therefore, it is possible to reduce the size of the apparatus while reducing the detection of stray light and improving the parallelism of the quadrupole electrode.
  • the electrode 104a and the electrode 104b are fitted to the insulating support 112a, and the electrode 104c and the electrode 104d are fitted to the insulating support 112b. Then, the insulating support 112a and the insulating support 112b are fitted together via the insulating supports 111a and 111b, and the insulating supports 112a and 112b are fixed to the insulating supports 111a and 111b with screws 114. In this way, the quadrupole mass analyzer 102 in which the annular electrodes 104a to 104d are arranged with high parallelism is formed.
  • a circularly symmetric object can achieve high accuracy with respect to the size of the diameter.
  • the absolute value of the dimension itself may vary by several tens of ⁇ to several hundreds of ⁇ , but the value must match within a few microns in the longitudinal direction of the electrode. I must. This demands that there is little dimensional variation at each point on the circumference, which is in good agreement with the processing characteristics of a circularly symmetric object.
  • the gap in the fitting can be made very small. There is always a gap required for fitting, which is a deviation, but there is a technology established by many years of research on this value for fittings that are circularly symmetric, and design, processing, and assembly are performed accordingly. If this is done, the minimum gap can be realized. Specifically, a gap of several tens of micrometers or less is sufficiently possible.
  • the electrodes 104a to 104d which are metal cylinders, are partially cut away to avoid interference. That is, the notch 110 a is provided in the electrode 104 around the ion source 101, and the notch 110 b is provided in the electrode 104 around the detector 103. This may have some effect on the accuracy of a circularly symmetric object, but mass separation is not performed at the notched part, and the circular shape of the metal cylinder remains unchanged (the ring is broken). Is not considered to be a big problem.
  • the four electrodes 104 in order to realize a mass analysis function in the quadrupole mass analyzer 102 formed by the four electrodes 104, it is an object to arrange the four electrodes 104 with high parallelism to each other. Although it is one, it is not intended to be completely parallel. Although it is of course a preferred embodiment to be perfectly parallel, the above object of the present invention can be achieved even if it is not perfectly parallel. For example, even if the annular electrode 104 and the insulating supports 112a and 112b are manufactured with high accuracy, an error always occurs. Therefore, even if the quadrupole mass analyzer is configured by the method of this embodiment, the electrode 104 is It may be displaced from parallel.
  • the degree of parallelism can be realized so that the measurement desired by the user at that time can be performed.
  • the electrodes bent in order to reduce the influence of the stray light 106 are arranged with a low degree of parallelism, the mass spectrometry function may not be achieved. Therefore, if the electrodes 104a to 104d can be arranged with a high degree of parallelism, the mass analyzer formed by the electrodes can realize a mass analysis function sufficient for performing the measurement desired by the user, and is favorable. Mass spectrometry can be performed. Therefore, in this embodiment, it is only necessary that the longitudinal directions of the respective electrodes are aligned to such an extent that a desired measurement accuracy can be realized, and the electrodes need not be completely parallel.
  • the four quadrupole electrodes for forming a quadrupole electric field with U which are constituent elements of a quadrupole mass spectrometer, are non-linear (annular or the like).
  • These four electrodes an annular cylindrical electrode as in the present embodiment, an annular conductive film as in the second embodiment, etc.
  • the four quadrupole electrodes are formed into an annular shape, and the closed loop of the annular electrode of the quadrupole electrode is formed. Ion source and detector are built in.
  • the quadrupole electrodes are connected in a closed loop shape as in this embodiment, a high-frequency voltage and a direct-current voltage may be applied to a region where ions do not actually pass.
  • the quadrupole electrode is formed in an annular shape, an ion source and a detector are incorporated in the annular quadrupole electrode, and the quadrupole mass analyzer itself has a function of reducing stray light.
  • the fact that the ions emitted from the ion source are separated by mass in a quadrupole electric field with U and made incident on the detector is the same as before. Therefore, in the present invention, a region in which a quadrupole electric field with U is formed and ions fly (pass through) (that is, a mass separation region) is called a quadrupole mass analyzer.
  • a metal film coated on the surface of an insulating support is used as an electrode of a quadrupole mass spectrometer, not a metal cylinder.
  • the metal film is not limited, gold (Au) or chromium (Cr) can be used, and the thickness is preferably about 1 micrometer.
  • the member formed on the surface of the insulating support is formed to form a quadrupole electric field with U, and a conductive material that can form a quadrupole electric field with U by applying a high-frequency voltage and a DC voltage. If it is a film
  • the portion of the insulating support on which the electrode film is formed is processed into a shape in which a quadrupole electric field is formed.
  • This shape is not an arc shape but a hyperbolic shape capable of forming a more accurate quadrupole electric field.
  • the portion of the insulating support corresponding to the electrode is circularly symmetric with respect to the concentric point. It is only necessary to slowly shift the cutting blade (bite) applied to to the concentric point direction.
  • a hyperbolic shape is realized in the insulating support by simply matching the shift shape of the cutting blade to the hyperbola, but this is not a problem at all if it is an NC (numerical) control type processing apparatus.
  • rotating around the concentric point greatly contributes to the improvement of parallelism. Even when a die is used instead of cutting each time, the same merit is obtained in the production of the die. Others are the same as those in the first embodiment.
  • FIG. 4A is a diagram showing a configuration of a quadrupole mass spectrometer according to the present embodiment.
  • 4A is a cross-sectional view perpendicular to the flight direction of the ions 105 (4 ⁇ cross-section of the right view of FIG. 4A), and the right view of FIG. 4A is a cross-sectional view of the ions 105 on the annular flight surface (FIG. 4).
  • 4A (the 4 ⁇ cross section in the left figure).
  • each of the insulating supports 141a to 141d is a concentric annular shape and has a hyperbolic surface.
  • the hyperbolic surfaces are each formed in an annular shape.
  • the annular insulating supports 141a and 141c have the same diameter, and the annular insulating supports 141b and 141d have the same diameter.
  • Metal films 140a to 140d are formed in an annular shape on the hyperbolic surfaces of the insulating supports 141a to 141d, respectively.
  • FIG. 4B is a diagram showing the insulating supports 141a to 141d shown in FIG. 4A.
  • the insulating supports 141d and 141b are just in a mirror image relationship (first mirror image relationship)
  • the insulating supports 141a and 141c are just in a mirror image relationship (second mirror image relationship).
  • the insulating support 141a is configured to fit with the insulating support 141b
  • the insulating support 141c in a second mirror image relationship with the insulating support 141a is configured to fit with the insulating support 141d. ing.
  • the insulating support 141b is configured to be fitted to both of the insulating supports 141a and 141d, and the insulating support 141d in a first mirror image relation with the insulating support 141b is the insulating support 141b. It is configured to fit both sides.
  • FIG. 4C shows how the insulating supports 141a to 141d are fitted.
  • a fitting portion is formed by fitting the annular insulating supports 141b and 141d in a mirror image relationship, and the fitting portion is fixed using screws 114.
  • the insulating support 141a and the insulating support 141b are fitted together so as to be concentric to form a fitting portion, and the fitting portion is fixed by using a screw 114.
  • the insulating support 141c and the insulating support 141d are fitted together so as to be concentric to form a fitting portion, and the fitting portion is fixed using a screw 114.
  • the insulating support 141a having the second mirror image relationship and the insulating support 141b having the first mirror image relationship are positioned by fitting the circularly symmetrical objects, and the second mirror image relationship is obtained.
  • the insulating support 141c which is the first mirror image and the insulating support 141d which is the first mirror image relationship are positioned by fitting the circularly symmetrical objects. Therefore, the first structure of the fitted insulating support 141a and the insulating support 141b and the second structure of the fitted insulating support 141c and the insulated support 141d are just the third.
  • the hyperbolic surfaces of the insulating supports 141a to 141d have high parallelism. Can be arranged. Therefore, the metal films 140a to 140d can be arranged with a high degree of parallelism.
  • each of the annular insulating supports 141a to 141d on which a conductive film such as a metal film is formed is configured to be fitted with at least one of the other insulating supports.
  • each of the annular insulating supports 141a to 141d is arranged with reference to the same reference point (concentric point), and as a result, the metal films 140a to 140d are made highly parallel to each other. Can be arranged. Therefore, a configuration in which the four conductive films are arranged in a highly parallel state and the detector cannot be seen through the portion surrounded by the four conductive films (for example, metal films 140a to 140d) from the ion source is realized. it can. Therefore, it is possible to reduce the incidence of stray light on the detector without providing an ion guide, and to perform mass analysis satisfactorily.
  • FIGS. 5A, 5B, and 5C A quadrupole mass spectrometer according to a third embodiment of the present invention will be described with reference to FIGS. 5A, 5B, and 5C.
  • this embodiment there are two insulating supports, and metal films as two conductive films are formed on each insulating support. Others are the same as those in the second embodiment.
  • FIG. 5A is a diagram showing a configuration of a quadrupole mass spectrometer according to the present embodiment.
  • 5A is a cross-sectional view perpendicular to the flight direction of the ions 105 (5 ⁇ cross-section of the right view of FIG. 5A), and the right view of FIG. 5A is a cross-sectional view of the ions 105 on the annular flight surface (FIG. 5). 5A in the left figure of 5A).
  • the insulating support 151a has an annular shape, and has two hyperbolic surfaces formed in an annular shape in the in-plane vertical direction of the annular shape. Each has an annular metal coating 150a, 150b. Similarly, the insulating support 151b has an annular shape, and has two hyperbolic surfaces formed in an annular shape in the in-plane vertical direction, and each of the hyperbolic surfaces. Are formed with an annular metal coating 150c, 150d.
  • FIG. 5B is a diagram showing the insulating supports 151a and 151b shown in FIG. 5A.
  • the insulating supports 151a and 151b are just mirror images of each other, and the insulating supports 151a and 151b are opposed to the formed metal film (with the central axis of the mass analyzer in between).
  • hyperbolic surfaces 152a and 152b are formed in the in-plane vertical direction of the ring of the insulating support 151a.
  • These hyperbolic surfaces 152a and 152b have an annular shape concentric with the insulating support 151a, and are formed so as to be arranged with a high degree of parallelism.
  • hyperbolic surfaces 152c and 152d are formed in the in-plane vertical direction of the ring of the insulating support 151b. These hyperbolic surfaces 152c and 152d have an annular shape concentric with the insulating support 151b, and are formed so as to be arranged with a high degree of parallelism.
  • FIG. 5C shows how the insulating supports 151a and 151b are fitted together.
  • a fitting portion is formed by fitting annular insulating supports 151a and 151b having a mirror image relationship, and the fitting portion is fixed using screws 114.
  • the insulating support 151a and the insulating support 151b that are mirror images are set to have the same reference point (concentric point) so that the metal films 150a and 150b and the metal films 150c and 150d face each other. Fits to the standard. Therefore, the pair of metal films 150a and 150b arranged with high parallelism and the pair of metal films 150c and 150d arranged with high parallelism can be arranged with high parallelism.
  • the annular insulating supports 151a and 151b on which a conductive film such as a metal film is formed are configured to fit with each other.
  • the annular insulating supports 151a and 151b are arranged with reference to the same reference point (concentric point), and as a result, the metal films 150a to 150d can be made highly parallel to each other. Can be arranged. Therefore, a configuration in which the four conductive films are arranged in a highly parallel state and the detector cannot be seen through the portion surrounded by the four conductive films (for example, metal films 150a to 150d) from the ion source is realized. it can. Therefore, it is possible to reduce the incidence of stray light on the detector without providing an ion guide, and to perform mass analysis satisfactorily.
  • the number of insulating supports on which the metal film is formed is two and four, but may be three.
  • two hyperbolic surfaces are formed on one insulating support, one hyperbolic surface is formed on the remaining two insulating supports, and the three insulating supports are connected to each other. What is necessary is just to comprise so that it may fit.
  • a relatively large hyperbolic surface 161a is formed on the inside of the ring of the insulating support 151a, and a relatively small hyperbolic surface 161b is formed on the outside of the ring.
  • a relatively large metal film 160a is formed on the hyperbolic surface 161a, and a relatively small metal film 160b is formed on the hyperbolic surface 161b.
  • a relatively large hyperbolic surface 161c is formed inside the ring of the insulating support 151b, and a relatively small hyperbolic surface 161d is formed outside the ring.
  • a relatively large metal film 160c is formed on the hyperbolic surface 161c, and a relatively small metal film 160d is formed on the hyperbolic surface 161d. That is, in this embodiment, as can be seen from FIG. 6, the metal coatings 160a and 161d arranged inside the ring and the metal coatings 160b and 160c arranged outside the ring The cross-sectional shape in the perpendicular direction is different.
  • the region surrounded by the metal films 160a to 160d (the ions are A quadrupole electric field is formed with U in the flying region.
  • the traveling direction of the ions 105 is curved.
  • the centrifugal force generated in the ions 105 due to the curve in the traveling direction is almost canceled by the high potential in the cross-sectional direction, but strictly speaking, there is a force toward the outside.
  • the electrode shape is symmetric in every cross section, the electric field in a certain cross section is an accumulation of the electric fields from not only the surface but also the electrodes before and after that, so strictly speaking, the electric field is not symmetric and distortion is generated. It has occurred.
  • the shapes of the electrodes (conductive films) on the outer side and the inner side of the ring are determined so as to correct these effects. That is, in this embodiment, the influence of the centrifugal force is further reduced by making the size of the metal films 160a and 160c inside the ring larger than the size of the metal films 160b and 160d outside the ring. be able to. Considering the influence of the centrifugal force in this way is unique to the present invention in which the electrode of the mass analyzer is bent. In the present embodiment, in consideration of the phenomenon peculiar to the present invention, the outer and inner shapes of the conductive film formed in an annular shape are set to be different.
  • the inner hyperbolic surfaces 161a and 161b and the outer hyperbolic surfaces 161b and 161d are changed in size, but the inner hyperbolic surfaces and the outer hyperbolic surfaces 161b and 161d are changed in size. It is not essential to change the size of the curved surface, but to change the shape of the inner electrode (conductive film) and the outer electrode (conductive film). Therefore, as long as the shape can be changed between the metal films 160a and 160c and the metal films 160b and 160d, the shapes and sizes of the hyperbolic surfaces 161a to 161d are not limited.
  • a quadrupole mass spectrometer according to a fifth embodiment of the present invention will be described with reference to FIG.
  • the entire position of the electrode (conductive film) is rotated by 45 ° as a whole, and the electrode film of the insulating support is formed.
  • the shape is different on the outside, middle and inside. Others are the same as those in the fourth embodiment.
  • the insulating support 151a is formed with two hyperbolic surfaces 171a and 171b formed along the ring of the insulating support 151a, and the hyperbolic surfaces 171a, 171a,
  • the metal films 170a and 170b are formed on 171b.
  • the metal film 170b corresponds to the outer electrode of the ring, and the metal film 170a corresponds to the intermediate electrode. Therefore, the metal film 170b has the smallest shape and the metal film 170c has the intermediate size. Have.
  • two hyperbolic surfaces 171c and 171d formed along the ring of the insulating support 151b are formed on the insulating support 151b, and the hyperbolic surfaces 171c and 171d are formed on the hyperbolic surfaces 171c and 171d.
  • the metal film 170c corresponds to the inner electrode of the ring
  • the metal film 170c corresponds to the intermediate electrode. Therefore, the metal film 170c has the largest shape, and the metal film 170d has the intermediate size.
  • the four electrodes for forming a U-shaped quadrupole electric field have three radii (the largest radius electrode, the middle radius electrode, and the smallest radius electrode). Electrode).
  • the metal film 170c disposed inside the ring, the metal film 170b disposed outside the ring, and the metal films 170a and 170d disposed in the middle. are different from each other in the cross-sectional shape in the direction perpendicular to the ion traveling direction.
  • the region surrounded by the metal coatings 170a to 170d (the ions are A quadrupole electric field is formed with U in the flying region.
  • the insulating supports 151a and 151b on which the metal films 170a to 170d are formed are annular and curved, so that the traveling direction of the ions 105 is curved.
  • the shape of the three types of electrodes is determined so as to more accurately correct the influence of the centrifugal force generated in the ions and the distortion of the electric field due to the curved traveling direction.
  • three types of electrodes are used, but it is needless to say that all may have the same shape, or two types or four types. Furthermore, cylindrical electrodes having different shapes may be used.
  • FIG. 8 is a diagram showing a quadrupole mass spectrometer according to the present embodiment.
  • an ion source 181 larger than the ion source 101 is arranged in a case 184a larger than the case 108a, and a detector 183 larger than the detector 103 is arranged in a case 184b larger than the case 108b.
  • a notch 182 is formed in a part of a region (for example, hyperbolic surfaces 152a to 152d) along the circumference of the annular insulating supports 151a and 151b.
  • the notch 182 is also formed in a part (1/4 region) of the metal films 150a to 150d formed on the hyperbolic surfaces 152a to 152d. Note that the insulating supports 151a and 151b are only partially removed from the surface, so there is almost no deterioration in accuracy.
  • the notch portion 182 by providing the notch portion 182 and notching at least part of the metal film, a large ion source and a large detector can be provided, and formation of a useless metal film can be suppressed. it can. Since the notch 182 of this embodiment is not a region that should function as a mass separation region, it is not necessary to form an essential metal film in the mass separation region. Accordingly, by avoiding the formation of the metal film in the region other than the region functioning as the mass separation region, it is possible to reduce the formation of useless metal film, thereby further reducing the cost.
  • the notch 182 it is important to provide the notch 182 in a part of the metal films 150a to 150d, and it is not essential to form the notch 182 in the hyperbolic surfaces 152a to 152d. That is, in this embodiment, by providing a notch in at least a part of the metal film, the restriction on the size of the ion source and the detector can be relaxed, and the formation of a useless metal film can be suppressed.
  • FIG. 9 is a diagram showing a quadrupole mass spectrometer according to the present embodiment.
  • an ion source 191 larger than the ion source 181 is arranged in a case 194a larger than the case 184a, and a detector 193 larger than the detector 183 is arranged in a case 194b larger than the case 184b.
  • a cutout portion 192 is formed in a partial region along the circumference of the annular insulating supports 151a and 151b and the metal films 150a to 150d.
  • the insulating support is made of a very hard ceramic. Therefore, even if there is a cutout in a part, it is considered that there is little deterioration in accuracy and does not pose a major problem.
  • the ion source and the detector are arranged in the notch, and the insulating supports 151a and 151b and the metal films 150a to 150d may be arranged based on the same reference point (concentric point).
  • the annular metal coatings 150a to 150d are used to form a U-equipped quadrupole electric field, but the electrode portion for mass separation has a quadrupole mass. What is necessary is just to be formed at least in the area
  • an ion source 211 capable of emitting ions in two opposing directions is arranged in a case 218a having openings on opposing surfaces.
  • a detector 213 is arranged in a case 128b having openings on the opposing surfaces.
  • an extraction electrode 211a having an opening spaced from one ion emission portion of the ion source 211 is disposed, and an extraction electrode 211b having an opening spaced from the other ion emission portion is disposed.
  • the ion 215a ion that flies clockwise in FIG.
  • Reference numeral 214 denotes four annular electrodes for forming a quadrupole electric field with U, which are the cylindrical electrodes or metal films described in the first to fifth embodiments.
  • the annular electrodes 214 are arranged concentrically. A high-frequency voltage is applied to two of the four annular electrodes 214 facing each other, and a high-frequency voltage and a direct-current voltage between the remaining two electrode sets (facing each other with the central axis of the mass analyzer in between). Is applied to form a quadrupole electric field 217 with U.
  • mass separation can be performed either clockwise or counterclockwise using the ion source 211 that can emit ions in both directions and the detector 213 that can detect ions from both directions. It is the extraction electrodes 211a and 211b that can switch the voltage application to determine the ion emission. That is, when a predetermined voltage is applied to the extraction electrode 211a and 211b on the side from which ions are emitted, ions are extracted to the extraction electrode to which the voltage is applied, and formed on the extraction electrode. Ions are released through the openings.
  • the ions 215a are curved by 270 ° in the ring of the quadrupole electric field 217 with U, and the detector 218. Will be incident on.
  • the ions 215b enter the detector 218 after being curved by 90 ° in the ring of the quadrupole electric field 217 with U. Will do.
  • there are two mass separation regions having different lengths.
  • the applied voltages to the two sets of electrodes are common in the clockwise mass analyzing unit and the counterclockwise mass analyzing unit. Yes. Therefore, although it is structurally the same as one set of mass analyzers, two types of mass analyzers having different characteristics can be made to function.
  • the specific assembly structure uses any of the first to fifth embodiments.
  • the optimal length (longitudinal direction) of the electrode of the quadrupole mass spectrometer varies depending on the atmospheric pressure, select either one according to the pressure and perform measurement. Thereby, the measurable pressure range can be widened.
  • the quadrupole mass spectrometer (mass separation region) described in the above-described embodiment is arranged in multiple lanes in the radial direction of the annular electrode.
  • an ion source 221a is disposed in the case 222a
  • a detector 223a is disposed in the case 222b.
  • Reference numeral 224a denotes four annular electrodes for forming a U-folded quadrupole electric field, which are the cylindrical electrodes or metal films described in the first to fifth embodiments. Each of the annular electrodes 224a is disposed concentrically.
  • a quadrupole electric field 227a with U is generated. It is formed.
  • a quadrupole mass spectrometer of the inner lane is formed, and the ions 225a emitted from the ion source 221a are detected by a detector 223a arranged so as not to be expected from the ion source 221a.
  • Reference numeral 224b denotes four annular electrodes for forming a U-shaped quadrupole electric field, which are the cylindrical electrodes or metal films described in the first to fifth embodiments.
  • Each of the annular electrodes 224b is disposed concentrically with the annular electrode 224a outside the annular electrode 224a.
  • a high-frequency voltage and a direct-current voltage are applied between two opposing electrode sets among the four annular electrodes 224b, whereby a U-containing quadrupole electric field 227b is formed.
  • These components form a quadrupole mass spectrometer in the outer lane, and ions 225b emitted from the ion source 221b are detected by a detector 223b arranged so as not to be expected from the ion source 221b.
  • two sets of annular electrodes (4 ⁇ 2; 224a, 224b) having different radii have a fitting structure with respect to the same concentric point and are assembled by the same insulating support.
  • the radial distance between the electrodes is changed. Therefore, two types of mass analyzers having different characteristics can be made to function although they are structurally substantially the same as one set of mass analyzers.
  • the specific assembly structure uses any of the first to fifth embodiments. Since not only the length in the longitudinal direction of the electrodes but also the distance in the radial direction between the electrodes varies depending on the required performance, the applicable range can be widened by making a difference in the distance between the electrodes.
  • two U-quadrupole electric fields 227a and 227b are formed by disposing a two-lane quadrupole mass spectrometer in the radial direction of the annular electrode. Since ions are passed through a region where a quadrupole electric field with U is formed, the radial direction of an annular electrode (quadrupole mass spectrometer formed in an annular shape) There will be two mass fractionation regions. In the present embodiment, two lanes (quadrupole mass spectrometer) are arranged in the radial direction, but two or more lanes (quadrupole mass spectrometer) may be arranged. At this time, two or more mass separation regions exist in the radial direction.
  • the quadrupole mass spectrometer (mass separation region) described in the above-described embodiment is arranged in multiple lanes in the axial direction of the annular electrode (the vertical direction in the plane of the ring).
  • the insulating support 231a has an annular shape, and has two hyperbolic surfaces formed in an annular shape in the in-plane vertical direction of the annular shape. Each has an annular metal coating 230a, 230b.
  • the insulating support 231b has an annular shape, and has two hyperbolic surfaces formed in an annular shape on opposite surfaces in the axial direction of the annular shape. Each is formed with an annular metal coating 230c to 230f.
  • the insulating support 231c has an annular shape, and has two hyperbolic surfaces formed in an annular shape in the in-plane vertical direction, and each of the hyperbolic surfaces has an annular shape.
  • a quadrupole mass spectrometer formed of the metal films 230a to 230d and a quadrupole mass spectrometer formed of the metal films 230e to 230h are arranged in the axial direction of the ring.
  • a structure arranged in parallel is formed.
  • the region surrounded by the metal coatings 230a to 230d (the ions fly).
  • the quadrupole electric field is formed in the region U).
  • two sets of annular electrodes having the same radius (4 ⁇ 2; set of metal films 230a, 230c, 230e, and 230g, and set of metal films 230b, 230d, 230f, and 230h) are related to the same concentric point.
  • a single insulating support 231b is used as a common structure.
  • the two sets of electrodes are all the same including the length and the distance between the electrodes, but the voltage applied to the two sets of electrodes can be set independently, that is, ions of different mass numbers can be passed. Yes. Therefore, although it is structurally close to one set of mass analyzers, it is possible to function two sets of mass analyzers that are independent and have the same characteristics.
  • the specific assembly structure is the same as that of the third embodiment.
  • two U-equipped quadrupoles are provided. An electric field is formed. Since ions are passed through a region where a quadrupole electric field with U is formed, the axial direction of an annular electrode (a quadrupole mass spectrometer formed in an annular shape) There will be two mass fractionation regions.
  • two lanes quadrupole mass spectrometer
  • two or more lanes quadrupole mass spectrometer
  • N is an integer of 2 or more mass analysis regions are formed in the axial direction
  • the insulating supports 231a and 231c (on one of the opposing surfaces in the axial direction)
  • An insulating support having two metal films formed thereon is disposed, and N ⁇ 1 insulating supports 231b (the metal films are formed on each of the axially opposed surfaces) between the insulating supports 231a and 231c.
  • Insulating supports formed by two) are arranged. Then, in the arrangement of N-1 insulating supports 231b, the insulating support 231b and the insulating support 231a at one end in the axial direction are fitted together, and the insulating support 231b and the insulating support 231c at the other end are fitted together.
  • the remaining insulating supports 231b are fitted together.
  • N U-quadrupole electric fields can be formed, and N mass analysis regions can be formed in the axial direction.
  • N 2
  • the configuration is as shown in FIG. 13, so that one insulating support 231 b is arranged between the insulating support 231 a and the insulating support 231 c.
  • the insulating support that is fitted into each of the insulating supports 231a and 231c is the same insulating support 231b.
  • two or more mass separation regions having different lengths can exist in the same quadrupole mass spectrometer.
  • the operation is as follows.
  • a detector 223b is provided at a position 180 ° from the ion source 221b, the ion sources 221a and 221b are changed to the ion source 211, and extraction electrodes 211a and 211b are provided in the respective ion sources. Further, the detectors 223a and 223b are changed to the detector 213.
  • three mass fractionation regions having different lengths can exist in the same quadrupole mass spectrometer.
  • quadrupole mass analyzers mass fractionation regions
  • FIG. 14 A quadrupole mass spectrometer according to the twelfth embodiment of the present invention will be described with reference to FIG.
  • an annular soft spacer 241 is provided at the fitting portion between the electrode 104b and the insulating support 112a, and the insulating support 112a and the insulating support 112b are fitted.
  • An annular soft spacer 242 is provided at the mating portion.
  • the soft spacer 241 is used in each of the fitting portion between the electrode 104a and the insulating support 112a, the fitting portion between the electrode 104c and the insulating support 112b, and the fitting portion between the electrode 104d and the insulating support 112b. Is provided.
  • annular spacer made of a soft material is sandwiched between the fitting portions.
  • the soft spacer is preferably made of aluminum (Al), copper (Cu), or indium (In).
  • the thickness should be within the range that can be assembled (usually equal to or more than twice the gap between the two to be accurate) but less uneven thickness (circular symmetry variation). Therefore, it is preferable to use one having an average thickness of about 10 micrometers and non-uniformity within about several tens of percent.
  • a ribbon slightly shorter than the circumferential length to be actually used is used.
  • the force applied between the two should be equal, that is, circularly symmetrical, so that the accuracy of concentricity of the two sandwiching the soft spacer can be further increased. it can.
  • the fitting portions are all cylindrical (the cross section is parallel to the axis). However, as shown in FIG. 15, this is tapered (the cross section is inclined with respect to the axis). Positioning of the ring in the axial direction (left-right direction in the figure) can be realized at the same time. Further, in the above embodiment, not only the electrodes but also the insulating support and soft spacer are all annular, but if the quadrupole electric field is formed with high accuracy, the fitting portion of the insulating support and soft spacer is not necessarily provided.
  • the electrodes 104a to 104d for forming the U-folded quadrupole electric field 107 described in the first embodiment are concentric toric rings, but the embodiment is modified so that the electrodes 104a to 104d It can be fitted to an insulating support at the top few points. Further, by modifying the twelfth embodiment, several small pieces of soft spacers can be arranged and sandwiched.
  • the points are arranged so that the intervals between the points are as uniform as possible.
  • the fitting since one of the fittings is a point, the fitting is not strictly circularly symmetric. However, since the fitting is almost circularly symmetric as a whole, the electrodes 104a to 104d are made highly parallel. Can be arranged in degrees. Therefore, in the present invention, it is sufficient that the fitting is almost circularly symmetric as a whole. Therefore, although the electrode is basically an annular shape, the insulating support may be a plate having a fitting portion that is nearly circularly symmetric. . In addition, the soft spacer may have any shape as long as it can be finally arranged in the fitting portion in a shape close to circular symmetry.
  • FIG. 16 is a diagram illustrating an example in which the quadrupole mass spectrometer according to the above-described embodiment is attached to a sputtering apparatus.
  • reference numeral 160 denotes a sputtering apparatus provided with a vacuum vessel, a film forming mechanism, an exhaust mechanism and the like, and a commonly used apparatus can be applied.
  • the sputtering apparatus 160 is provided with an opening 161, and a pipe 162 having a vacuum flange 163 (for example, a vacuum flange (70 ICF) having an outer diameter of 70 mm) is connected to the opening 161.
  • a vacuum pipe 165 (for example, a vacuum pipe with an inner diameter of 38 mm) is connected to the vacuum flange 164 (for example, 70 ICF), and one embodiment of the present invention is included in the vacuum pipe 165.
  • a quadrupole mass spectrometer 166 according to the embodiment is incorporated. In such a configuration, the quadrupole mass spectrometer 166 is attached to the sputtering apparatus 160 by connecting the vacuum flange 163 and the vacuum flange 164.
  • the quadrupole mass spectrometer 166 can be incorporated in the vacuum flange 164 and attached to a film forming apparatus such as the sputtering apparatus 160.
  • a film forming apparatus such as the sputtering apparatus 160.
  • the quadrupole mass spectrometer 166 according to an embodiment of the present invention is easy to downsize, it is incorporated into a vacuum flange ( ⁇ 70 ICF) having a general outer diameter of ⁇ 70 mm in a vacuum device such as a sputtering device. It is possible to attach.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Electron Tubes For Measurement (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

La présente invention a trait à un spectromètre de masse quadripolaire capable d'augmenter la sensibilité (S/N) en réduisant l'incidence de la lumière diffuse provenant d'une source d'ions sur un détecteur. Plus particulièrement, la présente invention a trait à un spectromètre de masse quadripolaire (100) équipé d'une source d'ions (101), d'un spectromètre de masse quadripolaire (102) qui est pourvu de films métalliques annulaires et d'un détecteur (103) qui détecte, en tant que signal, un ion qui est passé par le spectromètre de masse quadripolaire. Le spectromètre de masse quadripolaire est non linéaire et, grâce à ce spectromètre de masse quadripolaire non linéaire, le spectromètre de masse quadripolaire est configuré de manière à ce que le détecteur ne puisse pas être vu à travers le spectromètre de masse quadripolaire à partir de la source d'ions. Les films métalliques sont formés sur des supports isolants et assemblés en faisant correspondre les supports isolants les uns avec les autres.
PCT/JP2010/073736 2009-12-28 2010-12-28 Spectromètre de masse quadripolaire WO2011081188A1 (fr)

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GB2492893A (en) * 2011-07-14 2013-01-16 Bruker Daltonics Inc A linear multipole ion collision cell
WO2014103100A1 (fr) * 2012-12-27 2014-07-03 キヤノンアネルバ株式会社 Spectroscope de masse
EP2804201A3 (fr) * 2013-05-13 2016-05-25 Thermo Finnigan LLC Composants optiques ioniques et leur procédé de fabrication
EP3008748A4 (fr) * 2011-12-30 2017-02-15 Dh Technologies Development Pte. Ltd. Éléments optiques ioniques
CN112687518A (zh) * 2020-12-21 2021-04-20 天津国科医工科技发展有限公司 一种便于修研装配的四极杆结构
JP2022546579A (ja) * 2019-09-10 2022-11-04 アプライド マテリアルズ インコーポレイテッド 熱的に隔離したリペラおよび電極
WO2023181013A1 (fr) * 2022-03-25 2023-09-28 Thermo Finnigan Llc Améliorations de géométrie de guide d'ions

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US8481929B2 (en) 2011-07-14 2013-07-09 Bruker Daltonics, Inc. Lens free collision cell with improved efficiency
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EP3008748A4 (fr) * 2011-12-30 2017-02-15 Dh Technologies Development Pte. Ltd. Éléments optiques ioniques
WO2014103100A1 (fr) * 2012-12-27 2014-07-03 キヤノンアネルバ株式会社 Spectroscope de masse
JP5922256B2 (ja) * 2012-12-27 2016-05-24 キヤノンアネルバ株式会社 質量分析装置
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EP2804201A3 (fr) * 2013-05-13 2016-05-25 Thermo Finnigan LLC Composants optiques ioniques et leur procédé de fabrication
EP3629363A1 (fr) * 2013-05-13 2020-04-01 Thermo Finnigan LLC Composants optiques ioniques et leur procédé de fabrication
JP2022546579A (ja) * 2019-09-10 2022-11-04 アプライド マテリアルズ インコーポレイテッド 熱的に隔離したリペラおよび電極
JP7314408B2 (ja) 2019-09-10 2023-07-25 アプライド マテリアルズ インコーポレイテッド 熱的に隔離したリペラおよび電極
CN112687518A (zh) * 2020-12-21 2021-04-20 天津国科医工科技发展有限公司 一种便于修研装配的四极杆结构
WO2023181013A1 (fr) * 2022-03-25 2023-09-28 Thermo Finnigan Llc Améliorations de géométrie de guide d'ions

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