JPH07239310A - Electromagnetic wave detector and substrate processing apparatus - Google Patents

Abstract

PURPOSE:To obtain an electromagnetic wave detector capable of detecting even a weak electromagnetic wave when a plurality of electromagnetic waves large in intensity ratio are measured and a substrate processing apparatus having a function capable of measuring the change of a compsn. during substrate processing work. CONSTITUTION:A total reflection mirror 31 as an optical element allowing the characteristic X-rays 7a from an element high in intensity among characteristic X-rays emitted from a sample 1C to selectively transmit to attenuate the same and selectively reflecting the characteristic X-rays 7b from an element low in intensity and a slit 32 as an intensity adjusting mechanism adjusting the intensity of characteristic X-rays 7a are provided. The characteristic X-rays 7b reflected by the total reflection mirror 31 and the characteristic X-rays 7a adjusted in intensity by the slit 32 are detected by the same semiconductor X-ray detector 6 and, when characteristic X-rays large in intensity ratio generated from the elements in the sample 1C are measured, even a weak electromagnetic wave can be detected.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention relates to X-rays, electron beams,
Electromagnetic wave detection device for exciting an element by an excitation source such as an ion beam and detecting electromagnetic waves emitted from the excited element, particularly characteristic X-rays (hereinafter characteristic X-rays include fluorescent X-rays) and electromagnetic wave detection The present invention relates to a substrate processing apparatus that can detect a change in composition during processing of a substrate using the apparatus.

[0002]

2. Description of the Related Art In recent years, with high integration and miniaturization of electronic devices and semiconductors, extremely small amounts of impurities have come to influence device characteristics. Therefore, it is becoming important to investigate the trace amount of impurity contamination. As a method for measuring such a trace amount of impurity contamination, an impurity element is excited by an excitation source such as an X-ray, an electron beam or an ion beam, and an electromagnetic wave emitted from the excited element, particularly a characteristic X-ray is detected. Therefore, there is a method of measuring an impurity element. This measuring method has been widely used in recent years because it can measure an impurity element without destroying a sample.

FIG. 21 shows an X-ray detector as a conventional electromagnetic wave detector for measuring an impurity element without destroying a sample. For example, "synchrotron radiation technology" is shown.
(Takio Tomasu, Ed., Industrial Research Group, 1990, p.49
It is similar to that shown in 7). In FIG. 21, 1A indicates, for example, iron Fe or copper Cu on a silicon Si substrate.
Sample 2 in which impurities of isobaric metal are mixed, Sample 1A
An excitation source such as synchrotron radiation for exciting the element (3), a spectroscope (3) for separating the X-ray (5) from the excitation source (2), and (4a, 4b) for determining the incident and outgoing angles of the spectroscope (3). A slit, 6 is a semiconductor X-ray detector for detecting a characteristic X-ray 7 generated by an element in the sample 1A excited by the X-ray 5 from the excitation source 2, and 8 is a wave height analyzer and a storage / display device. A signal processing circuit including the signal processing circuit for processing the detection signal from the semiconductor X-ray detector 6, and 9 is a sample container.

Next, the operation of the above configuration will be described. The X-rays 5 emitted from the excitation source 2 such as synchrotron radiation light are separated by the spectroscope 3 at the entrance / exit angles determined by the slits 4a and 4b, and are irradiated onto the sample 1A.
As a result, the element of the sample 1A is excited, and the characteristic X-ray 7 emitted by the excited element is detected by the semiconductor X-ray detector 6. The characteristic X-ray 7 detected by the semiconductor X-ray detector 6 is processed by the signal processing circuit 8 and stored / displayed as a spectrum.

As the semiconductor X-ray detector 6, an energy dispersive detector capable of simultaneously observing the entire X-ray spectrum is used. The principle of X-ray detection of the semiconductor X-ray detector 6 and the above FIG. 22A shows the signal processing in the wave height analyzer (not shown) included in the signal processing circuit 8.
This will be described with reference to (c). In FIG. 22 (a), 6A is a number of electrons corresponding to the energy value of the characteristic X-ray 7 generated when the characteristic X-ray 7 emitted from the sample 1A enters the semiconductor X-ray detector 6. Hole pair, 8
A and 8B are the bias voltage and current pulse of the signal processing circuit 8.

That is, when the characteristic X-rays 7 are incident on the semiconductor X-ray detector 6, a number of electron-hole pairs 6A which are proportional to the energy value of each characteristic X-ray 7 are generated and output as current pulses 8B. Then, the signal processing circuit 8 converts this current pulse 8B into a voltage pulse proportional to the amount of the current pulse through an internal amplifier, and then stores it in a channel corresponding to each pulse peak value by an internal pulse height analyzer. It is designed to obtain an energy spectrum.
FIG. 22B is a schematic diagram showing a current pulse obtained when the semiconductor X-ray detector 6 detects characteristic X-rays emitted from a sample, for example, characteristic X-rays 7 having three different energy values. Also, FIG. 22C is a diagram showing the result of pulse height analysis of the current pulse of FIG. 22B, and the current pulses P1, P2, and P3 are displayed as the number of pulses corresponding to each energy.

Further, conventionally, with the high integration and miniaturization of electronic devices and semiconductors as described above, the quality of thin films has come to influence the performance of electronic devices. For example, in a silicon dioxide SiO ₂ film, silicon Si and oxygen O
If the ratio of the ratio and the ratio deviates from 1: 2, it means that a substance other than SiO ₂ is mixed in the film, and the dielectric constant changes, and desired high frequency characteristics may not be obtained. Furthermore, when forming a thin film of a compound, it is often difficult to obtain a desired composition due to a difference in sputtering rate, a difference in sticking coefficient, etc. Conventionally, a composition analyzer was used after forming a thin film with a thin film forming apparatus. However, in that case, it was difficult to correct the composition change during the thin film formation due to the change in the conditions during the thin film formation. Therefore, attempts have been made to sequentially measure changes in composition during thin film formation.

23A and 23B show, for example, "RHE
Study of Surfaces by ED Excited X-ray Total Reflectance Angle Spectroscopy (TRAXS) "(Ino et al., Applied Physics, Volume 56, No. 7, 19)
87, p. 843 to 850) and is a configuration diagram showing a conventional thin film forming apparatus to which the semiconductor X-ray detector 6 is added, and an enlarged configuration diagram of the inside of the semiconductor X-ray detector 6. In FIG. 23A, 1B is gallium arsenide GaAs obtained by vapor-depositing gallium Ga or arsenic As on a silicon Si substrate.
A sample on which a thin film is formed, 10 is a vacuum chamber of a thin film forming apparatus,
Reference numeral 11 is an exhaust mechanism for exhausting the inside of the vacuum chamber 10, 12 is a manufacturing mechanism for forming a thin film on a base material such as a substrate, which will be described later, and 13 is a characteristic X while maintaining a vacuum state inside the vacuum chamber 10.
An X-ray transmission window for transmitting rays, and 14 is a liquid nitrogen dewar for cooling a detection element 6a of the semiconductor X-ray detector 6 described later.

As a structure of the semiconductor X-ray detector 6 used here, as shown in FIG. 23B, for example, gallium GaAs or arsenic As is deposited on a silicon Si substrate to form a gallium arsenide GaAs thin film. A detection element 6a for detecting the characteristic X-rays excited by the excitation source 2 from the sample 1B in which is formed, a vacuum container 6b for keeping the detection element 6a in vacuum, a characteristic X-ray while maintaining the internal vacuum state. X-ray transmission window 6c for transmitting the radiation, the amplifier 6d for amplifying the detection signal from the detection element 6a, the detection signal amplified by the amplifier 6d is led to the outside of the vacuum, and heat is applied to cool the detection element 6a. It has a rod 6e leading to the outside.

Next, the operation of the thin film forming apparatus having the above structure will be described. In the manufacturing mechanism 12, for example, gallium Ga or arsenic As is put in an evaporation crucible (not shown) and heated in a vacuum, so that the gallium Ga or arsenic As is vapor-deposited on the silicon Si substrate of the sample 1B to form gallium arsenide GaAs. Form a thin film. During the formation of the thin film of the sample 1B thus formed, the excitation source 2 excites the characteristic X-rays of gallium Ga and arsenic As that form the above-mentioned thin film, and the X-ray transmission window 13 once extracts it into the atmosphere. By detecting with the detector 6 through the X-ray transmission window 6c on the front surface of the semiconductor X-ray detector 6, the change in composition during thin film formation is sequentially measured.

[0011]

Since the conventional X-ray detector shown in FIG. 21 is constructed as described above, the intensity of the characteristic X-ray from the impurity element of heavy metal such as iron Fe or copper Cu is The ratio of the intensity of the characteristic X-rays from the matrix such as the silicon Si substrate is large. Therefore, in such a measurement method, for example, in FIGS. 22B and 22C, the energy of the characteristic X-ray from the substrate is indicated by the current pulse P3, and the energy of the characteristic X-ray of the impurity element is indicated by the current pulse P1. , P2
24, the intensity of the characteristic X-rays from the substrate is very strong, and as shown in FIG. 24, the current pulses P3 are arranged in a row with a short time interval, thereby increasing the pulse amount. The probability that the current pulse P3 and the current pulses P1 and P2 overlap with each other increases, and correct analysis becomes difficult. Also,
In order to analyze the pulse height of a current pulse, it is necessary to integrate the amount of current in time and it takes time to convert the pulse. Therefore, when the pulse train becomes dense, it becomes difficult to count all the pulses. Therefore, there is a problem that it is difficult to measure characteristic X-rays from a weak impurity element with high sensitivity.

Further, since the conventional thin film forming apparatus having the function of measuring X-rays shown in FIG. 23 is configured as described above, it has the following problems. 1) Conventionally, beryllium Be is used for the X-ray transmission windows 6c and 13.
Since foil is used and soft X-rays with an X-ray energy of 1 keV or less are absorbed at a thickness that maintains a normal vacuum state, characteristic X-rays of substances containing light elements such as oxides and carbides. Was difficult to measure. 2) Even if an organic substance that transmits the soft X-rays (for example, parylene) is used as the X-ray transmission windows 6c and 13, the X-rays are generated by the radiant heat from the substrate or the like during formation of the thin film.
The line transmission windows 6c and 13 may soften or melt. 3) In addition, even if a light element is devised so that it can be measured, especially in the case of a light element such as oxygen, nitrogen, or carbon, the characteristic X-ray generation efficiency becomes extremely low as the atomic number becomes small. In compounds containing such light elements,
Even if the composition ratio is 1: 1, when pulse measurement is performed on the photons of the characteristic X-ray, the count rate of the pulse measurement becomes very small, so the measurement time is lengthened in order to perform measurement with a certain accuracy. There was a need. 4) Therefore, when measuring substances containing the above light elements,
It takes a long measuring time, it is difficult to follow the thin film forming speed, and it is difficult to measure the composition of the sample step by step in the thin film forming process.

The present invention has been made in order to solve the problems of the conventional example as described above, and provides an electromagnetic wave detecting device capable of detecting even weak electromagnetic waves when measuring a plurality of electromagnetic waves having a large intensity ratio. The purpose is to get.

It is another object of the present invention to provide a substrate processing apparatus having a function of measuring the composition of a sample or a target during the process when the composition is measured by using electromagnetic waves having greatly different intensity ratios during the substrate processing process. .

[0015]

The electromagnetic wave detecting device according to claim 1 of the present invention is an electromagnetic wave detecting device having a detector for detecting electromagnetic waves of a plurality of wavelengths generated by elements in the sample, At least one of electromagnetic waves of a plurality of wavelengths generated from the sample, which is installed between the detector and the detector.
An optical element that selectively reflects or transmits one or more wavelengths, and an intensity adjusting mechanism that is installed between the sample and the detector to adjust the intensity of electromagnetic waves, and is reflected or transmitted by the optical element. The electromagnetic wave and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector.

The electromagnetic wave detecting device according to claim 2 is
The wavelength of the electromagnetic wave is in the X-ray region.

The electromagnetic wave detecting device according to claim 3 is
The detector is an energy dispersive detector.

The electromagnetic wave detecting device according to a fourth aspect is
It is characterized by comprising a heat-resistant shield that shields light and heat entering the detector and transmits X-rays including soft X-rays of 1 keV or less.

An electromagnetic wave detecting device according to a fifth aspect is
The strength adjusting joint mechanism is a slit.

The electromagnetic wave detecting device according to claim 6 is
It is characterized in that the optical element is an optical element that utilizes a total reflection phenomenon.

An electromagnetic wave detecting device according to a seventh aspect is
It is characterized in that the optical element is an optical element utilizing a diffraction phenomenon.

In the substrate processing apparatus according to the eighth aspect, the processing mechanism for processing the substrate, the excitation source for exciting a plurality of elements contained in the substrate being processed, and the element excited by the excitation source are A detector for detecting emitted electromagnetic waves of a plurality of wavelengths, and a detector installed between the substrate being processed and the detector to selectively reflect at least one or more wavelengths of the electromagnetic waves of a plurality of wavelengths. An optical element that transmits, an intensity adjusting mechanism that is installed between the substrate being processed and the detector to adjust the intensity of electromagnetic waves, and is reflected by the optical element during processing of the substrate by the processing mechanism. It is characterized in that the detector detects the transmitted electromagnetic wave and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism.

A substrate processing apparatus according to a ninth aspect of the invention is a thin film forming mechanism for forming a thin film on a substrate by using a sputtering phenomenon, an excitation source for exciting an element in a target material to be sputtered, and this excitation. And a detector for detecting an electromagnetic wave emitted by the element excited by the source.

A substrate processing apparatus according to claim 10 is
An optical element that is installed between the target material and the detector and transmits or reflects the electromagnetic wave, and an intensity adjusting mechanism that is installed between the target material and the detector and adjusts the intensity of the electromagnetic wave. It is characterized by that.

A substrate processing apparatus according to claim 11 is
The wavelength of the electromagnetic wave is in an X-ray region according to any one of claims 8 to 10.

A substrate processing apparatus according to claim 12 is
The detector according to any one of claims 8 to 11, wherein the detector is an energy dispersive detector.

The substrate processing apparatus according to claim 13 is
13. The heat resistant shield according to claim 8, which shields light and heat entering the detector and transmits X-rays including soft X-rays of 1 keV or less. Is.

A substrate processing apparatus according to claim 14 is
In any one of claims 8 to 13, the strength adjusting mechanism is a slit.

A substrate processing apparatus according to claim 15 is
The optical element according to any one of claims 8 to 14, wherein the optical element is an optical element utilizing a total reflection phenomenon.

A substrate processing apparatus according to claim 16 is
The optical element according to any one of claims 8 to 14, wherein the optical element is an optical element utilizing a diffraction phenomenon.

[0031]

In the electromagnetic wave detecting device according to the first aspect of the present invention, the optical element selectively reflects or transmits at least one or more wavelengths of electromagnetic waves of a plurality of wavelengths generated by elements in the sample. By adjusting the intensity of the electromagnetic wave by the intensity adjusting mechanism, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector, and the intensity ratio is large. When measuring the electromagnetic waves of, even weak electromagnetic waves can be detected.

Further, in the electromagnetic wave detection device according to the second aspect, when measuring a plurality of electromagnetic waves having a large intensity ratio, the wavelength of the electromagnetic waves is set to the X-ray region, so that the element Facilitate type identification.

Further, in the electromagnetic wave detecting apparatus according to the third aspect, the detector is an energy dispersive type detector, and when a plurality of electromagnetic waves having a large intensity ratio are detected, the counting rate is determined by the electromagnetic waves having a large intensity. Enables weak electromagnetic waves to be detected at the same time without being rate-controlled.

Further, in the electromagnetic wave detecting apparatus according to the fourth aspect, the light and heat entering the detector are shielded, and at the same time 1 k
By providing a heat-resistant shield that transmits X-rays containing eV or less soft X-rays, the adverse effect of light or heat on the detector is prevented, and X-rays containing soft X-rays 1 keV or less are emitted. Light elements can also be detected.

Further, in the electromagnetic wave detecting device according to the fifth aspect of the invention, the intensity adjusting mechanism is constituted by the slit, so that the aperture ratio of the slit is changed to enable simple intensity adjustment.

Further, in the electromagnetic wave detecting device according to the sixth aspect, by using an optical element utilizing a total reflection phenomenon as the optical element, a plurality of electromagnetic waves are reflected by causing the electromagnetic waves to be reflected and reflected at a predetermined incident and reflected angle. Among these, it is possible to simultaneously reflect electromagnetic waves emitted from a plurality of elements that emit electromagnetic waves having an energy lower than a predetermined energy, and to simultaneously measure the elements that emit the reflected electromagnetic waves.

Further, in the electromagnetic wave detecting device according to the seventh aspect, by using an optical element utilizing a diffraction phenomenon as the optical element, the electromagnetic wave is weakly intensityed by reflecting and reflecting the electromagnetic wave at a predetermined incident and reflection angle. It is possible to selectively extract the electromagnetic wave of a specific element regardless of the energy level of the strong electromagnetic wave, and unlike the case of using an optical element that utilizes the total reflection phenomenon, the energy is stronger than the strong electromagnetic wave. This makes it possible to selectively extract only the electromagnetic wave of an element that emits an electromagnetic wave having a high energy, even when the strength of the element that emits a high electromagnetic wave is present as an impurity and the amount thereof is very small and the strength is weak.

Further, in the substrate processing apparatus according to the eighth aspect, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector during the processing of the substrate by the processing mechanism. By doing so, it is possible to detect even weak electromagnetic waves when measuring a plurality of electromagnetic waves having a large intensity ratio during processing of the substrate, and it is possible to measure a change in composition.

Further, in the substrate processing apparatus according to the ninth aspect, when the thin film is formed on the substrate by the thin film forming mechanism by using the sputtering phenomenon, the element in the target material to be sputtered is excited by the excitation source and detected. A change in the composition of the target material can be detected by detecting the electromagnetic wave emitted by the element excited by the vessel.

Further, in the substrate processing apparatus according to the tenth aspect, at least one or more wavelengths of the electromagnetic waves generated by the element in the target material are selectively reflected by the optical element, and the intensity adjusting mechanism is used. By adjusting the intensity of the electromagnetic wave, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector, and the intensity ratio of the elements in the target material is increased. Even weak electromagnetic waves can be detected when measuring multiple large electromagnetic waves.

According to the eleventh aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to tenth aspects, when measuring a plurality of electromagnetic waves having a large intensity ratio during the substrate processing, the wavelength of the electromagnetic wave is X. By defining a line area, X
It facilitates the identification of the element type of the substrate or target material to be the sample based on the energy value of the line.

Further, in the substrate processing apparatus according to the twelfth aspect of the present invention, according to any one of the eighth to eleventh aspects, the detector is an energy dispersive detector to detect a plurality of electromagnetic waves having a large intensity ratio. In this case, it is possible to detect weak electromagnetic waves at the same time without limiting the counting rate by electromagnetic waves having high intensity.

Further, in a substrate processing apparatus according to a thirteenth aspect, in any one of the eighth to twelfth aspects, the light and heat entering the detector are shielded and X-rays including soft X-rays of 1 keV or less are transmitted. The use of a heat-resistant shield prevents adverse effects of light and heat on the detector.
It also makes it possible to detect light elements that emit X-rays including soft X-rays of keV or less.

Further, in the substrate processing apparatus according to claim 14, in any one of claims 8 to 13, the strength adjusting mechanism is constituted by a slit, whereby the aperture ratio of the slit is changed and a simple strength is obtained. Allows adjustment.

According to the fifteenth aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to fourteenth aspects, by using an optical element utilizing a total reflection phenomenon as the optical element, an electromagnetic wave is emitted at a predetermined incident / reflection angle. By reflecting and reflecting, it is possible to simultaneously reflect electromagnetic waves emitted from a plurality of elements that emit an electromagnetic wave having an energy lower than a predetermined energy among a plurality of electromagnetic waves, and the element that emits the reflected electromagnetic waves. Can be measured at the same time.

Further, in the substrate processing apparatus according to the sixteenth aspect, in any one of the eighth to fifteenth aspects, by using an optical element utilizing a diffraction phenomenon as the optical element, an electromagnetic wave is emitted at a predetermined incident / reflection angle. High and low energy levels of weak and strong electromagnetic waves are obtained by collecting and reflecting the electromagnetic waves of the element to be measured, which are emitted from the sample by inputting and reflecting, or placing the sample and the detector at a predetermined focus position. It is possible to selectively extract the electromagnetic wave of a specific element, regardless of the case, and unlike the case of using an optical element that utilizes the total reflection phenomenon, the element that emits the electromagnetic wave having higher energy than the strong electromagnetic wave is an impurity. It is possible to selectively extract only the electromagnetic waves of the element that emits high-energy electromagnetic waves, even when the strength is weak due to the existence of .

[0047]

【Example】

Example 1. Hereinafter, description will be given based on illustrated embodiments. Figure 1
FIG. 21 is a configuration diagram showing a main part of an X-ray detection apparatus as an electromagnetic wave detection apparatus according to the first embodiment, showing the configuration inside the sample container 9 in the conventional example shown in FIG. 21. In FIG. 1, 1C is a compound sample containing a light element such as oxygen, such as a magnesium oxide substrate, 5, 6, 8 and 9 have the same configuration as that of a conventional X-ray detector, and 5 is an excitation source (not shown). X-rays, 6 are semiconductor X-ray detectors for detecting characteristic X-rays generated by the elements in the sample 1C excited by the X-rays 5, and an energy dispersive detector capable of simultaneously observing the entire X-ray spectrum. Consists of Reference numerals 7a and 7b are characteristic X-rays, 8 is a signal processing circuit that includes a wave height analyzer and a storage / display device, and processes a detection signal from the semiconductor X-ray detector 6, and 9 is a sample container.

Further, 31 is a total reflection mirror as an optical element utilizing the total reflection phenomenon, 32 is a slit which is an intensity adjusting mechanism, 33 is a shield for light and heat, and X-rays including soft X-rays of 1 keV or less are transmitted. It is a heat-resistant shield. In addition,
Although not shown, the X-ray detection apparatus according to the first embodiment
Similar to the conventional example shown in FIG. 21, an excitation source 2 such as synchrotron radiation for exciting the element of the sample 1C, an excitation source 2
It is provided with a spectroscope 3 for spectrally separating the X-rays 5 from, and slits 4a, 4b for determining the incident and outgoing angles of the spectroscope 3.

The total reflection mirror 31 shown in FIG.
As shown in (a), in order to improve the reflectance at the same incident / reflection angle, for example, a metal thin film 31b such as gold Au or platinum Pt having a high density is formed on the surface of a glass substrate 31a made of SiO ₂ as a mirror material. When the electromagnetic wave is incident from a medium with a large refractive index to a medium with a small refractive index, the total reflection occurs when the incident angle (here, the angle from the mirror surface: the glancing angle) is less than a certain angle. In the X-ray region, the refractive index in the vacuum is higher than the refractive index of the material of the mirror. Therefore, the X-ray in the vacuum is reflected by the mirror. When incident, total reflection occurs below the critical angle,
The reflectance increases.

As can be understood from FIG. 2B, the relationship between the glancing angle and the reflectance and energy is, for example, between the critical angle of the characteristic X-ray of oxygen and the critical angle of the characteristic X-ray of carbon. When the glancing angle is set to and the incident reflection is performed, the characteristic X-ray of carbon has a large reflectance, but the characteristic X-ray of oxygen has a small reflectance, and only the characteristic X-ray of carbon can be selectively extracted. It will be possible. Therefore, when the incident / reflection angle is set as described above, the reflectance of not only the characteristic X-rays of carbon but also the characteristic X-rays of energy lower than the energy of the characteristic X-rays of carbon is high. An element that emits a characteristic X-ray having an energy lower than the energy of the characteristic X-ray can be measured at the same time.

Further, the slit 32 which is a strength adjusting mechanism.
For example, as shown in FIG. 3, a plate 32a and a plate 32b having the same openings are provided, and the plate 3 having two openings is provided.
The intensity of the characteristic X-ray 7a is adjusted by changing the aperture ratio by shifting 2a and 32b.

Further, as shown in FIG. 4, for example, the shield 33 is formed by forming a support film 33b on the silicon Si substrate 33c with a good adhesion by a CVD method or the like, as in JP-A-3-276089. A metal thin film 33a is formed by vapor deposition on the support film 33b, and the metal thin film 10a is made to have a minimum thickness that blocks light and heat so that soft X-rays can be transmitted. The support film 33b is desired to be one that transmits soft X-rays well and has a high structural strength, and is also required to have heat resistance because it receives radiant heat. Further, in order to release heat to the metal thin film 33a, a material having a high thermal conductivity is required, and as the material, X-rays having an X-ray energy of 1 keV or less are transmitted, so a material having a low atomic number is desired and stability is also high. In consideration of,
The metal thin film 33a is aluminum Al or beryllium B.
e is suitable, and for the support film 33b, silicon nitride, carbon, silicon carbide, or the like may be used instead of boron nitride BN.

Next, the operation of the above configuration will be described. The X-ray 5 emitted from the excitation source 2 (not shown) such as synchrotron radiation light has an entrance / exit angle determined by the slits 4a and 4b (not shown), and the spectroscope 3 (not shown).
And is irradiated onto the sample 1C. This allows
The element of the sample 1C is excited, and the characteristic X-ray 7a emitted by the excited element passes through the slit 32 which is the intensity adjusting mechanism and is detected by the semiconductor X-ray detector 6. Also, similarly,
The characteristic X-ray 7b emitted by the excited element is reflected by the total reflection mirror 31 and then detected by the semiconductor X-ray detector 6. These characteristic X-rays 7 detected by the semiconductor X-ray detector 6
The signals a and 7b are processed by the signal processing circuit 8 and stored / displayed as spectra.

Here, for example, magnesium oxide MgO
When measuring the amount of oxygen deficiency of the substrate, reference 1 (“X-ray diffraction”, Shizuo Miyake, Asakura Shoten) and reference 2 (MJJaniak,
T, Arai: Abstr.1979, Pittsburgh Conf.Anal.Chem.Appl.
Spectros., P701) and the like, the total reflection mirror 31 has a high energy X-ray at a certain incident / emission angle.
Since the X-ray has a lower reflectance, the X-rays are incident and emitted at the incident and emission angles of the total reflection mirror 31, so that, for example, only X-rays having low energy out of the X-rays having two energy values. Can be reflected. That is, by setting the entrance and exit angles to be equal to or less than the critical angle of the X-ray of the weak element of the sample 1C to be analyzed and equal to or higher than the critical angle of the X-ray of the strong element, the low energy characteristics can be obtained. The element that emits X-rays can be efficiently measured.

When measuring a sample 1C containing magnesium Mg and oxygen O in a ratio of almost one body such as magnesium oxide MgO, generation efficiency of characteristic X-ray of magnesium Mg and characteristic X-ray of oxygen O is generated. Is very different. In general, an element that emits high-energy characteristic X-rays, such as a heavy metal, has a higher generation efficiency of characteristic X-rays, so that the characteristic X-ray of magnesium Mg and the characteristic X-ray of oxygen O have a large intensity ratio.

Therefore, since it is possible to selectively reflect the characteristic X-rays from the light element having a low generation efficiency and not to reflect the characteristic X-rays from the heavy metal having high intensity, the characteristic X-rays emitted from the sample 1C can be prevented. Among them, magnesium Mg with high strength
The characteristic X-rays from 1 can be attenuated by the total reflection mirror 31, and the characteristic X-rays 7b reflected by the total reflection mirror 31 are mostly low-energy characteristic X-rays emitted from oxygen O. Then, the intensity of the characteristic X-ray 7b of oxygen O after being reflected by the total reflection mirror 31 and the intensity of the characteristic X-ray 7a from magnesium Mg whose intensity is adjusted using the slit 32 are made substantially equal to each other. The same semiconductor X-ray detector 6 can be simultaneously detected.

That is, the aperture ratio can be changed by shifting the plates 32a and 32b having the two openings of the slit 32 which is the strength adjusting mechanism shown in FIG.
By changing the aperture ratio by shifting the plates 32a and 32b having one opening, the characteristic X from magnesium Mg can be obtained.
The intensity of the line 7a is made substantially equal to the intensity of the characteristic X-ray 7b of the oxygen O after being reflected by the total reflection mirror 31, and the same semiconductor X-ray detector 6 is used to efficiently measure both elements simultaneously. I am able to do so.

Further, X was formed on the magnesium oxide MgO substrate.
When irradiated with a ray or an electron beam, light in the visible region may be emitted. The semiconductor X-ray detector 6 is also sensitive to this visible light. Therefore, the shield 33 blocks the visible light and only the X-rays are detected by the semiconductor X-ray detector 6, so that the influence of the visible light on the semiconductor X-ray detector 6 can be prevented. .

In Example 1, as described above, not only the characteristic X-ray from oxygen O but also magnesium M
Since the characteristic X-ray from g can also be measured at the same time, it is possible to normalize the fluctuation of the incident X-ray using the characteristic X-ray from magnesium Mg. In addition, by forming the total reflection mirror 31 with a curved mirror or a plurality of mirrors, it becomes possible to have a condensing function and to increase the sensitivity to light elements. Further, the shape of the plate having the opening forming the slit 32 which is the strength adjusting mechanism is not limited to that of the first embodiment.

Further, in the first embodiment, the total reflection mirror 31 does not selectively take out X-rays of a specific energy like an optical element using diffraction, but a predetermined angle defined by a critical angle. Since all the X-rays having energy lower than that of X are selectively extracted, characteristic X-rays having lower energy than oxygen O can be measured when measuring the above-mentioned magnesium oxide MgO, and therefore, characteristic X-rays lower in energy than oxygen O are emitted. Impurities such as carbon can be measured at the same time.

Therefore, according to the first embodiment, the total reflection mirror 31 is used as the optical element, and the characteristic X-rays from the selectively reflected weak light elements having low intensity are compared with the characteristic X rays from the heavy metal having high intensity. By adjusting the intensity of the rays with the slit 32 that is the intensity adjusting mechanism, it is possible to set an appropriate intensity ratio, and among the characteristic X-rays emitted from the elements excited from the sample 1C, the intensity adjusting mechanism is used. By making the intensity of the characteristic X-ray 7a having a high energy equal to the intensity of the characteristic X-ray 7b having a low energy reflected by the total reflection mirror 31, the same semiconductor X-ray detector 6 can be efficiently used. Both elements can be detected almost equally at the same time. Further, by blocking the visible light with the shield 33 so that only the X-rays are detected by the semiconductor X-ray detector 6, the influence of the visible light on the semiconductor X-ray detector 6 can be prevented.

Example 2. Next, FIG. 5 shows X according to the second embodiment.
It is a block diagram which shows the principal part of a line detection apparatus. 5, the same parts as those in the first embodiment shown in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted. As a new code, 1D is silicon S
A sample in which boron B is doped on the i substrate, and 34 is a multilayer film mirror which is an optical element using a diffraction phenomenon provided in place of the total reflection mirror 31 which is an optical element using the total reflection phenomenon of the first embodiment. , 35a and 35b are multilayer mirrors 3
4 is a slit that defines an entrance / exit angle to / from the light source 4. Others
This is the same as in the first embodiment.

Here, the multilayer mirror 34, which is an optical element utilizing the diffraction phenomenon, as shown in FIG. 6, in the X-ray region, for example, molybdenum Mo as a heavy metal having a different refractive index on the silicon Si substrate 34a. The thin film 34b and the silicon Si thin film 34c as a light metal are alternately stacked by several hundred layers. In this way,
When the layers are laminated over a certain period, a high reflectance can be obtained where the black condition is satisfied due to the light diffraction phenomenon. For example, when the characteristic X-rays are incident and reflected at an angle that satisfies the black condition at the wavelength of the characteristic X-rays emitted from the element to be measured, the characteristic X-rays emitted from the element to be measured have a high reflectance. The characteristic X-rays of elements other than the above have a low reflectance and can be attenuated.

Therefore, the characteristic X-rays of a specific element can be selectively extracted regardless of the energy levels of the characteristic X-rays of low intensity and the characteristic X-rays of high intensity. That is, the total reflection mirror 3 utilizing the total reflection phenomenon of the first embodiment.
Unlike the case where 1 is used, even if the strength is weak because the element that emits the characteristic X-ray having a higher energy than the strong characteristic X-ray exists as an impurity and the amount is small, Only the characteristic X-rays of the element to be emitted can be selectively extracted.

The X-ray detection apparatus constructed as described above operates in the same manner as in the first embodiment. That is, X from an excitation source 2 (not shown) such as synchrotron radiation light.
Line 5 illuminates sample 1D. As a result, the element of the sample 1D is excited, and the characteristic X-ray (fluorescent X-ray) 7a emitted by the excited element passes through the slit 32 which is the intensity adjusting mechanism and is detected by the semiconductor X-ray detector 6. Further, similarly, characteristic X-rays (fluorescent X-rays) 7 emitted by the excited element are emitted.
b is reflected by the multilayer film mirror 34 at an incident / emission angle defined by the slits 35a and 35b, and then detected by the semiconductor X-ray detector 6. These characteristic X-rays 7a and 7b detected by the semiconductor X-ray detector 6 are processed by the signal processing circuit 8 and stored / displayed as a spectrum.

When measuring the doped boron B on the silicon Si substrate, the multilayer mirror 34 satisfies the black condition at the wavelength of the characteristic X-ray emitted by the element to be measured, as described above. By reflecting / reflecting the characteristic X-rays at an angle, the characteristic X-rays emitted from the sample 1D are attenuated, and the characteristic X-rays 7b from the boron B are reflected. The characteristic X-rays reflected by the multilayer mirror 34 are mostly characteristic B-rays of boron B. And the multilayer film mirror 3
The intensity of the characteristic X-ray 7b of boron B after being reflected at 4,
By adjusting the intensity of the characteristic X-ray 7a from the silicon Si by using the slit 32 to make the intensity substantially equal, both elements can be efficiently measured simultaneously by the same semiconductor X-ray detector 6.

In the second embodiment, as described above, not only the characteristic X-ray of boron B but also the characteristic X-ray from silicon Si can be measured at the same time. It becomes possible to normalize using X-rays.

Therefore, according to the second embodiment, the multilayer mirror 34 is used as the optical element utilizing the diffraction phenomenon, and the intensity is high with respect to the characteristic X-ray from the selectively reflected weak intensity impurity element. The intensity of the characteristic X-ray from the heavy metal is adjusted by the slit 32 which is an intensity adjusting mechanism.
Among the characteristic X-rays which can be set to an appropriate intensity ratio and which are emitted from the elements excited from the sample 1D, the slit 32 serving as the intensity adjusting mechanism allows the characteristic X-rays 7 with high intensity to be strong.
By making the intensity of a equal to the intensity of the characteristic X-ray 7b having a small intensity reflected by the multilayer mirror 34, the same semiconductor X-ray detector 6 can efficiently detect both elements simultaneously. it can.

Example 3. Next, FIG. 7 shows X according to the third embodiment.
It is a block diagram which shows the principal part of a line detection apparatus. In FIG. 7, the same parts as those in the first embodiment shown in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted. As a new code, 1E is a sample in which an impurity of carbon C is contained in a fluorescent substance of zinc oxide ZnO, and 36 is provided in place of the total reflection mirror 31 which is an optical element utilizing the total reflection phenomenon of the first embodiment. A transmission type diffraction grating such as a Fresnel zone plate as a transmission type imaging element utilizing the diffraction phenomenon, 6f is a semiconductor X-ray detector 6
It is an opening / closing mechanism provided on the front surface of the. Others are the same as in the first embodiment.

Here, the transmission type diffraction grating 36 is shown in FIG.
As shown in FIG. 2, a ring of concentric circles whose radius Rm is proportional to the square root of an integer m, which is a type of transmissive imaging element that utilizes the diffraction phenomenon, is provided with an opaque portion 36a and a transparent ring portion 36b. Light of a specific wavelength is condensed at the focal plane, and gold or the like is used for the opaque portion 36a in the X-ray region.

The characteristic X emitted by the element to be measured is
The sample 1E and the semiconductor X-ray detector 6 are placed at the positive and negative focus positions f = Rm ² / mλ at the wavelength λ of the line, and the characteristic X-rays of the element to be measured emitted from the sample 1E are sent to the semiconductor X-ray detector 6. By condensing the light, the intensity of the characteristic X-rays emitted by the element to be measured becomes relatively larger than the characteristic X-rays of other elements by this condensing action, and the characteristic X-rays of a specific element are collected. It becomes possible to take out selectively.

Therefore, it is possible to selectively extract the characteristic X-rays of a specific element regardless of the energy levels of the characteristic X-rays of low intensity and the characteristic X-rays of high intensity. That is, the total reflection mirror 3 utilizing the total reflection phenomenon of the first embodiment.
Unlike the case where 1 is used, even if the strength is weak because the element that emits the characteristic X-ray having a higher energy than the strong characteristic X-ray exists as an impurity and the amount is small, Only the characteristic X-rays of the element to be emitted can be selectively extracted.

In the X-ray detection apparatus constructed as described above, the inside of the sample container 9 is evacuated by the exhaust mechanism (not shown). Opening and closing mechanism 6 under vacuum
f is opened and the front surface of the semiconductor X-ray detector 6 is opened. Then, in the same manner as in Example 1, the sample 1E is irradiated with X-rays 5 from an excitation source 2 (not shown) such as synchrotron radiation. As a result, the elements of the sample 1E are excited, and the characteristic X-rays (fluorescent X-rays) 7a emitted by the excited elements pass through the slit 32, which is an intensity adjusting mechanism, and pass through the shield 33 and the semiconductor X-ray detector 6. Detected in. Similarly, the characteristic X-ray (fluorescent X-ray) 7b emitted by the excited element is diffracted by the transmission diffraction grating 36, and then detected by the semiconductor X-ray detector 6 through the shield 33. These characteristic X-rays 7a and 7b detected by the semiconductor X-ray detector 6 are processed by the signal processing circuit 8 and stored / displayed as a spectrum.

In Example 3, the case where the concentration of impurities contained in the fluorescent substance is measured is taken into consideration. When the sample 1E is irradiated with X-rays or electron beams, zinc oxide ZnO as the fluorescent substance is detected. , Characteristic X-ray (fluorescent X
Line) and at the same time emits strong visible light.
The line detector 6 is also sensitive to this visible light. Therefore, in the same manner as in the first embodiment, the shield 33 shields visible light and only the X-rays are detected by the semiconductor X-ray detector 6, and the influence of visible light on the semiconductor X-ray detector 6 is affected. I am trying to prevent it.

In the transmission type diffraction grating 36 such as the Fresnel zone plate described above, the positive and negative focal positions f = Rm at the wavelength λ of the characteristic X-ray emitted by the element to be measured.
^By placing the sample 1E and the semiconductor X-ray detector 6 at ² / mλ and collecting the characteristic X-rays of the element to be measured emitted from the sample 1E on the semiconductor X-ray detector 6, the X-rays of a specific energy can be obtained. Of the characteristic X-rays (fluorescent X-rays) emitted from the sample 1E.
Line) is diffracted by the transmission diffraction grating 36, and the characteristic X-ray (fluorescence X) of carbon C diffracted by the transmission diffraction grating 36 is diffracted.
By setting the slit 32 which is the strength adjusting mechanism so that the strength of the (line) and the strength of the zinc Zn which has passed through the slit 32 which is the strength adjusting mechanism are substantially equal to each other, the impurity element can be simultaneously measured efficiently. .

In Example 3, as described above, not only the characteristic X-ray (fluorescent X-ray) of carbon but also zinc Zn
Since the characteristic X-rays (fluorescent X-rays) of oxygen and oxygen O can be measured at the same time, it is possible to normalize the variation of the incident X-rays by using the intensity of the characteristic X-rays (fluorescent X-rays) of zinc Zn and oxygen O. Become.

Therefore, according to the third embodiment, the transmission type diffraction grating 36 is used as the optical element utilizing the diffraction phenomenon,
Diffract characteristic X-ray (fluorescent X-ray) of carbon C
By setting the slit 32 which is the intensity adjusting mechanism so that the intensity of the characteristic X-ray (fluorescent X-ray) and the intensity of zinc Zn which has passed through the slit 32 which is the intensity adjusting mechanism are substantially equal, Can be detected by the same semiconductor X-ray detector 6. Further, by the shield 33,
By blocking the visible light and detecting only the X-rays by the semiconductor X-ray detector 6, the influence of the visible light on the semiconductor X-ray detector 6 can be prevented.

Example 4. Next, FIG. 9 is a configuration diagram showing an elemental analysis device according to the fourth embodiment. In FIG. 9, 1F is a sample in a plasma state that emits light, which is an electromagnetic wave peculiar to each element in a discharge tube, which will be described later, 32 is a slit as a strength adjusting mechanism similar to that of the first embodiment shown in FIG.
Is a discharge tube, 38a and 38b are inlet / outlet ports for introducing and discharging a sample to be analyzed into the discharge tube 37, 39 is a power source for putting the introduced sample into a plasma state, 40a, 40b, 4
0c is the light emitted from the sample 1F in the plasma state, 41
Reference numerals a, 41b, 42a, 42b are slits, and 43, 44 are diffraction gratings as optical elements using a diffraction phenomenon, and the entrance and exit angles to and from the diffraction gratings 43, 44 are the slits 41.
a, 41b, 42a, 42b. Also,
Reference numeral 60 denotes a detector for detecting light of a plurality of wavelengths generated by the elements in the sample 1F, which is an energy dispersive detector different from the semiconductor X-ray detector 6 of Examples 1 to 3, and is a tunnel junction in a superconductor. Is a detector using.

Here, the diffraction gratings 43 and 44 have a large number of grooves 43 on the surface of the substrate 43, for example, as shown in FIG.
When b is engraved at a certain period, the wavelength of monochromatic light is λ, the distance between the centers of the grooves 43b is d, and the integer n is, for example,
When an electromagnetic wave having a wavelength λ emitted by the element to be measured is incident and reflected at an incident angle i and a diffraction angle θ shown in the following equation, d (sini-sin θ) = nλ The electromagnetic wave emitted from the element to be measured has a high reflectance. The obtained electromagnetic wave of other elements has a lower reflectance and can be attenuated. Therefore, it becomes possible to selectively extract the electromagnetic waves of a specific element, and it is possible to selectively extract only the electromagnetic waves of the element to be measured.

Further, as shown in FIG. 11, the detector 60 using the tunnel junction in the above superconductor is tin Sn.
Tin oxide Sn is formed between the thin film superconductors 60a and 60c.
It is a tunnel junction having a structure in which an insulator 60b made of an O thin film is interposed, and the size of the energy gap of the superconductor is about meV, which is 3 more than the energy gap of the semiconductor.
Nearly small. Therefore, in the semiconductor X-ray detector 6 used in Examples 1 to 3, the energy gap of the semiconductor is several eV, so that energy can be decomposed into electromagnetic waves in the X-ray region. Energy cannot be decomposed into electromagnetic waves of small energy, but the detector 60 using a tunnel junction in a superconductor
In the case, the energy of the electromagnetic wave having a smaller energy than that of the X-ray region can be decomposed, and the energy can be decomposed also in the region of ultraviolet to visible light.

When light is incident on the detector 60 using the tunnel junction in such a superconductor as shown in FIG. 11, a number of electron-hole pairs proportional to the energy of each light are generated. , Is output as a current pulse. This current pulse is input to the signal processing circuit 8 in the same manner as in the conventional example and the first to third embodiments, converted into a voltage pulse proportional to the amount of the current pulse through the built-in amplifier, and then by the built-in wave height analyzer. The energy spectrum is obtained by accumulating in the channel corresponding to each pulse peak value.

In the elemental analyzer constructed as described above, the light 40 emitted from the sample 1F in the plasma state is used.
The light a passes through the slit 32, which is an intensity adjusting mechanism, and is incident on the detector 60. Also, similarly, the emitted light 40
The beam b is reflected by the diffraction grating 43 at an incident / emission angle defined by the slits 41a and 41b, and then is incident on the detector 60. Further, similarly, the emitted light 40c is incident on the detector 60 after being reflected by the diffraction grating 44 at an incident / emission angle defined by the slits 42a and 42b. The light 40a, 40b, 40c incident on the detector 60 is processed by the signal processing circuit 8 as described above, and stored / displayed as a spectrum.

Here, for example, when measuring a sample containing an extremely small amount of impurities atomized, the diffraction gratings 43 and 44 are used.
As described above, it becomes possible to selectively extract the electromagnetic wave of a specific element by selectively reflecting and reflecting at a predetermined incident angle i and diffraction angle θ, and selectively select only the electromagnetic wave of the element to be measured. Since the light from the impurity element having a low intensity can be selectively reflected and the light having a high intensity can be prevented from being reflected, the intensity of the light emitted from the sample 1F in the plasma state can be extracted. Light from a strong substance can be attenuated by the diffraction gratings 43 and 44, and most of the light reflected by the diffraction gratings 43 and 44 is emitted from an extremely small amount of impurities. Further, by using a plurality of diffraction gratings, it is possible to increase the sensitivity and reflect light emitted from a plurality of trace amounts of impurities. Then, the intensity of the light 40b, 40c emitted from the trace amount of impurities after being reflected by the diffraction gratings 43, 44 and the intensity of the light 40a emitted from a substance having a high intensity are adjusted using the slit 32. By making them substantially equal, it is possible to efficiently measure a plurality of elements.

In the fourth embodiment, as described above, not only the light emitted from an extremely small amount of impurities,
Since the light emitted from the strong substance can be measured at the same time, the fluctuation of the light emitted from the sample 1F in the plasma state can be normalized by using the light emitted from the strong substance.

Therefore, according to the fourth embodiment, the diffraction gratings 43 and 44 are used as the optical elements utilizing the diffraction phenomenon,
With respect to the light from the impurity element that is selectively reflected and has a low intensity, the intensity of the high intensity light can be adjusted by the slit 32 that is the intensity adjusting mechanism, and an appropriate intensity ratio can be set. Of the light emitted by the element excited from the sample 1F, the intensity of the light 40a having high energy is changed by the slit 32 serving as the intensity adjusting mechanism.
Low energy light 40b, 40 selectively reflected by
By making the intensity equal to that of c, both elements can be efficiently detected by the same detector 60.

Example 5. Next, FIG. 12 is a configuration diagram showing a main part of the X-ray detection apparatus according to the fifth embodiment, showing the configuration inside the sample container 9. 12, the same reference numerals as those of the first embodiment shown in FIG. 1 indicate the same parts, and the description thereof will be omitted. As a new code, 1G is a sample in which fluorine F on a silicon Si substrate is mixed, and 45 is a diffraction phenomenon that reflects only the characteristic X-ray having a specific energy among the characteristic X-rays emitted from the sample 1G. Organic crystal (or inorganic crystal) 46a, 46b as an optical element utilizing is a solar slit that defines an incident / emission angle to / from the organic crystal 45. Others are the same as the first embodiment shown in FIG.

Here, the organic crystal 45 has a periodic structure in which the lattice planes of crystal atoms are separated by an interval d, as shown in the schematic crystal cross section of FIG. A strong reflectance is obtained when the conditions are satisfied. Therefore, the characteristic X emitted by the element to be measured
Characteristic X at an angle that satisfies the black condition at the wavelength of the line
Characteristic X emitted by the element to be measured when a line is reflected and reflected
The line has a high reflectance and the characteristic X-rays of the other elements have a lower reflectance and can be attenuated.

Therefore, it is possible to selectively extract the characteristic X-rays of a specific element regardless of the energy levels of the characteristic X-rays of low intensity and the characteristic X-rays of high intensity.
That is, unlike the case where the total reflection mirror 31 utilizing the total reflection phenomenon of Example 1 is used, an element that emits a characteristic X-ray having a higher energy than a characteristic X-ray having a high intensity is present as an impurity and its amount is very small. Therefore, even when the strength is weak,
It is possible to selectively extract only the characteristic X-rays of the element that emits the high-energy characteristic X-rays.

In the X-ray detection apparatus configured as described above, the sample 1G is irradiated with X-rays emitted from the excitation source 2 (not shown) such as synchrotron radiation. As a result, the element of the sample 1G is excited, and the characteristic X-ray 7a emitted by the excited element passes through the slit 32 which is the intensity adjusting mechanism and is detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-ray 7b emitted by the excited element is detected by the semiconductor X-ray detector 6 after being reflected by the organic crystal 45 at an incident / emission angle defined by the solar slits 46a, 46b. These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by the signal processing circuit 8 and stored / displayed as a spectrum.

For example, when measuring the fluorine F on the silicon Si substrate, the organic crystal 45 (or the inorganic crystal) has weak intensity when the characteristic X-rays are incident and reflected at an angle satisfying the black condition as described above. Since the characteristic X-rays from the impurity element can be selectively reflected and the characteristic X-rays with high intensity can be prevented from being reflected, the characteristic X-rays from silicon Si with high intensity out of the characteristic X-rays emitted from the sample 1G. Is an organic crystal 4
The characteristic X-rays reflected by the organic crystal 45 are mostly the characteristic X-rays of the fluorine F. Then, the characteristic X-ray intensity of the fluorine F after being reflected by the organic crystal 45 and the characteristic X-ray intensity from the silicon Si are made substantially equal by using the slit 32, so that both elements can be efficiently measured.

In the fifth embodiment, as described above, not only the characteristic X-ray of fluorine F, which is an impurity element having a low intensity, but also the characteristic X-ray from silicon Si having a high intensity can be measured at the same time. It is possible to normalize the variation of the incident X-ray using the characteristic X-ray from silicon Si.

Therefore, according to the fifth embodiment, the organic crystal 45 (or the inorganic crystal) is used as the optical element utilizing the diffraction phenomenon, and the black condition at the wavelength of the characteristic X-ray emitted by the element to be measured is satisfied. By reflecting / reflecting the characteristic X-rays at an angle, it is possible to selectively reflect the element to be measured, and from the selectively reflected, characteristic X-rays from the weakly impurity element, the heavy metal having high strength is used. The intensity of the characteristic X-ray can be adjusted to a proper intensity ratio by adjusting the intensity of the slit 32, which is an intensity adjusting mechanism, and among the light emitted by the element excited from the sample 1G,
The slit 32 serving as an intensity adjusting mechanism makes the intensity of the characteristic X-ray 7a having a high energy equal to the intensity of the characteristic X-ray 7b having a low energy selectively reflected by the organic crystal 45, whereby the same semiconductor X-ray is obtained. Both elements can be efficiently detected by the detector 6.

Example 6. Next, FIG. 14 is a configuration diagram showing a thin film forming apparatus according to the sixth embodiment. In FIG. 14, the same parts as those of the conventional example shown in FIG. 23 are denoted by the same reference numerals, 1H is a sample in which a trace amount of light element impurities such as a natural oxide film or carbon is mixed on a silicon Si substrate, and 2 is a sample 1H. An excitation source such as an electron beam source for exciting the element of, a semiconductor X-ray detector,
10 is a vacuum tank of the thin film forming apparatus, 11 is an exhaust mechanism for exhausting the inside of the vacuum tank 10, 12 is a manufacturing mechanism for forming a thin film on the sample 1H, and 14 is a detection element of the semiconductor X-ray detector 6. Liquid nitrogen duer for cooling. Also, 3
Reference numerals 1 and 32 are total reflection mirrors made of, for example, soda lime glass as optical elements similar to those of the first embodiment shown in FIG. 1, and slits which are an intensity adjusting mechanism, and 7a and 7b are characteristic X-rays.

As the semiconductor X-ray detector 6 used here, the characteristic X-ray excited by the excitation source 2 from the sample 1H is detected as shown in FIG. For detecting the detection element 6a, a vacuum container 6b for keeping the detection element 6a in a vacuum, an X-ray transmission window 6c for transmitting characteristic X-rays, an amplifier 6d for amplifying a detection signal from the detection element 6a, and an amplifier 6d. It has a rod 6e for leading out the amplified detection signal to the outside of the vacuum and also for leading out heat to cool the detection element 6a, and newly opens and closes a part of the vacuum container 6b on the front face of the detector. It has a mechanism 6f.

In the thin film forming apparatus configured as described above, first, the semiconductor X-ray detector 6 is kept in vacuum with the opening / closing mechanism 6f closed, and the evacuation mechanism 11 evacuates the vacuum chamber 10. Then, the opening / closing mechanism 6 is operated in a vacuum state.
f is opened and the front surface of the semiconductor X-ray detector 6 is opened. In that state, the electron beam emitted from the excitation source 2 is applied to the sample 1H. As a result, the element of the sample 1H is excited, and the characteristic X-ray 7a emitted by the excited element passes through the slit 32 which is the intensity adjusting mechanism and is detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-ray 7b emitted by the excited element is reflected by the total reflection mirror 31 and then detected by the semiconductor X-ray detector 6. These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by a signal processing circuit (not shown) and stored / displayed as a spectrum.

When the vacuum chamber 10 is exposed to the atmosphere for maintenance or the like, the opening / closing mechanism 6f is closed to maintain the vacuum of the semiconductor X-ray detector 6 and protect the semiconductor X-ray detector 6.
This is a procedure necessary for cooling the semiconductor X-ray detector 6 in order to reduce the noise of the semiconductor X-ray detector 6.
In the case of a detector that does not require cooling, the same effect can be obtained even if a detector without the opening / closing mechanism 6f is used.

When measuring a trace amount of light element impurities such as a natural oxide film on a silicon Si substrate or carbon in the thin film forming apparatus having the above-mentioned structure, the intensity of the characteristic X-rays emitted from the sample 1H is The characteristic X-ray from the strong silicon Si can be attenuated by the total reflection mirror 31.
The characteristic X-rays reflected by 1 are mostly low-energy characteristic X-rays such as oxygen and carbon. Then, the total reflection mirror 31
Characteristic X-ray intensity of oxygen and carbon and silicon S after being reflected by
By making the characteristic X-ray intensities from i almost equal using the slit 32, both elements can be efficiently measured.

In the sixth embodiment, as described above, not only the characteristic X-rays of oxygen, carbon, etc., but also the characteristic X-rays from silicon Si can be measured at the same time. It becomes possible to perform normalization using the characteristic X-rays.

Therefore, according to the sixth embodiment, during the thin film formation, the sample 1H is irradiated with the electron beam from the excitation source 2 to emit the characteristic X-rays from the excited element of the sample 1H, and the total reflection mirror. The characteristic X-ray 7b reflected by 31 and the characteristic X-ray 7a whose intensity is adjusted by the slit 32 are the same semiconductor X.
Since the line detector 6 is used for detection, even weak characteristic X-rays can be detected when measuring characteristic X-rays of a plurality of elements having a large intensity ratio, and composition changes are measured step by step during thin film formation. can do.

Example 7. Next, FIG. 15 is a configuration diagram showing a thin film forming apparatus according to the seventh embodiment. 15, the same parts as those of the fifth embodiment shown in FIG. 6 are designated by the same reference numerals, and the description thereof will be omitted. Further, 33 is a shield similar to that of the first embodiment shown in FIG. 1, 34, 35a and 35b are multilayer film mirrors similar to those of the second embodiment shown in FIG. 5, and slits that define the entrance and exit angles to and from the multilayer film mirror. Further, as a new code, 1I is silicon dioxide SiO ₂ by this thin film forming apparatus.
A sample on which a thin film is formed, and 47 is a valve.

In the thin film forming apparatus configured as described above, first, the semiconductor X-ray detector 6 is kept in vacuum with the opening / closing mechanism 6f for opening and closing a part of the vacuum container 6b in front of the detector closed. The vacuum chamber 10 is evacuated by the exhaust mechanism 11 and the opening / closing mechanism 6f is opened in a vacuum state to open the front surface of the detector. At this time, the valve 47 is open. In the process of introducing steam or gas generated in the vacuum chamber 10 during thin film formation by the manufacturing mechanism 12, the steam or gas affects the detector, and the valve 47 is closed to prevent it.

In this state, the electron beam emitted from the excitation source 2 is applied to the sample 1I. As a result, the element of the sample 1I is excited, the characteristic X-ray 7a emitted by the excited element passes through the shield 33, further passes through the slit 32 which is the intensity adjusting mechanism, and the semiconductor X-ray detector 6 To be detected. Similarly, the characteristic X-ray 7b emitted from the excited element passes through the shield 33, is reflected by the multilayer film mirror 34 at the entrance / exit angle defined by the slits 35a and 35b, and is then subjected to semiconductor X-ray detection. It is detected by the device 6. These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by a signal processing circuit (not shown) and stored / displayed as a spectrum.

When the vacuum chamber 10 is exposed to the atmosphere for maintenance or the like, the opening / closing mechanism 6f is closed and the semiconductor X-ray detector 6 is closed.
Keep the vacuum at and protect the detector. Further, in order to eliminate the pressure difference applied to the shield 33, the valve 47 is opened and then the vacuum chamber 10 is exposed to the atmosphere.

Then, for example, when a silicon dioxide SiO ₂ thin film is formed by a thin film forming apparatus, it is reflected and reflected by the multilayer mirror 34 at a predetermined incident / reflection angle at the wavelength of the characteristic X-ray emitted by the element to be measured. Among the characteristic X-rays emitted from the sample 1I, it is possible to attenuate the characteristic X-rays from silicon Si having high intensity by the multilayer film mirror 34 and to reflect the characteristic X-rays of oxygen O of low energy. The characteristic X-rays 7b reflected by the multilayer film mirror 34 are mostly characteristic X-rays of oxygen O having low energy. Then, the intensity X of the characteristic X-ray 7b of oxygen O after being reflected by the multilayer film mirror 34 and the intensity 7a of the characteristic X-ray from the silicon Si are made substantially equal by using the slit 32, so that the characteristic X from the silicon Si is obtained. Make sure that the lines do not limit the counting rate.

At this time, by shielding the light and heat generated from the manufacturing mechanism 12 by the shield 33, the influence on the semiconductor X-ray detector 6 can be prevented, and the shield 33 is heat resistant. Since it has a property, it is not deformed or melted by radiant heat due to substrate heating during thin film formation, so that the characteristic X-rays can be measured point by point during the thin film formation process. Thus, even when forming a thin film containing a light element such as oxygen O having a low generation efficiency of characteristic X-rays, the composition of the sample 1I can be measured in accordance with the thin film formation rate, and the thin film formation process can be performed. Since it is possible to prevent the influence of the light and heat generated therein on the semiconductor X-ray detector 6, it is possible to measure the composition of the sample step by step during the formation process.

Therefore, according to the seventh embodiment, the sample 1I is irradiated with the electron beam from the excitation source 2 during the thin film formation to emit the characteristic X-rays from the excited element of the sample 1I, and the multilayer mirror is obtained. The characteristic X-ray 7b reflected by the reference numeral 34 and the characteristic X-ray 7a whose intensity is adjusted by the slit 32 are the same semiconductor X.
Since the line detector 6 is used for detection, even weak characteristic X-rays can be detected when measuring characteristic X-rays of a plurality of elements having a large intensity ratio, and composition changes are measured step by step during thin film formation. At the same time, by blocking the light and heat generated from the manufacturing mechanism 12 for forming the thin film by the shield 33, the influence on the semiconductor X-ray detector 6 can be prevented. Even when forming a thin film containing a light element having a low characteristic X-ray generation efficiency, the composition of the sample can be measured in accordance with the thin film formation rate.

Example 8. Next, FIG. 16 is a configuration diagram showing a thin film forming apparatus according to the eighth embodiment. 16, the same parts as those of the sixth and seventh embodiments shown in FIGS. 14 and 15 are designated by the same reference numerals, and the description thereof will be omitted. Also, 45 and 46a
Reference numerals 46b and 46b are organic crystals similar to those of Example 5 shown in FIG. 12 and solar slits that define the entrance and exit angles to and from the organic crystals. Furthermore, as a new code, 1J is a titanium nitride TiN thin film in this thin film forming apparatus. Samples on which are formed 4
Reference numeral 8 is a gate valve, 49 is an exhaust mechanism, and 50 is a vacuum box, which shows a case where the above-mentioned gate valve 48 can detach a part that cannot be baked out when the vacuum tank 10 is baked out. In the mounting path, an exhaust mechanism 49 independent of the exhaust mechanism 11 of the vacuum chamber 10 is used to attach and detach the vacuum box 50.
Is evacuated, and then the gate valve 48 is opened.

In the thin film forming apparatus configured as described above, the electron beam emitted from the excitation source 2 is applied to the sample 1J. As a result, the elements of the sample 1J are excited, and the characteristic X-rays 7a emitted by the excited elements pass through the slit 32 which is the intensity adjusting mechanism, further pass through the shield 33, and the semiconductor X-ray detector 6 To be detected. Similarly, the characteristic X-ray 7b emitted by the excited element is the solar slit 46b.
After being reflected by the organic crystal 45 at the incident / emission angle defined by a and 46b, it passes through the shield 33 and the semiconductor X-ray detector 6
Detected in. These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by a signal processing circuit (not shown) and stored / displayed as a spectrum.

For example, in a thin film forming apparatus, titanium nitride TiN is used.
When forming a thin film, of the characteristic X-rays emitted from the sample 1J, the characteristic X-rays emitted by the element to be measured are reflected by the organic crystal 45 at a high reflectance, and the characteristic X-rays of the other elements are also reflected. By setting the incident / reflection angle to the organic crystal in order to reduce the reflectance and attenuate the characteristic X-ray of K line from titanium Ti having high strength is attenuated by the organic crystal 45 and the nitrogen N is reduced. Energy characteristics X
The characteristic X-rays 7b that can reflect the rays can be mostly the low energy characteristic X-rays of nitrogen N. Then, the intensity of the characteristic X-rays 7b of nitrogen N after being reflected by the organic crystal 45 and the intensity of the characteristic X-rays 7a of K rays from titanium Ti are made substantially equal using the slit 32, so that the titanium Ti The counting rate is not limited by the characteristic X-rays, and the characteristic X-rays of weak elements can be detected at the same time, and both elements can be measured.

At this time, by blocking the light and heat generated from the manufacturing mechanism 12 for forming the thin film by the shield 33, the influence on the semiconductor X-ray detector 6 can be prevented, and Since the shield 33 has heat resistance, it is not deformed or melted by radiant heat due to substrate heating during thin film formation, so that the above characteristic X-rays are not affected by heat during the thin film formation process. It can be measured point by point. In addition, since the organic crystal 45 is reflected at the incident and outgoing angles defined by the solar slits 46a and 46b, the K line of nitrogen N and the L line of titanium Ti can be separated.

Therefore, according to the above-mentioned Example 8, the intensity of the characteristic X-ray 7b of nitrogen N reflected by the organic crystal 45 and the intensity of the characteristic X-ray 7a of K line from titanium Ti are slit 3.
By using 2 to make them substantially equal, the counting rate is not limited by the characteristic X-rays from titanium Ti, and both elements are detected by the same semiconductor X-ray detector 6, so that multiple intensity ratios are increased. When measuring the characteristic X-rays of an element, even weak characteristic X-rays can be detected, and the change in composition can be measured step by step during thin film formation.
By shielding the light and heat generated from the manufacturing mechanism 12 by the above, it is possible to prevent the influence on the semiconductor X-ray detector 6 and to form a thin film containing a light element having low characteristic X-ray generation efficiency. Moreover, the measurement of the composition of the sample can follow the thin film formation rate. In addition, the solar slits 46a, 46
Since the light is reflected by the organic crystal 45 at the entrance / exit angle defined by b, the K line of nitrogen N and the L line of titanium Ti can be separated.

Example 9. Next, FIG. 17 is a configuration diagram showing a thin film forming apparatus for forming a thin film by using the sputtering phenomenon according to the ninth embodiment. In FIG. 17, the same parts as those in each of the above-described embodiments are designated by the same reference numerals, and the description thereof will be omitted. Further, as new symbols, 1K is a sample in which a titanium nitride TiN thin film is formed on the substrate, 51 is a gas introduction mechanism,
52 is a power source for generating plasma, 53 is a target material, 54 and 55 are gate valves, and 56 is a plurality of inorganic substances as optical elements using the same diffraction phenomenon as the organic crystal 45 of Example 5 shown in FIG. It is a crystal.

In the thin film forming apparatus constructed as described above, first, a gas such as argon is introduced by the gas introduction mechanism 51, and a plasma of argon gas is generated by the power supply 52. A thin film is formed on the substrate of the sample 1K by sputtering the target material 53 with argon ions in the plasma. The gate valves 54 and 55 are closed during sputtering, the gate valves 54 and 55 are opened after the thin film formation, and the target material 53 is irradiated with the electron beam emitted from the excitation source 2. As a result, the target material 5
Characteristic X that the element of 3 is excited and the excited element emits
The line 7a passes through the slit 32, which is an intensity adjusting mechanism, and is detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-ray 7b emitted by the excited element is reflected and condensed by the plurality of inorganic crystals 56, and then detected by the semiconductor X-ray detector 6. These characteristic X detected by the semiconductor X-ray detector 6
The line is processed by a signal processing circuit (not shown) and stored / displayed as a spectrum.

For example, with this thin film forming apparatus, titanium nitride T
When forming the iN thin film, impurities such as carbon C and oxygen O of the target material 53 change the sputtering rate or enter as impurities in the thin film. Therefore, it is necessary to check the impurity contamination of the target material 53 from time to time. Of the characteristic X-rays emitted from the target material 53, the characteristic X-rays are reflected and reflected by the plurality of inorganic crystals 56 at an angle that satisfies the black condition at the wavelength of the characteristic X-rays emitted by the element to be measured. It is possible to reflect the characteristic X-rays of oxygen C and carbon O by the plurality of inorganic crystals 56, respectively, and attenuate the K-rays and the characteristic X-rays of nitrogen N from titanium Ti, which have high strength. Then, the characteristic X-ray intensities of carbon C and oxygen O after being reflected by the plurality of inorganic crystals 56 and K from titanium Ti.
By making the characteristic X-ray intensities of the lines almost equal using the slit 32, it is possible to efficiently measure the impurity element at the same time.

Further, not only the characteristic X-rays of oxygen O and carbon C but also the characteristic X-rays from titanium Ti can be measured at the same time, so the fluctuation of the incident electron beam is normalized using the characteristic X-rays from titanium Ti. It becomes possible. Further, by reflecting and condensing the characteristic X-rays of oxygen O and carbon C by the plurality of inorganic crystals 56, it becomes possible to increase the sensitivity to the impurity element.

Therefore, according to the ninth embodiment, when the thin film is formed by using the sputtering phenomenon, the characteristic X-ray emitted by the element in the target material 53 excited by the excitation source 2 is detected. Therefore, depending on the composition of the thin film formed on the substrate, it may be damaged when it is directly irradiated with an electron beam or X-ray. In such a case, the thin film is not damaged during the formation of the thin film. The composition change can be measured step by step, and the composition of the thin film formed on the sample 1K can be prevented from changing due to the composition change of the target material 53.

Example 10. Next, FIG. 18 is a configuration diagram showing a thin film forming apparatus for forming a thin film using the sputtering phenomenon according to the tenth embodiment. In FIG. 18, the same reference numerals as those in the above-described embodiments indicate the same parts, and the description thereof will be omitted. As a new code, 1 L is yttrium barium copper oxide (Y
A sample on which a Ba ₂ Cu ₃ O _8-x ) thin film is formed, 57 is an exhaust mechanism, and 58 is a gas introduction mechanism.

In the thin film forming apparatus constructed as described above, first, a gas such as argon is introduced by the gas introduction mechanism 51, and plasma of argon gas is generated by the power supply 52. By sputtering the target material 53 with argon ions in the plasma, a thin film is formed on the substrate of the sample 1L. The target material 53 is irradiated with the electron beam emitted from the excitation source 2 during the thin film formation. This allows
The element of the target material 53 is excited, and the characteristic X-ray 7a emitted by the excited element is the slit 3 which is an intensity adjusting mechanism.
2 and is detected by the semiconductor X-ray detector 6. Also,
Similarly, the characteristic X-ray 7b emitted by the excited element is reflected by the total reflection mirror 31 and then detected by the semiconductor X-ray detector 6. These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by a signal processing circuit (not shown) and stored / displayed as a spectrum.

For example, in this thin film forming apparatus, yttrium barium copper oxide (YBa ₂ Cu) which is a high temperature superconducting material is used.
_{When a 3} O _8-x ) thin film is formed, it is necessary to monitor the composition of the target material 53 because the composition deviation of the target material 53 affects the composition deviation of the formed thin film. Of the characteristic X-rays emitted from the target material 53, the characteristic X-rays emitted from the element to be measured are reflected and reflected by the total reflection mirror 31 at a predetermined incident reflection angle so as to be selectively reflected. The characteristic X-rays of oxygen O are reflected at 31, and strong yttrium Y, barium Ba, and copper C
The characteristic X-ray from u can be attenuated. And
Characteristic X-ray 7 of oxygen O after being reflected by the total reflection mirror 31
By making the intensity of b and the intensity of the characteristic X-ray 7a from yttrium Y, barium Ba, or copper Cu approximately equal using the slit 32, it is possible to efficiently measure the composition of the target material 53.

Further, by differentially pumping the excitation source 2 by the pumping mechanism 57, it is possible to measure even in a state where the argon gas or the like during the thin film formation is introduced. Further, it is possible to prevent the sputtered particles from adhering to the shield 33 by using the gas introduction mechanism 58 to flow the gas so that the pressure difference is not applied to the shield 33. By shielding the light and heat generated from the plasma by the shield 33, it is possible to prevent the influence on the semiconductor X-ray detector 6, and since the shield 33 has heat resistance, it is possible to prevent it from radiant heat or the like. Because it does not deform or melt, during the thin film formation process,
The characteristic X-rays can be measured one by one.

Therefore, according to the tenth embodiment, when the thin film is formed by using the sputtering phenomenon, the characteristic X-ray emitted by the element in the target material 53 excited by the excitation source 2 is detected. Therefore, depending on the composition of the thin film formed on the substrate, it may be damaged when directly irradiated with an electron beam or X-ray, but in such a case,
It is possible to measure changes in composition during thin film formation step by step without damaging the thin film, and to prevent changes in composition of the thin film formed on the sample 1L due to changes in composition of the target material 53. By differentially exhausting the excitation source 2 by the exhaust mechanism 57, measurement can be performed even in a state where argon gas or the like during thin film formation is introduced, and the gas introduction mechanism 58 is used so that no differential pressure is applied to the shield 33. A semiconductor X-ray detector 6 can be provided by flowing a gas to prevent the sputtered particles from adhering to the shield 33 and shielding the light and heat generated from the plasma by the shield 33.
Can be prevented.

Example 11. Next, FIG. 19 is a configuration diagram showing an etching apparatus for performing dry cleaning according to the eleventh embodiment. In FIG. 19, the same parts as those in each of the above-described embodiments are designated by the same reference numerals, and the description thereof will be omitted. As new symbols, 1M is a sample in which impurities of light elements such as oxygen and carbon due to a natural oxide film on a silicon Si substrate are mixed, and 59 is an electrode for generating plasma.

In the etching apparatus configured as described above, the sample 1M is irradiated with the electron beam or X-ray emitted from the excitation source 2 such as the electron beam source or the X-ray source. As a result, sample 1
The element M is excited and the excited element emits a characteristic X
The line 7a passes through the slit 32, which is an intensity adjusting mechanism, and is detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-ray 7b emitted by the excited element is reflected by the total reflection mirror 31 and then detected by the semiconductor X-ray detector 6. The characteristic X-ray detected by the semiconductor X-ray detector 6 is the signal processing circuit 8
Processed and stored and displayed as a spectrum.

In the case of removing impurities of light elements such as oxygen and carbon by the natural oxide film on the silicon Si substrate of the sample 1M by etching, an etching gas is introduced by the gas introduction mechanism 51 and a power source 52 for generating plasma is used. Sample 1M
Plasma is generated between the electrode 59 and the electrode 59 to remove the impurities by etching. Then, the gate valves 54 and 55 are opened, and the element in the sample 1M is excited by the excitation source 2.
Of the characteristic X-rays emitted from the sample 1M among the characteristic X-rays emitted from the sample 1M, the characteristic X-rays emitted by the element to be measured are selectively reflected by the total reflection mirror 31 at a predetermined incident reflection angle.
The characteristic X-ray from silicon Si, which has high intensity, is reflected by the total reflection mirror 31
The characteristic X-rays reflected by the total reflection mirror 31 are mostly characteristic low-energy X-rays such as oxygen and carbon.

Then, the characteristic X-ray intensity from silicon Si is set to an intensity at which the signal processing circuit 8 operates normally by using the slit 32, so that a very small amount of impurities such as oxygen and carbon that could not be removed after etching. Elements can be measured efficiently. Moreover, since the sample 1M is not etched in the vacuum layer 10 and exposed to the atmosphere, the substrate surface is not oxidized and the amount removed by etching can be accurately measured.

Therefore, according to Example 11 above, the sample 1
In the case of removing impurities of light elements such as oxygen and carbon due to the natural oxide film on the silicon Si substrate of M, the sample 1M is removed by the excitation source 2 after the etching of the impurities.
Of the characteristic X-rays emitted from the sample 1M by exciting the elements therein, the characteristic X-ray intensity of impurities such as oxygen and carbon reflected by the total reflection mirror 31 and the characteristic X-ray intensity from silicon Si are determined by the slit 32. To make the signal processing circuit 8 operate normally so as to be approximately equal to each other, so that it is possible to efficiently measure the extremely small amount of oxygen and carbon impurity elements that could not be removed after etching. Since 1M is not exposed to the atmosphere, the substrate surface is not oxidized,
The amount removed by etching can be accurately measured.

Example 12. Next, FIG. 20 is a configuration diagram showing an ion implantation apparatus according to the twelfth embodiment. In FIG. 20, the same parts as those in each of the above-described embodiments are designated by the same reference numerals, and the description thereof will be omitted. As a new code, 1N is silicon Si
A sample in which phosphorus P is injected on the substrate, 60 is an ion beam 61 for generating ions to be injected for acceleration and mass separation.
Is an accelerator for irradiating the sample 1N, 62 is a rotating mechanism of the sample substrate, and 63 is a diffraction grating using a single crystal as an optical element utilizing a diffraction phenomenon.

In the ion implanter configured as described above, the ion beam 6 generated by the accelerator 60 is used.
1 is irradiated to the sample 1N. Since the ion beam 61 has acceleration energy, the elements in the sample 1L are excited,
The characteristic X-ray (fluorescent X-ray) 7a emitted by the excited element passes through the slit 32 which is an intensity adjusting mechanism and is detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-ray (fluorescent X-ray) 7b emitted by the excited element is diffracted by the diffraction grating 63 and then detected by the semiconductor X-ray detector 6. The characteristic X-ray (fluorescent X-ray) detected by the semiconductor X-ray detector 6 is processed by the signal processing circuit 8 and stored / displayed as a spectrum.

For example, the case of implanting phosphorus P into a silicon Si substrate will be taken up. Phosphorus P is generated by the accelerator 60, and the silicon Si substrate is irradiated with the phosphorus P ion beam 61.
Phosphorus ions are decelerated in the silicon Si substrate and implanted near a predetermined depth. At this time, since the phosphorus ions are given energy of several tens to several hundreds eV, the element of silicon Si is excited. Further, since the phosphorus P element previously implanted is also excited, when the ion beam 61 is irradiated, silicon S
i and phosphorus P emit characteristic X-rays (fluorescent X-rays). Silicon S
Since the atoms of the phosphorus P element are very small compared to the number of atoms of the i substrate, the characteristic X-ray (fluorescent X-ray) of phosphorus P is very weak. Therefore, the diffraction grating 63 and the solar slits 46a, 4
Only the characteristic X-rays (fluorescent X-rays) 7b of phosphorus P are guided via the 6b to the semiconductor X-ray detector 6. The characteristic X-rays (fluorescent X-rays) 7a from silicon Si, which has a high intensity, are made to have the same intensity as the characteristic X-rays (fluorescent X-rays) 7b of phosphorus P using the slit 32, and are guided to the semiconductor X-ray detector 6. Thereby, the characteristic X-ray (fluorescent X-ray) of silicon Si can be measured at the same time, and the fluctuation of the incident X-ray can be normalized by using the intensity of the characteristic X-ray (fluorescent X-ray) of silicon Si. .

Therefore, according to the twelfth embodiment, silicon S
When phosphorus P element is ion-implanted on the i substrate, the element in the sample 1L is excited by irradiation of the ion beam 61,
Of the characteristic X-rays (fluorescent X-rays) emitted from the sample 1N,
The characteristic X-rays (fluorescent X-rays) of phosphorus P that have passed through the diffraction grating 63 and the solar slits 46a and 46b and the characteristic X-rays (fluorescent X-rays) from silicon Si that have passed through the slits 32 are the same. Semiconductor X-ray detector 6 with about the same intensity
The characteristic X-rays (fluorescent X-rays) of phosphorus P and silicon Si can be simultaneously measured at the time of ion implantation.

[0131]

As described above, according to claim 1 of the present invention, in the electromagnetic wave detecting device having the detector for detecting the electromagnetic waves of a plurality of wavelengths generated by the elements in the sample, the sample and the detector are provided. And an optical element that selectively reflects or transmits at least one or more wavelengths of electromagnetic waves of a plurality of wavelengths generated from the sample, and is installed between the sample and the detector. A plurality of large intensity ratios are provided by including an intensity adjusting mechanism for adjusting the intensity of electromagnetic waves, and detecting the electromagnetic waves reflected or transmitted by the optical element and the electromagnetic waves whose intensity is adjusted by the intensity adjusting mechanism with the detector. It is possible to detect even weak electromagnetic waves when measuring the electromagnetic waves.

Further, according to the electromagnetic wave detecting apparatus of the second aspect, when measuring a plurality of electromagnetic waves having a large intensity ratio, the wavelength of the electromagnetic waves is set to the X-ray region, so that the element based on the energy value of the X-rays. There is an effect that it is possible to easily identify the type.

According to the electromagnetic wave detecting apparatus of the third aspect, the detector is an energy dispersive type detector, and when a plurality of electromagnetic waves having a large intensity ratio are detected, the electromagnetic waves having a large intensity are counted. It is possible to detect weak electromagnetic waves at the same time without the rate being limited.

Further, according to the electromagnetic wave detecting device of the fourth aspect, the light and heat entering the detector are shielded and at the same time 1 ke
By providing a heat-resistant shield that transmits X-rays containing V or less soft X-rays, the adverse effect of light or heat on the detector is prevented, and X-rays containing soft X-rays of 1 keV or less are emitted. The light element can be detected.

Further, according to the electromagnetic wave detecting device of the fifth aspect, the intensity adjusting mechanism is constituted by the slit, so that the aperture ratio of the slit can be changed and the intensity can be easily adjusted. Produce an effect.

According to the electromagnetic wave detecting device of the sixth aspect, by using an optical element utilizing the total reflection phenomenon as the optical element, the electromagnetic wave is reflected and reflected at a predetermined incident / reflection angle, so that a plurality of electromagnetic waves are reflected. Among them, it is possible to simultaneously reflect electromagnetic waves emitted from a plurality of elements that emit electromagnetic waves of energy lower than a predetermined energy, and to measure the elements that emit the reflected electromagnetic waves at the same time. Play.

According to the electromagnetic wave detecting device of the seventh aspect, by using an optical element utilizing a diffraction phenomenon as the optical element, the electromagnetic wave is incident / reflected at a predetermined incident / reflecting angle or at a predetermined focal position. By placing the sample and the detector and focusing the electromagnetic wave of the element to be measured emitted from the sample on the detector, the electromagnetic wave of the specific element can be generated regardless of the energy level of the weak electromagnetic wave and the strong electromagnetic wave. It is possible to take out selectively, and unlike the case of using an optical element that utilizes the total reflection phenomenon, the strength of the element that emits electromagnetic waves with higher energy than the strong electromagnetic waves is present as impurities Even if it is weak, it is possible to selectively extract only the electromagnetic wave of the element that emits the high-energy electromagnetic wave.

Further, according to the substrate processing apparatus of the eighth aspect, during processing of the substrate by the processing mechanism, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector. By detecting, it is possible to detect weak electromagnetic waves when measuring a plurality of electromagnetic waves having a large intensity ratio during the processing of the substrate, and it is possible to measure a change in composition.

According to the substrate processing apparatus of the ninth aspect, when the thin film is formed on the substrate by the thin film forming mechanism using the sputtering phenomenon, the elements in the target material to be sputtered are excited by the excitation source, By detecting the electromagnetic wave emitted by the element excited by the detector, it is possible to detect the change in the composition of the target material.

According to the substrate processing apparatus of the tenth aspect, the optical element selectively reflects at least one or more wavelengths of the electromagnetic waves generated by the element in the target material, and the intensity adjusting mechanism is used. By adjusting the intensity of the electromagnetic wave, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism are detected by the detector, and the intensity ratio of the elements in the target material is generated. It is possible to detect even weak electromagnetic waves when measuring a plurality of large electromagnetic waves.

According to the substrate processing apparatus of the eleventh aspect, in any one of the eighth to tenth aspects, when measuring a plurality of electromagnetic waves having a large intensity ratio during substrate processing,
By setting the wavelength of the electromagnetic wave in the X-ray region, it is possible to easily identify the type of the element of the substrate or the target material to be the sample based on the energy value of the X-ray.

According to a twelfth aspect of the present invention, in the substrate processing apparatus according to any of the eighth to eleventh aspects, the detector is an energy dispersive detector.
When a plurality of electromagnetic waves having a high intensity ratio are detected, it is possible to detect weak electromagnetic waves at the same time without the rate of counting being limited by the electromagnetic waves having a high intensity.

According to the substrate processing apparatus of the thirteenth aspect, in addition to the eighth aspect, the light and heat entering the detector are shielded and the soft X of 1 keV or less is used.
By including a heat-resistant shield that transmits X-rays including X-rays, the adverse effect of light and heat on the detector can be prevented.
It is possible to detect light elements that emit X-rays including soft X-rays of eV or less.

Further, according to the substrate processing apparatus of the fourteenth aspect, in any one of the eighth to thirteenth aspects, by forming the strength adjusting mechanism with a slit, the aperture ratio of the slit can be changed to be simple. This has the effect of enabling strength adjustment.

According to the substrate processing apparatus of the fifteenth aspect, in any one of the eighth to fourteenth aspects, by using the optical element utilizing the total reflection phenomenon as the optical element, the electromagnetic wave with a predetermined incident / reflection angle is obtained. By reflecting and reflecting, it is possible to simultaneously reflect electromagnetic waves emitted from a plurality of elements that emit an electromagnetic wave having an energy lower than a predetermined energy among a plurality of electromagnetic waves, and the element that emits the reflected electromagnetic waves. There is an effect that can be measured simultaneously.

According to the substrate processing apparatus of the sixteenth aspect, in any one of the eighth to fourteenth aspects, by using the optical element utilizing the diffraction phenomenon as the optical element, the electromagnetic wave is emitted at a predetermined incident / reflection angle. By inputting / reflecting or placing the sample and the detector at a predetermined focus position and concentrating the electromagnetic wave of the element to be measured emitted from the sample on the detector,
Electromagnetic waves of a specific element can be selectively taken out regardless of the energy level of weak electromagnetic waves and strong electromagnetic waves, and strong electromagnetic waves are stronger than when using optical elements that utilize the total reflection phenomenon. Even if the strength is weak because an element that emits an electromagnetic wave having a higher energy than an electromagnetic wave exists as an impurity and its amount is very small, it is possible to selectively extract only the electromagnetic wave of an element that emits an electromagnetic wave having a high energy. Play.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing a main part of an X-ray detection apparatus according to a first embodiment of the present invention.

FIG. 2 is a structural schematic diagram and a characteristic curve diagram showing an example of a total reflection mirror as an optical element of FIG.

FIG. 3 is an explanatory diagram showing an example of a slit which is a strength adjusting mechanism of FIG.

FIG. 4 is a structural diagram showing an example of the shield of FIG.

FIG. 5 is a configuration diagram showing a main part of an X-ray detection apparatus according to a second embodiment of the present invention.

6 is a structural schematic diagram showing an example of a multilayer film mirror as the optical element of FIG.

FIG. 7 is a configuration diagram showing a main part of an X-ray detection apparatus according to a third embodiment of the present invention.

8 is a structural schematic diagram showing an example of a transmission type diffraction grating as the optical element of FIG.

FIG. 9 is a configuration diagram showing an elemental analysis device according to a fourth embodiment of the present invention.

10 is a structural schematic view showing an example of a diffraction grating as the optical element of FIG.

11 is a structural schematic view showing an example of a detector using the junction in the superconductor of FIG.

FIG. 12 is a configuration diagram showing a main part of an X-ray detection apparatus according to a fifth embodiment of the present invention.

13 is a structural schematic diagram showing an example of an organic crystal as an optical element of FIG.

FIG. 14 is a configuration diagram showing a thin film forming apparatus and a semiconductor X-ray detector according to Embodiment 6 of the present invention.

FIG. 15 is a configuration diagram showing a thin film forming apparatus according to Embodiment 7 of the present invention.

FIG. 16 is a configuration diagram showing a thin film forming apparatus according to Embodiment 8 of the present invention.

FIG. 17 is a configuration diagram showing a thin film forming apparatus for forming a thin film by using a sputtering phenomenon according to a ninth embodiment of the present invention.

FIG. 18 is a configuration diagram showing a thin film forming apparatus for forming a thin film by using a sputtering phenomenon according to Embodiment 10 of the present invention.

FIG. 19 is a configuration diagram showing an etching apparatus for performing dry cleaning according to an eleventh embodiment of the present invention.

FIG. 20 is a configuration diagram showing an ion implantation apparatus according to embodiment 12 of the present invention.

FIG. 21 is a configuration diagram showing a conventional X-ray detection device.

22 is an explanatory diagram showing an X-ray detection principle in the semiconductor X-ray detector and the pulse height analyzer in the signal processing circuit of FIG. 21, and an explanatory diagram showing current pulses and their pulse height analysis results.

FIG. 23 is a configuration diagram showing a conventional thin film forming apparatus and a semiconductor X-ray detector.

FIG. 24 is a schematic diagram showing an example of a current pulse P3 train output from the detector when the characteristic X-ray energy intensity is high in the conventional X-ray detection device.

[Explanation of symbols]

 1C sample 1D sample 1E sample 1F sample 1G sample 1H sample 1I sample 1J sample 1K sample 1L sample 1M sample 1N sample 2 excitation source 5 X-ray 6 semiconductor X-ray detector 7a characteristic X-ray 7b characteristic X-ray 12 signal processing Mechanism 31 Total reflection mirror 32 Slit 33 Shield 34 Multilayer film mirror 35a Slit 35b Slit 36 Transmission type diffraction grating 43 Diffraction grating 44 Diffraction grating 45 Organic crystal 53 Target material 56 Multiple inorganic crystals 60 Tunnel junction in superconductor was used Detector 63 Diffraction grating

Claims (16)

[Claims] 1. An electromagnetic wave detection device having a detector for detecting electromagnetic waves of a plurality of wavelengths generated by elements in a sample, wherein the plurality of wavelengths generated from the sample are installed between the sample and the detector. The optical element that selectively reflects or transmits at least one or more wavelengths of the electromagnetic waves of the above, and an intensity adjusting mechanism that is installed between the sample and the detector to adjust the intensity of the electromagnetic waves. An electromagnetic wave detection device characterized in that the detector detects the electromagnetic wave reflected or transmitted by the element and the electromagnetic wave whose intensity is adjusted by the intensity adjusting mechanism. 2. The electromagnetic wave detection device according to claim 1, wherein the wavelength of the electromagnetic wave is in the X-ray region. 3. The electromagnetic wave detection device according to claim 1 or 2, wherein the detector is an energy dispersive detector. 4. A heat-resistant shield that shields light and heat entering the detector and transmits X-rays including soft X-rays of 1 keV or less.
The electromagnetic wave detection device according to any one of 1. 5. The electromagnetic wave detecting device according to claim 1, wherein the strength adjusting joint mechanism is a slit. 6. The electromagnetic wave detecting device according to claim 1, wherein the optical element is an optical element utilizing a total reflection phenomenon. 7. The electromagnetic wave detection device according to claim 1, wherein the optical element is an optical element that utilizes a diffraction phenomenon. 8. A processing mechanism for processing a substrate, an excitation source for exciting a plurality of elements contained in the substrate being processed, and detecting electromagnetic waves of a plurality of wavelengths emitted by the elements excited by the excitation source. A detector, an optical element installed between the substrate being processed and the detector, for selectively reflecting or transmitting at least one wavelength of electromagnetic waves having a plurality of wavelengths; An intensity adjusting mechanism that is installed between the substrate and the detector to adjust the intensity of the electromagnetic wave is provided, and during processing of the substrate by the processing mechanism, the electromagnetic wave reflected or transmitted by the optical element and the intensity adjusting mechanism are used. A substrate processing apparatus, wherein the intensity of the electromagnetic wave adjusted is detected by the detector. 9. A thin film forming mechanism for forming a thin film on a substrate using a sputtering phenomenon, an excitation source for exciting an element in a target material to be sputtered, and an electromagnetic wave emitted by the element excited by this excitation source. A substrate processing apparatus, comprising: a detector for detecting 10. An optical element installed between the target material and the detector to transmit or reflect the electromagnetic wave, and a strength installed between the target material and the detector to adjust the strength of the electromagnetic wave. The substrate processing apparatus according to claim 9, further comprising an adjusting mechanism. 11. The substrate processing apparatus according to claim 8, wherein the wavelength of the electromagnetic wave is in the X-ray region. 12. The substrate processing apparatus according to claim 8, wherein the detector is an energy dispersive detector. 13. A heat-resistant shield that shields light and heat entering the detector and transmits X-rays including soft X-rays of 1 keV or less. The substrate processing apparatus according to any one of claims. 14. The substrate processing apparatus according to claim 8, wherein the strength adjusting mechanism is a slit. 15. The optical element according to claim 8, wherein the optical element is an optical element utilizing a total reflection phenomenon.
The substrate processing apparatus according to any one of 1. 16. The substrate processing apparatus according to claim 8, wherein the optical element is an optical element that utilizes a diffraction phenomenon.