JP3078168B2 - Electromagnetic wave detection device and substrate processing device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
An electromagnetic wave detection device that excites an element by an excitation source such as an ion beam and detects an electromagnetic wave emitted from the excited element, in particular, a characteristic X-ray (hereinafter, characteristic X-ray includes a fluorescent X-ray) and this electromagnetic wave detection The present invention relates to a substrate processing apparatus capable of detecting a change in composition during substrate processing using the apparatus.

[0002]

2. Description of the Related Art In recent years, along with the high integration and miniaturization of electronic devices and semiconductors, a trace amount of impurities has influenced device characteristics. For this reason, it is becoming important to examine a very small amount of impurity contamination. As a method for measuring such a minute amount of impurity contamination, an impurity element is excited by an excitation source such as an X-ray or an electron beam / ion beam, and electromagnetic waves emitted from the excited element, particularly characteristic X-rays, are detected. Thus, there is a method of measuring an impurity element. This measuring method has recently been often used because an impurity element can be measured without breaking 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"
(Edited by T. Fumasu, Industrial Research Committee, 1990, p. 49
It is similar to that shown in 7). In FIG. 21, 1A is, for example, iron Fe or copper Cu on a silicon Si substrate.
A sample containing impurities of an equal heavy metal, 2 was a sample 1A
An excitation source such as a synchrotron radiation for exciting the elements 3 is a spectroscope for dispersing the X-rays 5 from the excitation source 2, and 4 a and 4 b are for determining an incident / emission angle of the spectroscope 3. A slit 6 is a semiconductor X-ray detector for detecting characteristic X-rays 7 generated by elements in the sample 1A excited by the X-rays 5 from the excitation source 2, and 8 is a pulse height analyzer and a storage / display device. A signal processing circuit for processing a detection signal from the semiconductor X-ray detector 6 includes a sample container 9.

Next, the operation of the above configuration will be described. The X-rays 5 emitted from the excitation source 2 such as synchrotron radiation are split by the spectroscope 3 at the incidence / emission angle determined by the slits 4a and 4b, and are applied to the sample 1A.
As a result, the elements of the sample 1A are excited, and the characteristic X-rays 7 emitted by the excited elements are detected by the semiconductor X-ray detector 6. The characteristic X-rays 7 detected by the semiconductor X-ray detector 6 are processed by the signal processing circuit 8 and stored and displayed as a spectrum.

Here, as the semiconductor X-ray detector 6, an energy dispersive detector capable of simultaneously observing the entire X-ray spectrum is used. FIG. 22A shows a signal processing in a wave height analyzer (not shown) included in the signal processing circuit 8.
This will be described with reference to FIGS. In FIG. 22A, reference numeral 6A denotes a number of electrons / electrons corresponding to the energy value of the characteristic X-ray 7 generated when the characteristic X-ray 7 emitted from the sample 1A is incident on the semiconductor X-ray detector 6. Hole pairs, 8
A and 8B are a bias voltage and a current pulse of the signal processing circuit 8, respectively.

That is, when characteristic X-rays 7 are incident on the semiconductor X-ray detector 6, a number of electron-hole pairs 6A in proportion to the energy value of each characteristic X-ray 7 are generated and output as a current pulse 8B. Then, the signal processing circuit 8 converts the current pulse 8B into a voltage pulse proportional to the amount of the current pulse through a built-in amplifier, and then accumulates it in a channel corresponding to each pulse crest value by a built-in crest analyzer. An energy spectrum is obtained.
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, three types of characteristic X-rays 7 having different energy values. FIG. 22 (c) is a diagram showing a result of wave height analysis of the current pulse of FIG. 22 (b), and current pulses P1, P2, and P3 are displayed as pulse numbers corresponding to respective energies.

[0007] Conventionally, with the above-mentioned high integration and miniaturization of electronic devices and semiconductors as described above, the quality of thin films has influenced the performance of electronic devices. For example, silicon Si and oxygen O in a silicon dioxide SiO ₂ film
When the ratio deviates from 1: 2, a substance other than SiO ₂ is mixed into the film, and the dielectric constant changes, so that a desired high-frequency characteristic may not be obtained. Further, when forming a thin film of a compound, it is often difficult to obtain a desired composition due to a difference in a sputtering rate or a difference in an adhesion coefficient. However, in that case, it was difficult to correct a change in composition due to a change in conditions during the formation of the thin film during the formation of the thin film. Thus, attempts have been made to sequentially measure the change in composition during the formation of a thin film.

FIGS. 23A and 23B show, for example, “RHE
Study of Surface by ED Excited X-ray Total Reflection Angle Spectroscopy (TRAXS) Method ”(Ino et al., Applied Physics, Vol. 56, No. 7, 19)
87, p. 843 to 850), which are a configuration diagram showing a conventional thin film forming apparatus to which a semiconductor X-ray detector 6 is added, and an enlarged configuration diagram inside the semiconductor X-ray detector 6. In FIG. 23A, reference numeral 1B denotes gallium arsenide GaAs obtained by 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 denotes an exhaust mechanism for exhausting the inside of the vacuum chamber 10, reference numeral 12 denotes a manufacturing mechanism for forming a thin film on a base material such as a substrate described later, and reference numeral 13 denotes a characteristic X while maintaining a vacuum state inside the vacuum chamber 10.
An X-ray transmission window 14 for transmitting rays is a liquid nitrogen dual for cooling a detection element 6a of the semiconductor X-ray detector 6, which will be described later.

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

Next, the operation of the thin film forming apparatus according to the above configuration will be described. In the manufacturing mechanism 12, for example, gallium Ga or arsenic As is put in an evaporating crucible (not shown) and heated in a vacuum, thereby depositing the gallium Ga or arsenic As 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 formed in this manner, the characteristic X-rays of gallium Ga and arsenic As forming the thin film are excited by the excitation source 2 and are once taken out to the atmosphere through the X-ray transmission window 13. The change in the composition during the formation of the thin film is sequentially measured by detecting with the detector 6 through the X-ray transmission window 6c on the front surface of the semiconductor X-ray detector 6.

[0011]

Since the conventional X-ray detector shown in FIG. 21 described above is constructed as described above, the intensity of characteristic X-rays from an impurity element of a heavy metal such as iron Fe or copper Cu is reduced. The ratio of the intensity of characteristic X-rays from a matrix such as a 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
In the case of, the intensity of characteristic X-rays from the substrate is very strong, and therefore, as shown in FIG. 24, the current pulse P3 has a shorter time interval so as to form a row, 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 perform a peak analysis of a current pulse, the amount of current must be time-integrated and a time for converting the pulse is required. Therefore, when the pulse train is dense, it becomes difficult to count all the pulses. Therefore, there is a problem that it is difficult to measure characteristic X-rays from weak impurity elements with high sensitivity.

The conventional thin film forming apparatus having the function of measuring X-rays shown in FIG. 23 has the following problems because it is configured as described above. 1) Conventionally, beryllium Be is used for the X-ray transmission windows 6c and 13.
When a foil is used and the thickness is such that a normal vacuum state is maintained, soft X-rays with an X-ray energy of 1 keV or less are absorbed, so the characteristic X-rays of substances containing light elements such as oxides and carbides Was difficult to measure. 2) Even if an organic substance (for example, parylene) that transmits soft X-rays is used as the X-ray transmission windows 6c and 13, the X-rays are radiated from a substrate or the like during thin film formation.
The radiation transmitting windows 6c and 13 may be softened or melted. 3) Even if the light element is devised so that it can be measured, especially in the case of a light element such as oxygen, nitrogen or carbon, as the atomic number becomes smaller, the generation efficiency of the characteristic X-ray becomes extremely low. In a compound containing a light element,
Even if the composition ratio is 1: 1, when measuring the pulse of the photon of the characteristic X-ray, the counting rate of the pulse measurement becomes very small. Needed. 4) Therefore, when measuring the substance containing the light element,
It takes a long time to measure, it is difficult to follow the thin film forming speed, and it is difficult to measure the composition of the sample one by one during the thin film forming process.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems of the prior art, and an electromagnetic wave detecting device capable of detecting a weak electromagnetic wave when measuring a plurality of electromagnetic waves having a large intensity ratio. The purpose is to get.

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

[0015]

According to a first aspect of the present invention, there is provided an electromagnetic wave detecting apparatus having a detector for detecting electromagnetic waves of a plurality of wavelengths generated by elements in a sample. At least one of a plurality of electromagnetic waves having a plurality of wavelengths generated from the sample and installed between the detector and the detector;
An optical element that selectively reflects or transmits one or more wavelengths, between the sample and the detector, and from the sample.
The intensity of the electromagnetic wave that directly enters the detector among the generated electromagnetic waves
Only the intensity of the electromagnetic wave entering the optical element is adjusted
An intensity adjustment mechanism installed at a position not to adjust the intensity of the electromagnetic wave, wherein the detector detects the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjustment mechanism. It is a feature.

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

Further, the electromagnetic wave detecting device according to claim 3 is:
The detector is an energy dispersive detector.

Further, the electromagnetic wave detection device according to claim 4 is
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 is provided.

Further, the electromagnetic wave detecting device according to claim 5 is
The intensity adjusting mechanism changes the aperture ratio to change the power.
The slit is a slit for adjusting the intensity of the magnetic wave .

The electromagnetic wave detecting device according to claim 6 is
The optical element is an optical element utilizing a total reflection phenomenon.

Further, the electromagnetic wave detecting device according to claim 7 is
The optical element is an optical element utilizing a diffraction phenomenon.

Further, a substrate processing apparatus according to claim 8 is a processing mechanism for processing a substrate, an excitation source for exciting a plurality of elements contained in the substrate being processed, and an element excited by the excitation source. A detector that detects electromagnetic waves of a plurality of wavelengths to be emitted, and is provided between the substrate under processing and the detector to selectively reflect or reflect at least one wavelength of the electromagnetic waves of the plurality of wavelengths. Generated between the transmitting optics, the substrate being processed and the detector , and from the substrate
Only the intensity of the electromagnetic wave that enters the detector directly
And the intensity of electromagnetic waves entering the optical element should not be adjusted.
And an intensity adjusting mechanism for adjusting the intensity of the electromagnetic wave installed at a position where the electromagnetic wave reflected or transmitted by the optical element and the intensity are adjusted by the intensity adjusting mechanism during the processing of the substrate by the processing mechanism. An electromagnetic wave is detected by the detector.

According to a ninth aspect of the present invention, there is provided a substrate processing apparatus comprising: 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; A detector that detects an electromagnetic wave emitted by the element excited by the source, an optical element that is installed between the target material and the detector, and transmits or reflects the electromagnetic wave, and the target material and the detector. Between the target material and
Adjusts only the intensity of electromagnetic waves that directly enter the above detector among magnetic waves
An intensity adjusting mechanism is provided at a position where the intensity of the electromagnetic wave entering the optical element is not adjusted and adjusts the intensity of the electromagnetic wave.

[0024]

Further, the substrate processing apparatus according to claim 10 is
According to claim 8 or 9 , the wavelength of the electromagnetic wave is in an X-ray region.

The substrate processing apparatus according to claim 11 is
In any one of claims 8 to 10, the detector is an energy dispersive detector.

Further, the substrate processing apparatus according to claim 12 is
In any of claims 8 to 11, which is characterized in that it comprises a shield having heat resistance which transmits X-rays, including the following soft X-ray 1keV with shielding the light and heat entering the detector It is.

Further, the substrate processing apparatus according to claim 13 is
In any one of claims 8 to 12 , wherein the intensity adjusting mechanism changes the aperture ratio to reduce the intensity of the electromagnetic wave.
The slit is an adjusting slit.

Further, the substrate processing apparatus according to claim 14 is
In any one of the eighth to thirteenth aspects, the optical element is an optical element utilizing a total reflection phenomenon.

The substrate processing apparatus according to claim 15 is
In any one of the eighth to thirteenth aspects, 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 of the electromagnetic waves of a plurality of wavelengths generated by the elements in the sample. , by the intensity adjustment mechanism, above
By adjusting the intensity of the electromagnetic wave that directly enters the detector and does not enter the optical element, the detector detects the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity is adjusted by the intensity adjustment mechanism. Then, when measuring a plurality of electromagnetic waves having a large intensity ratio, even a weak electromagnetic wave can be detected.

Further, in the electromagnetic wave detecting 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 in the X-ray region, whereby the element of the element is determined based on the energy value of the X-rays. Facilitate type identification.

Further, in the electromagnetic wave detecting device according to the third aspect, the detector is an energy dispersive detector, so that when detecting a plurality of electromagnetic waves having a high intensity ratio, the counting rate is increased by the electromagnetic waves having a high intensity. Makes it possible to detect weak electromagnetic waves at the same time without being limited.

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

Further, in the electromagnetic wave detecting device according to the fifth aspect, the intensity adjusting mechanism may change an aperture ratio.
By using the slit for adjusting the intensity of the electromagnetic wave, the aperture ratio of the slit can be 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, the electromagnetic wave can be reflected and reflected at a predetermined incident / reflection angle, thereby forming a plurality of electromagnetic waves. Among them, 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 can be reflected and reflected at a predetermined incident and reflected angle, so that the electromagnetic wave having low intensity can be obtained. It is possible to selectively extract electromagnetic waves of specific elements regardless of the strength of the electromagnetic waves with high intensity, and unlike the case of using an optical element utilizing the total reflection phenomenon, the energy is higher than that of electromagnetic waves with strong intensity This makes it possible to selectively extract only the electromagnetic waves of elements emitting high-energy electromagnetic waves, even when the strength of the elements emitting high-energy electromagnetic waves is low due to the presence and small amount of elements that emit high-energy electromagnetic waves.

Further, in the substrate processing apparatus according to 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 reflected by the optical element are controlled by the intensity adjusting mechanism .
A plurality of electromagnetic waves having a large intensity ratio are measured during processing of the substrate by detecting , with the detector, the electromagnetic waves that directly enter the detector and the electromagnetic waves that do not enter the optical element and the intensity of which is adjusted. In this case, even a weak electromagnetic wave can be detected, and a change in composition can be measured.

In the substrate processing apparatus according to the ninth aspect, when the thin film is formed on the substrate by using the sputtering phenomenon, the element in the target material to be sputtered is excited by the excitation source to detect the thin film. Detects changes in the composition of the target material by detecting the electromagnetic waves emitted by the elements excited by the detector, and selects at least one or more wavelengths of the electromagnetic waves generated by the elements in the target material using an optical element. And directly enters the detector by the intensity adjustment mechanism.
By adjusting the intensity of the electromagnetic wave that does not enter the optical element, the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity has been adjusted by the intensity adjustment mechanism are detected by a detector, and the element in the target material is detected. When measuring a plurality of electromagnetic waves which generate a large intensity ratio, even a weak electromagnetic wave can be detected.

[0040]

Further, in the substrate processing apparatus according to claim 10, in claim 8 or 9, in the substrate processing, when measuring a plurality of electromagnetic waves having a large intensity ratio, the wavelength of the electromagnetic wave and the X-ray region By doing so, it is easy to identify the type of element of the substrate or the target material to be a sample based on the energy value of the X-ray.

According to a eleventh aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to tenth aspects, the detector is an energy dispersive detector to detect a plurality of electromagnetic waves having a large intensity ratio. In this case, a weak electromagnetic wave can be detected at the same time without the counting rate being limited by the strong electromagnetic wave.

According to a twelfth aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to eleventh aspects, light or heat entering the detector is shielded and X-rays including soft X-rays of 1 keV or less are transmitted. By providing a heat-resistant shield that prevents light and heat from affecting the detector,
Light elements that emit X-rays including soft X-rays below keV can also be detected.

According to a thirteenth aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to twelfth aspects, the strength adjusting mechanism is constituted by a slit, so that the aperture ratio of the slit is changed to achieve a simple strength. Allow adjustment.

According to a fourteenth aspect of the present invention, there is provided a substrate processing apparatus according to any one of the eighth to thirteenth aspects, wherein an optical element utilizing a total reflection phenomenon is used as the optical element, so that the By reflecting the electromagnetic waves emitted from a plurality of elements that emit electromagnetic waves having an energy lower than a predetermined energy among a plurality of electromagnetic waves, the element that emits the reflected electromagnetic waves can be simultaneously reflected. Can be measured simultaneously.

According to a fifteenth aspect of the present invention, in the substrate processing apparatus according to any one of the eighth to thirteenth aspects, by using an optical element utilizing a diffraction phenomenon as the optical element, electromagnetic waves can be emitted at a predetermined incident / reflection angle. Increasing or lowering the energy of the weak electromagnetic wave and the strong electromagnetic wave by causing the sample and detector to enter and reflect, or by placing the sample and the detector at a predetermined focal position and concentrating the electromagnetic waves of the element to be measured emitted from the sample on the detector. It is possible to selectively extract the electromagnetic waves of a specific element regardless of the element, and unlike the case of using an optical element utilizing the total reflection phenomenon, the element that emits electromagnetic waves with higher energy than electromagnetic waves with strong intensity is an impurity It is possible to selectively extract only the electromagnetic waves of the elements that emit high-energy electromagnetic waves, even when the strength is weak due to the presence of a small amount. .

[0047]

【Example】

Embodiment 1 FIG. Hereinafter, a description will be given based on the illustrated embodiment. FIG.
21 is a configuration diagram showing a main part of an X-ray detection device as an electromagnetic wave detection device according to the first embodiment, and shows a configuration inside a sample container 9 in the conventional example shown in FIG. In FIG. 1, 1C is a compound sample containing a light element such as oxygen, for example, a magnesium oxide substrate, and 5, 6, 8, and 9 are the same as those of a conventional X-ray detector. X-rays and 6 are semiconductor X-ray detectors for detecting characteristic X-rays generated by elements in the sample 1C excited by the X-rays 5, and are energy dispersive detectors capable of simultaneously observing the entire X-ray spectrum. Consists of 7a and 7b are characteristic X-rays, 8 is a signal processing circuit including a pulse height analyzer and a storage / display device for processing a detection signal from the semiconductor X-ray detector 6, and 9 is a sample container.

Reference numeral 31 denotes a total reflection mirror as an optical element utilizing a total reflection phenomenon; 32, a slit as an intensity adjusting mechanism; 33, which shields light and heat and transmits X-rays including soft X-rays of 1 keV or less. It is a heat-resistant shield that does. In addition,
Although not shown in the X-ray detection apparatus according to the first embodiment,
As in the conventional example shown in FIG. 21, an excitation source 2 such as a synchrotron radiation for exciting the elements of the sample 1C, an excitation source 2
A spectroscope 3 for separating the X-rays 5 from the light source, and slits 4a and 4b for determining the incident and exit angles of the spectroscope 3.

Here, the total reflection mirror 31 corresponds to 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 of SiO ₂ as a mirror material. When electromagnetic waves are incident from a medium having a large refractive index to a medium having a small refractive index, when the incident angle (here, the angle from the mirror surface: the glancing angle) is smaller than a certain angle, total reflection is performed. This is an optical element that utilizes the total reflection phenomenon that causes the reflectance to suddenly increase. In the X-ray region, the refractive index in vacuum is larger than the refractive index of the material of the mirror. When entering, 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 and the incoming reflection is performed, the characteristic X-ray of carbon has a large reflectance, but the reflectance of characteristic X-ray of oxygen is small, and only the characteristic X-ray of carbon can be selectively extracted. Will be possible. Accordingly, when the incident / reflection angle is set as described above, not only the characteristic X-rays of carbon but also the reflectivity of characteristic X-rays having an energy lower than that of the characteristic X-rays of carbon are high, and not only carbon but also carbon. Elements that emit characteristic X-rays with lower energy than characteristic X-rays can be measured at the same time.

A slit 32 serving as a strength adjusting mechanism is provided.
Is provided with plates 32a and 32b each having the same opening, as shown in FIG. 3, for example.
By changing the aperture ratio by shifting 2a and 32b, the intensity of characteristic X-ray 7a is adjusted.

Further, as shown in FIG. 4, for example, as shown in FIG. 4, for example, as shown in FIG. 4, a support film 33b is formed on a silicon Si substrate 33c with good adhesion by a CVD method or the like. The 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 transmit soft X-rays well and to have high structural strength, and is also required to have heat resistance since it receives radiant heat. Further, a material having good thermal conductivity is required to release heat to the metal thin film 33a, and as a material, an X-ray having an X-ray energy of 1 keV or less is transmitted. In consideration of,
The metal thin film 33a is made of aluminum Al or beryllium B
e is suitable, and silicon nitride, carbon, silicon carbide, or the like may be used for the support film 33b in addition to boron nitride BN.

Next, the operation according to the above configuration will be described. X-rays 5 emitted from an excitation source 2 (not shown), such as synchrotron radiation light, are incident on and emitted from the spectroscope 3 (not shown) at angles of incidence determined by the slits 4a and 4b (not shown).
To irradiate the sample 1C. This allows
The elements of the sample 1C are excited, and the characteristic X-rays 7a emitted by the excited elements pass through the slit 32, which is an intensity adjusting mechanism, and are detected by the semiconductor X-ray detector 6. Similarly,
The characteristic X-rays 7 b emitted by the excited element are 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
a and 7b are processed by the signal processing circuit 8 and stored and displayed as a spectrum.

Here, for example, magnesium oxide MgO
When measuring the 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), the total reflection mirror 31 has a high energy X at a certain incidence / emission angle.
Since the reflectivity of the X-rays is lower for the X-rays, the X-rays are incident and emitted at the incident / exit angle at the total reflection mirror 31 so that, for example, of the X-rays having two energy values, only the X-rays of almost low energy are emitted. Can be reflected. That is, by setting the incident angle to be equal to or smaller than the critical angle of the X-ray of the weak element of the sample 1C to be analyzed and equal to or larger than the critical angle of the X-ray of the strong element, the characteristic of low energy is obtained. X-ray emitting elements can be measured efficiently.

Almost one pair like magnesium oxide MgO
When measuring the sample 1C containing magnesium Mg and oxygen O at a ratio of 1 , the generation efficiencies of characteristic X-rays of magnesium Mg and characteristic X-rays of oxygen O are significantly different. In general, an element that emits high-energy characteristic X-rays, for example, a heavy metal has higher generation efficiency of characteristic X-rays, so that the characteristic ratio of the characteristic X-rays of magnesium Mg and the characteristic X-rays of oxygen O is large.

Therefore, characteristic X-rays from light elements having a low generation efficiency can be selectively reflected, and characteristic X-rays from heavy metals having high intensity can be prevented from being reflected. Inside, strong magnesium Mg
Can be attenuated by the total reflection mirror 31, and most of the characteristic X-rays 7b reflected by the total reflection mirror 31 are low energy characteristic X-rays emitted from oxygen O. Then, by making the intensity of the characteristic X-ray 7b of oxygen O after being reflected by the total reflection mirror 31 substantially equal to the intensity of the characteristic X-ray 7a from magnesium Mg whose intensity is adjusted using the slit 32, The same semiconductor X-ray detector 6 can detect at the same time.

That is, it is possible to change the aperture ratio by shifting the plates 32a and 32b having 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 a plurality of openings, the characteristic X
The intensity of the line 7a is made substantially equal to the intensity of the characteristic X-ray 7b of oxygen O after being reflected by the total reflection mirror 31, detected by the same semiconductor X-ray detector 6, and both elements are efficiently measured simultaneously. To be able to.

In addition, X was added to the substrate of magnesium oxide MgO.
When light or an electron beam is irradiated, light in the visible region may be emitted. The semiconductor X-ray detector 6 has sensitivity to this visible light. Therefore, the visible light is blocked by the shield 33 and only the X-ray is 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 the first embodiment, as described above, not only characteristic X-rays from oxygen O but also magnesium M
Since characteristic X-rays from g can also be measured at the same time, fluctuations in incident X-rays can be normalized using characteristic X-rays from magnesium Mg. In addition, by configuring the total reflection mirror 31 with a curved mirror or a plurality of mirrors, it is possible to provide a light condensing function and increase the sensitivity to light elements. Further, the shape of the plate having the opening that forms the slit 32 that is the strength adjusting mechanism is not limited to the first embodiment.

In the first embodiment, the total reflection mirror 31 does not selectively extract X-rays having a specific energy as in the case of an optical element using diffraction. Since all X-rays having an energy of less than or equal to are selectively extracted, when measuring the magnesium oxide MgO, characteristic X-rays having an energy lower than that of oxygen O can also be measured. 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 an optical element, and the characteristic X-rays from a light element having a low intensity and the characteristics X from a heavy metal having a high intensity are selectively reflected. The intensity of the line is adjusted by the slit 32, which is an intensity adjusting mechanism, so that an appropriate intensity ratio can be set. Of the characteristic X-rays emitted from the element excited from the sample 1C, 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, by the slit 32, the same semiconductor X-ray detector 6 can efficiently perform the same operation. Both elements can be detected almost equally and simultaneously. In addition, by blocking visible light with the shield 33 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.

Embodiment 2 FIG. Next, FIG.
FIG. 3 is a configuration diagram illustrating a main part of the line detection device. 5, the same parts as those in the first embodiment shown in FIG. 1 are denoted 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 an i-substrate, a multilayer mirror 34 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, 35b are multilayer mirrors 3
4 is a slit for defining the angle of incidence and emission to the light source 4. Others
This is similar to the first embodiment.

As shown in FIG. 6, the multilayer mirror 34, which is an optical element utilizing the diffraction phenomenon, is composed of, for example, molybdenum Mo as a heavy metal having a different refractive index on a silicon Si substrate 34a in the X-ray region. A thin film 34b and a silicon Si thin film 34c serving as a light metal are alternately stacked in several hundred layers. As described above, two different refractive indexes are used.
When the layer films are stacked over a certain period, a high reflectance is obtained where the black condition is satisfied by the light diffraction phenomenon. For example, when characteristic X-rays are reflected 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 reflectivity. The reflectivity of characteristic X-rays of the other elements becomes lower and can be attenuated.

Therefore, it is possible to selectively extract characteristic X-rays of a specific element irrespective of the level of energy of characteristic X-rays having low intensity and characteristic X-rays having 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 when the intensity is low because the element which emits the characteristic X-ray having higher energy than the characteristic X-ray having high intensity exists as an impurity and has a small amount, the characteristic X-ray having high energy can be obtained. Only the characteristic X-rays of the element to be emitted can be selectively extracted.

The X-ray detector configured as described above operates in the same manner as in the first embodiment. That is, X from the excitation source 2 (not shown) such as synchrotron radiation
The line 5 is irradiated on the sample 1D. As a result, the elements of the sample 1D 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 are detected by the semiconductor X-ray detector 6. Similarly, characteristic X-rays (fluorescent X-rays) 7 emitted by the excited elements
b is reflected by the multilayer mirror 34 at the incidence / 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 and displayed as a spectrum.

Here, when measuring the boron B doped 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 and reflecting the characteristic X-rays at an angle, of the characteristic X-rays emitted from the sample 1D, the characteristic X-rays from the strong silicon Si 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 boron B characteristic X-rays. And the multilayer mirror 3
4, the intensity of the characteristic X-ray 7b of boron B after being reflected by
By adjusting the intensity of the characteristic X-rays 7a from silicon Si to be substantially equal by adjusting the intensity using the slit 32, the same semiconductor X-ray detector 6 can efficiently measure both elements simultaneously.

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. Normalization can be performed 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 impurity element having a low intensity. By adjusting the intensity of the characteristic X-ray from the heavy metal with the slit 32 which is an intensity adjusting mechanism,
An appropriate intensity ratio can be set, and among the characteristic X-rays emitted from the element excited from the sample 1D, the characteristic X-rays 7 having high intensity are formed by the slit 32 as an intensity adjusting mechanism.
By setting the intensity of a to be equal to the intensity of the characteristic X-ray 7b of low intensity reflected by the multilayer mirror 34, the same semiconductor X-ray detector 6 can efficiently detect both elements simultaneously. it can.

Embodiment 3 FIG. Next, FIG. 7 shows X according to the third embodiment.
FIG. 3 is a configuration diagram illustrating a main part of the line detection device. 7, the same parts as those in the first embodiment shown in FIG. 1 are denoted by the same reference numerals, and description thereof will be omitted. As a new reference numeral, 1E is a sample in which a phosphor of zinc oxide ZnO contains an impurity of carbon C, 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 obtained diffraction phenomenon, and 6f is a semiconductor X-ray detector 6
Is an opening / closing mechanism provided on the front surface of the camera. Others are the same as the first embodiment.

Here, the transmission type diffraction grating 36 shown in FIG.
As shown in FIG. 5, a ring formed by concentric circles whose radius Rm is proportional to the square root of an integer m is formed as an opaque portion 36a, and a transparent ring portion 36b is formed. Are collected in the same phase, and light of a specific wavelength is focused on the focal plane. In the X-ray region, gold or the like is used for the opaque portion 36a.

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 / negative focal position f = Rm ² / mλ at the wavelength λ of the ray, and the characteristic X-rays of the element to be measured emitted from the sample 1E are transmitted to the semiconductor X-ray detector 6. By condensing the light, the intensity of the characteristic X-ray emitted from the element to be measured becomes relatively higher than the characteristic X-ray of the other element, and the characteristic X-ray of a specific element is emitted. It becomes possible to take out selectively.

Accordingly, it is possible to selectively extract characteristic X-rays of a specific element regardless of the level of energy of the characteristic X-rays having a low intensity and the characteristic X-rays having a 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 when the intensity is low because the element which emits the characteristic X-ray having higher energy than the characteristic X-ray having high intensity exists as an impurity and has a small amount, the characteristic X-ray having high energy can be obtained. Only the characteristic X-rays of the element to be emitted can be selectively extracted.

In the X-ray detecting apparatus configured as described above, the inside of the sample container 9 is evacuated by an exhaust mechanism (not shown). In a vacuum state, the opening and closing mechanism 6
f is opened, and the front surface of the semiconductor X-ray detector 6 is opened. Then, similarly to the first embodiment, the sample 1E is irradiated with the X-rays 5 from the 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 from the excited elements pass through the slit 32, which is an intensity adjusting mechanism, pass through the shield 33, and pass through the semiconductor X-ray detector 6a. Is detected by Similarly, the characteristic X-rays (fluorescent X-rays) 7 b emitted by the excited element are 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 and displayed as a spectrum.

In the third embodiment, for example, the case of measuring the concentration of impurities contained in a fluorescent substance is taken. When the sample 1E is irradiated with an X-ray or an electron beam, zinc oxide ZnO as a fluorescent substance becomes , Characteristic X-ray (fluorescent X
Line), and at the same time emits strong visible light.
The line detector 6 has sensitivity also to this visible light. Therefore, in the same manner as in the first embodiment, the visible light is blocked by the shield 33 and only the X-rays are detected by the semiconductor X-ray detector 6, and the influence of the visible light on the semiconductor X-ray detector 6 is reduced. So that it can be prevented.

The transmission type diffraction grating 36 such as the Fresnel zone plate described above has a positive / negative focal point position f = Rm at the wavelength λ of the characteristic X-ray emitted by the element to be measured.
^The sample 1E and the semiconductor X-ray detector 6 are placed at ² / mλ, and the characteristic X-rays of the element to be measured emitted from the sample 1E are focused on the semiconductor X-ray detector 6, so that the X-rays of a specific energy are obtained. Can be diffracted, and among the characteristic X-rays (fluorescent X-rays) emitted from the sample 1E, the characteristic X-rays of carbon C (fluorescent X-rays)
) Is diffracted by the transmission diffraction grating 36, and characteristic X-rays (fluorescent X
By setting the slit 32 as the intensity adjusting mechanism so that the intensity of the line (2) and the intensity of zinc Zn passing through the slit 32 as the intensity adjusting mechanism are substantially equal, the impurity element can be efficiently measured simultaneously. .

In the third embodiment, as described above, not only characteristic X-rays (fluorescent X-rays) of carbon but also zinc Zn
And characteristic oxygen X-rays (fluorescent X-rays) can also be measured at the same time, making it possible to normalize the fluctuations in the incident X-rays using the intensity of zinc Zn and the characteristic X-rays (fluorescent X-rays) of oxygen O. Become.

Therefore, according to the third embodiment, the transmission type diffraction grating 36 is used as an optical element utilizing the diffraction phenomenon.
Diffraction of characteristic X-rays (fluorescent X-rays) of carbon C
By setting the slit 32 as the intensity adjusting mechanism so that the intensity of the characteristic X-ray (fluorescent X-ray) and the intensity of zinc Zn passing through the slit 32 as the intensity adjusting mechanism are substantially equal, the impurity element can be efficiently formed. Can be detected by the same semiconductor X-ray detector 6. In addition, by the shield 33,
By blocking visible light and detecting only 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.

Embodiment 4 FIG. Next, FIG. 9 is a configuration diagram illustrating an element analyzer according to the fourth embodiment. In FIG. 9, 1F is a sample in a plasma state that emits light that is an electromagnetic wave specific to each element in a discharge tube described later, 32 is a slit as an intensity adjustment mechanism similar to that of the first embodiment shown in FIG.
Is a discharge tube, 38a and 38b are introduction / derivation ports for introducing / deriving a sample to be analyzed into / from the discharge tube 37, 39 is a power supply for bringing the introduced sample into a plasma state, 40a / 40b / 4
0c is light emitted from the sample 1F in a plasma state, 41
Reference numerals a, 41b, 42a, and 42b denote slits, and reference numerals 43 and 44 denote diffraction gratings as optical elements using a diffraction phenomenon.
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 detectors 6 of the first to third embodiments. This is a detector using.

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

Further, as shown in FIG. 11, the detector 60 using the tunnel junction in the superconductor is made of tin Sn.
Tin oxide Sn between the thin film superconductors 60a and 60c
The tunnel junction has a structure in which an insulator 60b made of an O thin film is interposed, and the energy gap of the superconductor is about meV, which is three times larger than the energy gap of the semiconductor.
Nearly small. For this reason, in the semiconductor X-ray detector 6 used in the first to third embodiments, since the semiconductor has an energy gap of several eV, the energy can be resolved for electromagnetic waves in the X-ray region. Although energy cannot be resolved for electromagnetic waves having low energy, the detector 60 using a tunnel junction in a superconductor does not.
In the case of (1), the energy of the electromagnetic wave having smaller energy than the electromagnetic wave in the X-ray region can be decomposed, and the energy can be decomposed even in a region from ultraviolet to visible light.

As shown in FIG. 11, when light enters the detector 60 using a tunnel junction of such a superconductor, a number of electron-hole pairs proportional to the energy of each light is generated. Are output as current pulses. This current pulse is input to the signal processing circuit 8 and converted into a voltage pulse proportional to the amount of the current pulse through a built-in amplifier in the same manner as in the conventional example and the first to third embodiments. The energy spectrum is accumulated in a channel corresponding to each pulse peak value to obtain an energy spectrum.

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

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

In the fourth embodiment, as described above, not only light emitted from a trace amount of impurities, but also
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 using the light emitted from the strong substance.

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

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

The organic crystal 45 has a periodic structure in which the lattice planes of the crystal atoms are separated by a distance d as shown in, for example, a schematic sectional view of FIG. A strong reflectance is obtained where the conditions are satisfied. Therefore, the characteristic X emitted by the element to be measured is
Characteristic X at an angle that satisfies the black condition at the line wavelength
When a line is reflected and reflected, the characteristic X emitted by the element to be measured
The line has a high reflectance, and the reflectance of characteristic X-rays of other elements is low and can be attenuated.

For this reason, it is possible to selectively extract characteristic X-rays of a specific element regardless of the energy level of the characteristic X-rays having a low intensity and the characteristic X-rays having a high intensity.
That is, unlike the case of using the total reflection mirror 31 utilizing the total reflection phenomenon of the first embodiment, the element which emits the characteristic X-ray having higher energy than the characteristic X-ray having higher intensity exists as an impurity and the amount is small. Therefore, even when the strength is weak,
It is possible to selectively extract only characteristic X-rays of an element emitting high-energy characteristic X-rays.

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

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

In Example 5, as described above, not only characteristic X-rays of fluorine F, which is an impurity element having low intensity, but also characteristic X-rays from silicon Si having high intensity can be simultaneously measured. The fluctuation of the incident X-ray can be normalized using the characteristic X-ray from silicon Si.

Therefore, according to the fifth embodiment, the organic material 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 from the element to be measured is satisfied. By reflecting the characteristic X-rays at an angle, the element to be measured can be selectively reflected, and the characteristic X-rays from the selectively reflected low-impurity impurity elements can be selectively reflected from the heavy metal having a high intensity. By adjusting the intensity of the characteristic X-rays in the slit 32 as an intensity adjusting mechanism, an appropriate intensity ratio can be set, and among the light emitted by the excited elements from the sample 1G,
The slit 32 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, thereby providing the same semiconductor X-ray. The detector 6 can efficiently detect both elements.

Embodiment 6 FIG. Next, FIG. 14 is a configuration diagram illustrating a thin film forming apparatus according to a sixth embodiment. 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 elements of the formula, 6 is a semiconductor X-ray detector,
10 is a vacuum chamber of the thin film forming apparatus, 11 is an exhaust mechanism for exhausting the vacuum chamber 10, 12 is a manufacturing mechanism for forming a thin film on the sample 1H, and 14 is a detecting element of the semiconductor X-ray detector 6. Liquid nitrogen dual for cooling. Also, 3
Reference numerals 1 and 32 denote a total reflection mirror made of, for example, soda-lime glass as an optical element similar to that of the first embodiment shown in FIG. 1 and a slit as an intensity adjusting mechanism, and reference numerals 7a and 7b denote characteristic X-rays.

The semiconductor X-ray detector 6 used here detects characteristic X-rays excited by the excitation source 2 from the sample 1H as shown in FIG. Element 6a, a vacuum vessel 6b for keeping the 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 element 6a, and the amplifier 6d. It has a rod 6e for guiding the amplified detection signal out of the vacuum and drawing heat to the outside to cool the detection element 6a, and newly opens and closes a part of the vacuum vessel 6b on the front 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 a vacuum with the opening and closing mechanism 6f closed, and the evacuation mechanism 11 evacuates the vacuum chamber 10. Then, in a state where a vacuum is created, the opening / closing mechanism 6
f is opened, and the front surface of the semiconductor X-ray detector 6 is opened. In this state, the sample 1H is irradiated with an electron beam emitted from the excitation source 2. As a result, the elements of the sample 1H are excited, and the characteristic X-rays 7a emitted by the excited elements pass through the slit 32, which is an intensity adjusting mechanism, and are detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-rays 7 b emitted by the excited element are reflected by the total reflection mirror 31 and thereafter 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 and displayed as a spectrum.

When the vacuum chamber 10 is exposed to the atmosphere for maintenance or the like, the opening and closing mechanism 6f is closed to maintain the vacuum of the semiconductor X-ray detector 6, thereby protecting the semiconductor X-ray detector 6.
This is a necessary procedure 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, a similar effect can be obtained even if a detector without the opening / closing mechanism 6f is used.

When a very small amount of light element impurities such as a natural oxide film on a silicon Si substrate or carbon is measured in the thin film forming apparatus having the above structure, the intensity of the characteristic X-rays emitted from the sample 1H is measured. Characteristic X-rays from silicon Si having high intensity can be attenuated by the total reflection mirror 31 and the total reflection mirror 3
Most of the characteristic X-rays reflected at 1 are low-energy characteristic X-rays such as oxygen and carbon. And the total reflection mirror 31
X-ray intensity such as oxygen and carbon after being reflected by
By making the characteristic X-ray intensity from i almost equal using the slit 32, it becomes possible to measure both elements efficiently.

In the sixth embodiment, as described above, not only characteristic X-rays such as oxygen and carbon but also characteristic X-rays from silicon Si can be measured at the same time. It is possible to normalize using the characteristic X-ray.

Therefore, according to the sixth embodiment, during the formation of the thin film, the sample 1H is irradiated with the electron beam from the excitation source 2 to emit the characteristic X-rays from the excited elements of the sample 1H. The characteristic X-rays 7b reflected by 31 and the characteristic X-rays 7a of which the intensity is adjusted by the slit 32 are the same semiconductor X
Since it is detected by the line detector 6, when measuring characteristic X-rays of a plurality of elements having a large intensity ratio, it is possible to detect even weak characteristic X-rays, and the composition change is measured one by one during thin film formation. can do.

Embodiment 7 FIG. Next, FIG. 15 is a configuration diagram illustrating a thin film forming apparatus according to a seventh embodiment. 15, the same parts as those of the fifth embodiment shown in FIG. 6 are denoted by the same reference numerals, and the description thereof will be omitted. Reference numeral 33 denotes a shield similar to that of the first embodiment shown in FIG. 1, and reference numerals 34, 35a, and 35b denote a multilayer mirror similar to that of the second embodiment shown in FIG. 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, 47 is a bulb.

In the thin film forming apparatus configured as described above, first, the semiconductor X-ray detector 6 is maintained in a vacuum with the opening / closing mechanism 6f for opening and closing a part of the vacuum vessel 6b in front of the detector being closed. The vacuum chamber 10 is evacuated by the evacuation 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 the formation of a thin film by the manufacturing mechanism 12, the steam or gas affects the detector, and the valve 47 is closed to prevent the influence.

In this state, the sample 1I is irradiated with the electron beam emitted from the excitation source 2. As a result, the elements of the sample 1I are excited, and the characteristic X-rays 7a emitted from the excited elements pass through the shield 33, further pass through the slit 32, which is an intensity adjusting mechanism, and the semiconductor X-ray detector 6 Is detected. Similarly, the characteristic X-rays 7b emitted from the excited element pass through the shield 33 and are reflected by the multilayer mirror 34 at the incidence / emission angle defined by the slits 35a and 35b. Is detected by the 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 and 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 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.

For example, when a silicon dioxide SiO ₂ thin film is formed by a thin film forming apparatus, the element to be measured is reflected and reflected by the multilayer mirror 34 at a predetermined incident and reflection angle at the wavelength of the characteristic X-ray emitted by the element to be measured. Of the characteristic X-rays emitted from the sample 1I, the characteristic X-rays from the strong silicon Si can be attenuated by the multilayer mirror 34, and the characteristic X-rays of low energy oxygen O can be reflected. Most of the characteristic X-rays 7b reflected by the multilayer mirror 34 are low-energy oxygen O characteristic X-rays. Then, the intensity of the characteristic X-ray 7b of oxygen O after being reflected by the multilayer mirror 34 and the intensity 7a of the characteristic X-ray from silicon Si are made substantially equal using the slit 32, so that the characteristic X from silicon Si is obtained. The line does 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. Since it is not deformed or melted by radiant heat due to substrate heating during the formation of the thin film, the characteristic X-ray can be measured one by one during the thin film formation process. As described above, even when a thin film containing a light element having a low efficiency of generating characteristic X-rays such as oxygen O is formed, the measurement of the composition of the sample 1I can follow the thin film forming speed and the thin film forming process can be performed. Since the influence of light or heat generated therein on the semiconductor X-ray detector 6 can be prevented, the composition of the sample can be measured one by one during the formation process.

Therefore, according to the seventh embodiment, the characteristic X-ray is emitted from the excited element of the sample 1I by irradiating the sample 1I with the electron beam from the excitation source 2 during the formation of the thin film. The characteristic X-rays 7b reflected by 34 and the characteristic X-rays 7a of which the intensity is adjusted by the slits 32 are the same semiconductor X
Since it is detected by the line detector 6, when measuring characteristic X-rays of a plurality of elements having a large intensity ratio, it is possible to detect even weak characteristic X-rays, and the composition change is measured one by one during thin film formation. At this time, by shielding 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. Also, when forming a thin film containing a light element having low characteristic X-ray generation efficiency, the measurement of the composition of the sample can be made to follow the thin film forming speed.

Embodiment 8 FIG. Next, FIG. 16 is a configuration diagram illustrating a thin film forming apparatus according to an eighth embodiment. In FIG. 16, the same parts as those in the sixth and seventh embodiments shown in FIGS. 14 and 15 are denoted by the same reference numerals, and the description thereof will be omitted. Also, 45 and 46a
Numerals 46b denote an organic crystal similar to that of the fifth embodiment shown in FIG. 12 and solar slits for defining the angle of incidence and exit to the organic crystal. Further, 1J denotes a titanium nitride TiN thin film by this thin film forming apparatus. Sample on which is formed, 4
Reference numeral 8 denotes a gate valve, 49 denotes an exhaust mechanism, 50 denotes a vacuum box, and when baking out of the vacuum chamber 10, shows a case in which a part that cannot be burned out can be detached by the gate valve 48. An evacuation mechanism 49 independent of the evacuation mechanism 11 of the vacuum chamber 10 has a vacuum box 50 at
Is evacuated, and then the gate valve 48 is opened.

In the thin film forming apparatus configured as described above, the sample 1J is irradiated with an electron beam emitted from the excitation source 2. 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 an intensity adjusting mechanism, further pass through the shield 33, and are emitted from the semiconductor X-ray detector 6. Is detected. Similarly, the characteristic X-rays 7b emitted by the excited element are reflected by the solar slit 46.
After being reflected by the organic crystal 45 at the incidence / emission angle defined by a and 46b, the light passes through the shield 33 and passes through the semiconductor X-ray detector 6
Is detected by These characteristic X-rays detected by the semiconductor X-ray detector 6 are processed by a signal processing circuit (not shown), and stored and displayed as a spectrum.

For example, in a thin film forming apparatus, titanium nitride TiN
When a thin film is formed, of the characteristic X-rays emitted from the sample 1J, the characteristic X-rays emitted from the element to be measured by the organic crystal 45 are reflected at a high reflectance, and the characteristic X-rays of the other elements are reflected. By setting the angle of incidence and reflection to the organic crystal in order to lower the reflectance and attenuate the characteristic X-rays of the K-rays from the strong titanium Ti, the organic crystal 45 attenuates the characteristic X-rays and reduces the nitrogen N. Energy characteristic X
The characteristic X-rays 7b reflected by the organic crystal 45 can reflect most of the characteristic X-rays with low energy 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 slits 32, so that titanium Ti The counting rate is not limited by the characteristic X-rays, the characteristic X-rays of weak elements can be detected at the same time, and both elements can be measured.

At this time, by shielding light and heat generated from the manufacturing mechanism 12 for forming a thin film by the shield 33, the influence on the semiconductor X-ray detector 6 can be prevented. Since the shield 33 has heat resistance, it is not deformed or melted by radiant heat due to substrate heating or the like during the formation of the thin film. It can be measured one by one. Further, since the light is reflected by the organic crystal 45 at the incident and exit 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 eighth embodiment, 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-ray from titanium Ti are determined by the slit 3.
2, the two elements are detected by the same semiconductor X-ray detector 6 without the count rate being limited by the characteristic X-rays from titanium Ti. When measuring characteristic X-rays of elements, it is possible to detect even weak characteristic X-rays, and it is possible to measure changes in composition one by one during thin film formation.
By shielding light and heat generated from the manufacturing mechanism 12, 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. In addition, the measurement of the composition of the sample can follow the film formation speed. Also, the solar slits 46a, 46
Since the light is reflected by the organic crystal 45 at the incident / emission angle defined by b, the K line of nitrogen N and the L line of titanium Ti can be separated.

Embodiment 9 FIG. Next, FIG. 17 is a configuration diagram showing a thin film forming apparatus for forming a thin film using a sputtering phenomenon according to the ninth embodiment. In FIG. 17, the same portions as those in the above-described embodiments are denoted by the same reference numerals, and description thereof will be omitted. Further, as a new code, 1K is a sample on which a titanium nitride TiN thin film is formed on a 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, 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 configured 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. By sputtering argon ions in the plasma on the target material 53, a thin film is formed on the substrate of the sample 1K. During sputtering, the gate valves 54 and 55 are closed, and after the thin film is formed, the gate valves 54 and 55 are opened and the target 53 is irradiated with an electron beam emitted from the excitation source 2. Thereby, the target material 5
The element X3 is excited and the characteristic X emitted by the excited element is
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-rays 7b emitted from the excited element are reflected and collected by the plurality of inorganic crystals 56, and then detected by the semiconductor X-ray detector 6. These characteristics X detected by the semiconductor X-ray detector 6
The lines are processed by a signal processing circuit (not shown) and stored and displayed as a spectrum.

For example, in this thin film forming apparatus, titanium nitride T
When an iN thin film is formed, impurities of carbon C and oxygen O of the target material 53 change the sputtering rate or enter the thin film as impurities. Therefore, it is necessary to examine the target material 53 for impurity contamination from time to time. Of the characteristic X-rays emitted from the target material 53, the characteristic X-rays are incident and reflected on the plurality of inorganic crystals 56 at an angle that satisfies the black condition at the wavelength of the characteristic X-ray emitted by the element to be measured. The characteristic X-rays of oxygen C and carbon O are respectively reflected by the plurality of inorganic crystals 56, and the K-rays and the characteristic X-rays of nitrogen N from titanium Ti having high intensity can be attenuated. The characteristic X-ray intensity of carbon C and oxygen O after being reflected by the plurality of inorganic crystals 56 and the K
By making the characteristic X-ray intensities of the lines substantially equal using the slit 32, it becomes possible to efficiently measure impurity elements simultaneously.

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 that 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 with the plurality of inorganic crystals 56, it becomes possible to increase the sensitivity to impurity elements.

Therefore, according to the ninth embodiment, when a thin film is formed by using the sputtering phenomenon, the characteristic X-ray emitted from 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, direct irradiation with an electron beam or X-ray may cause damage, but in such a case, the thin film is not damaged without being damaged. The change in the composition can be measured one by one, and the composition of the thin film formed on the sample 1K can be prevented from changing due to the change in the composition of the target material 53.

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

In the thin film forming apparatus configured 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. The argon ions in the plasma sputter the target material 53, whereby a thin film is formed on the substrate of the sample 1L. The target material 53 is irradiated with an electron beam emitted from the excitation source 2 during the formation of the thin film. This allows
The elements of the target material 53 are excited, and the characteristic X-rays 7a emitted from the excited elements are emitted from the slit 3 as an intensity adjusting mechanism.
2 and is detected by the semiconductor X-ray detector 6. Also,
Similarly, the characteristic X-rays 7 b emitted by the excited element are 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 and displayed as a spectrum.

For example, with this thin film forming apparatus, yttrium barium copper oxide (YBa ₂ Cu
_In the case of forming a ₃ O _8-x ) thin film, 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. The characteristic X-rays emitted from the target material 53 are reflected and reflected by the total reflection mirror 31 at a predetermined incident / reflection angle so as to selectively reflect the characteristic X-rays emitted by the element to be measured. 31 reflects the characteristic X-rays of oxygen O and has a high intensity of yttrium Y, barium Ba or copper C.
Characteristic X-rays from u can be attenuated. And
Characteristic X-rays 7 of oxygen O after being reflected by total reflection mirror 31
By making the intensity of b and the intensity of characteristic X-rays 7a from yttrium Y, barium Ba, or copper Cu substantially equal using the slit 32, the composition of the target material 53 can be measured efficiently.

Further, the pumping source 2 is differentially evacuated by the evacuating mechanism 57 so that measurement can be performed even when argon gas or the like during the formation of the thin film is introduced. Further, by using the gas introducing mechanism 58 to flow a gas so that a differential pressure is not applied to the shield 33, it is possible to prevent sputtered particles from adhering to the shield 33. Then, by shielding light and heat generated from the plasma by the shield 33, the influence on the semiconductor X-ray detector 6 can be prevented. Further, since the shield 33 has heat resistance, it is not affected by radiant heat or the like. Since it does not deform or melt,
The characteristic X-rays can be measured one by one.

Therefore, according to the tenth embodiment, when a thin film is formed by using the sputtering phenomenon, the characteristic X-ray emitted from 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, direct irradiation with an electron beam or X-ray may cause damage, but in such a case,
A change in composition during thin film formation can be measured one by one without damaging the thin film, and a change in composition of the thin film formed on the sample 1L due to a change in composition of the target material 53 can be prevented. The pumping mechanism 2 is differentially evacuated by the exhaust mechanism 57 so that measurement can be performed even when argon gas or the like during the formation of the thin film is introduced, and the gas introducing mechanism 58 is used to prevent a differential pressure from being applied to the shield 33. By flowing a gas, it is possible to prevent the sputtered particles from adhering to the shield 33, and to shield the semiconductor X-ray detector 6 by shielding light and heat generated from the plasma by the shield 33.
Can be prevented.

Embodiment 11 FIG. Next, FIG. 19 is a configuration diagram illustrating an etching apparatus that performs dry cleaning according to the eleventh embodiment. In FIG. 19, the same portions as those in the above-described embodiments are denoted by the same reference numerals, and description thereof will be omitted. As a new code, 1M is a sample mixed with impurities of light elements such as oxygen and carbon by a natural oxide film on a silicon Si substrate, and 59 is an electrode for generating plasma.

In the etching apparatus configured as described above, the sample 1M is irradiated with an electron beam or X-ray from an excitation source 2 such as an electron beam source or X-ray source. Thereby, the sample 1
The element of M is excited and the characteristic X emitted by the excited element is released.
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-rays 7b emitted from the excited element are reflected by the total reflection mirror 31, and then detected by the semiconductor X-ray detector 6. The characteristic X-rays detected by the semiconductor X-ray detector 6 are applied to a signal processing circuit 8.
And stored and displayed as a spectrum.

In the case of removing the 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, the etching gas is introduced by the gas introduction mechanism 51 and the power supply 52 for generating plasma is used. Sample 1M
A plasma is generated between the electrode and the electrode 59 to remove the impurity by etching. Thereafter, the gate valves 54 and 55 are opened, and the elements in the sample 1M are excited by the excitation source 2.
The characteristic X-rays emitted from the sample 1M are reflected by the total reflection mirror 31 at a predetermined incident / reflection angle in order to selectively reflect the characteristic X-rays emitted from the element to be measured.
The characteristic X-rays from the strong silicon Si are reflected by the total reflection mirror 31.
The characteristic X-rays reflected by the total reflection mirror 31 are mostly low-energy characteristic X-rays such as oxygen and carbon.

The characteristic X-ray intensity from the silicon Si is adjusted to the intensity at which the signal processing circuit 8 operates normally using the slit 32, so that an extremely small amount of oxygen or carbon impurities which cannot be removed after etching. Elements can be measured efficiently. Moreover, since the sample 1M is not subjected to the etching treatment in the vacuum layer 10 and exposed to the atmosphere, the substrate surface is not oxidized, and the amount removed by the etching can be measured accurately.

Therefore, according to the eleventh embodiment, the sample 1
In the case where impurities of light elements such as oxygen and carbon are removed by etching with a natural oxide film on the silicon substrate of M, the sample 1M is excited by the excitation source 2 after the removal of the impurities.
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 of silicon Si among the characteristic X-rays emitted from the sample By making the signal processing circuit 8 operate at a level that allows the signal processing circuit 8 to operate normally, extremely small amounts of oxygen and carbon impurity elements that cannot be removed after etching can be efficiently measured. Since 1M is not exposed to the atmosphere, the substrate surface is not oxidized,
The amount removed by etching can be accurately measured.

Embodiment 12 FIG. Next, FIG. 20 is a configuration diagram illustrating the ion implantation apparatus according to the twelfth embodiment. 20, the same parts as those in the above-described embodiments are denoted by the same reference numerals, and the description thereof will be omitted. As a new code, 1N is silicon Si
A sample into which phosphorus P is to be implanted on the substrate, 60 is an ion beam which generates ions to be implanted, performs acceleration / mass separation, etc.
Is an accelerator for irradiating the sample 1N, 62 is a rotation 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 implantation apparatus configured as described above, the ion beam 6 generated by the accelerator 60 is used.
1 irradiates the sample 1N. Since the ion beam 61 has acceleration energy, the elements in the sample 1L are excited,
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 are detected by the semiconductor X-ray detector 6. Similarly, the characteristic X-rays (fluorescent X-rays) 7 b emitted by the excited element are diffracted by the diffraction grating 63 and then detected by the semiconductor X-ray detector 6. The characteristic X-rays (fluorescent X-rays) detected by the semiconductor X-ray detector 6 are processed by the signal processing circuit 8 and stored and displayed as a spectrum.

For example, a case where phosphorus P is implanted into a silicon Si substrate will be described. Phosphorus P is generated by the accelerator 60, and an ion beam 61 of phosphorus P is irradiated on the silicon Si substrate.
Phosphorus ions are decelerated in the silicon Si substrate and injected near a predetermined depth. At this time, since the energy of several tens to several hundreds eV is given to the phosphorus ions, the element of silicon Si is excited. Also, the previously implanted phosphorus P element is similarly excited, so that when irradiated with the ion beam 61, the silicon S
i and phosphorus P emit characteristic X-rays (fluorescent X-rays). Silicon S
Compared to the number of atoms in the i-substrate, the atoms of the phosphorus P element are very small, so that the characteristic X-rays (fluorescent X-rays) of phosphorus P are 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 reflected through the semiconductor X-ray detector 6 through the semiconductor X-ray detector 6. The characteristic X-rays (fluorescent X-rays) 7a from the silicon Si having 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. Thus, characteristic X-rays (fluorescent X-rays) of silicon Si can be measured at the same time, and fluctuations of incident X-rays can be normalized using the intensity of characteristic X-rays (fluorescent X-rays) of silicon Si. .

Therefore, according to the twelfth embodiment, the silicon S
When the phosphorus P element is ion-implanted on the i-substrate, the element in the sample 1L is excited by the 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 via the diffraction grating 63 and the solar slits 46a and 46b and the characteristic X-rays (fluorescent X-rays) from silicon Si via the slits 32 are made the same using the slits 32. Semiconductor X-ray detector 6
, 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 the first aspect of the present invention, there is provided an electromagnetic wave detecting apparatus having a detector for detecting electromagnetic waves of a plurality of wavelengths generated by elements in a sample. An optical element installed between the optical element for selectively reflecting or transmitting at least one or more wavelengths of electromagnetic waves of a plurality of wavelengths generated from the sample, between the sample and the detector , and Of electromagnetic waves generated from the sample
Adjust only the intensity of the electromagnetic wave that directly enters the detector
The intensity of the electromagnetic wave entering the optical element includes an intensity adjustment mechanism that is installed at a position where the intensity is not adjusted and adjusts the intensity of the electromagnetic wave,
By detecting the electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity has been adjusted by the intensity adjustment mechanism with the detector, even a weak electromagnetic wave can be detected when measuring a plurality of electromagnetic waves having a large intensity ratio. It has the effect that it can be done.

According to the electromagnetic wave detecting device of the second aspect, when measuring a plurality of electromagnetic waves having a large intensity ratio, the wavelength of the electromagnetic waves is set in the X-ray range, so that the element based on the energy value of the X-rays can be measured. This has the effect that the type can be easily identified.

According to the electromagnetic wave detecting device of the third aspect, the detector is an energy dispersive detector, so that when detecting a plurality of electromagnetic waves having a large intensity ratio, the electromagnetic wave is counted by the electromagnetic waves having a large intensity. There is an effect that a weak electromagnetic wave can be detected at the same time without the rate being controlled.

Further, according to the electromagnetic wave detecting device of the fourth aspect, light and heat entering the detector are shielded and 1 ke
Providing a heat-resistant shield that transmits X-rays including soft X-rays of V or less prevents adverse effects of light or heat on the detector, and emits X-rays including soft X-rays of 1 keV or less. There is an effect that light elements can be detected.

Further, according to the electromagnetic wave detection device of the fifth aspect, the intensity adjusting mechanism can change the aperture ratio.
By using a slit for adjusting the intensity of the electromagnetic wave, it is possible to change the aperture ratio of the slit to enable simple intensity adjustment.

According to the electromagnetic wave detecting device of the sixth aspect, by using an optical element utilizing a total reflection phenomenon as an optical element, the electromagnetic wave is reflected and reflected at a predetermined incident and reflected angle, so that a plurality of electromagnetic waves are reflected. Among them, the effect of being able to simultaneously reflect the 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 emitting the reflected electromagnetic waves. 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 can be incident and reflected at a predetermined incident / reflection angle or can be set at a predetermined focal position. By placing the sample and the detector and focusing the electromagnetic waves of the element to be measured emitted from the sample on the detector, the electromagnetic waves of a specific element can be emitted regardless of the energy level of the weak electromagnetic waves and the strong electromagnetic waves. Unlike the case where an optical element utilizing the total internal reflection phenomenon is used, an element that emits electromagnetic waves having higher energy than strong electromagnetic waves is present as an impurity and its amount is very small. Even in a weak case, there is an effect that it is possible to selectively extract only an electromagnetic wave of an element that emits a high-energy electromagnetic wave.

[0138] 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 above-described base by the intensity adjustment mechanism.
Of the electromagnetic waves generated from the plate, directly enter the detector,
By detecting the intensity of the electromagnetic waves that do not enter the optical element and the adjusted electromagnetic waves with a detector, during processing of the substrate, even when measuring a plurality of electromagnetic waves having a large intensity ratio, even weak electromagnetic waves can be detected. There is an effect that the change in composition can be measured by making it detectable.

Further, according to the substrate processing apparatus of the ninth aspect, when the thin film is formed on the substrate by the sputtering phenomenon by the thin film forming mechanism, 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 a change in the composition of the target material, and the optical element is used to adjust at least one wavelength of the electromagnetic wave generated by the element in the target material. While selectively reflecting,
The intensity adjustment mechanism directly enters the detector,
By adjusting the intensity of electromagnetic waves that do not enter the element ,
The electromagnetic wave reflected or transmitted by the optical element and the electromagnetic wave whose intensity has been adjusted by the intensity adjustment mechanism are detected by a detector, and when measuring a plurality of electromagnetic waves having a large intensity ratio at which an element in the target material is generated. There is an effect that even weak electromagnetic waves can be detected.

[0140]

[0141] Further, according to the substrate processing apparatus according to claim 10, in claim 8 or 9, in the substrate processing, when measuring a plurality of electromagnetic waves is large intensity ratio, X-rays region the wavelength of the electromagnetic wave By doing so, there is an effect that the type of the element of the substrate or the target material as the sample can be easily identified based on the energy value of the X-ray.

According to the substrate processing apparatus of the eleventh aspect , in any one of the eighth to tenth aspects, the detector is an energy dispersive detector.
When detecting a plurality of electromagnetic waves having a large intensity ratio, there is an effect that it is possible to simultaneously detect weak electromagnetic waves without controlling the counting rate by the electromagnetic waves having a large intensity.

According to a twelfth aspect of the present invention, there is provided the substrate processing apparatus according to any one of the eighth to eleventh aspects, wherein light and heat entering the detector are shielded and the soft X of 1 keV or less.
By providing a heat-resistant shield that transmits X-rays including X-rays, it is possible to prevent light and heat from adversely affecting the detector.
This has the effect that light elements that emit X-rays including soft X-rays of eV or less can also be detected.

According to the substrate processing apparatus of the thirteenth aspect , in any one of the eighth to twelfth aspects, the strength adjusting mechanism is constituted by a slit, so that the aperture ratio of the slit can be changed, thereby simplifying the operation. There is an effect that the strength can be adjusted.

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

According to the substrate processing apparatus of the fifteenth aspect , in any one of the eighth to thirteenth aspects, by using an optical element utilizing a diffraction phenomenon as the optical element, electromagnetic waves can be transmitted at a predetermined incident / reflection angle. By entering and reflecting, or by placing the sample and the detector at a predetermined focus position and focusing the electromagnetic waves of the element to be measured emitted from the sample on the detector,
It is possible to selectively extract electromagnetic waves of specific elements regardless of the level of energy of low intensity electromagnetic waves and high intensity electromagnetic waves, and unlike the case of using an optical element utilizing the total reflection phenomenon, high intensity Even when the element that emits electromagnetic waves with higher energy than the electromagnetic waves is present as an impurity and its intensity is low due to its small amount, it is possible to selectively extract only the electromagnetic waves of the elements that emit electromagnetic waves with high energy. Play.

[Brief description of the drawings]

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

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

FIG. 3 is an explanatory diagram illustrating an example of a slit that is the strength adjusting mechanism of FIG. 1;

FIG. 4 is a structural diagram showing an example of a shield of FIG. 1;

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

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

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

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

FIG. 9 is a configuration diagram showing an element analyzer according to Embodiment 4 of the present invention.

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

11 is a schematic structural view showing an example of a detector using a junction in the superconductor of FIG. 9;

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

FIG. 13 is a schematic structural view showing an example of an organic crystal as the 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 illustrating a thin film forming apparatus according to a seventh embodiment of the present invention.

FIG. 16 is a configuration diagram illustrating a thin film forming apparatus according to an eighth embodiment of the present invention.

FIG. 17 is a configuration diagram showing a thin film forming apparatus for forming a thin film 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 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 Embodiment 11 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.

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

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 a detector when the intensity of characteristic X-ray energy is high in a 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 8 Signal processing circuit Mechanism 31 Total reflection mirror 32 Slit 33 Shield 34 Multilayer mirror 35a Slit 35b Slit 36 Transmission diffraction grating 43 Diffraction grating 44 Diffraction grating 45 Organic crystal 53 Target material 56 Plural inorganic crystals 60 Tunnel junction in superconductor Detector 63 Diffraction grating

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-270953 (JP, A) JP-A-3-276089 (JP, A) JP-A-62-149157 (JP, U) JP-B-45 5360 (JP, B1)

Claims (15)

(57) [Claims] 1. An electromagnetic wave detection device having a detector for detecting electromagnetic waves of a plurality of wavelengths generated by an element in a sample, wherein the plurality of wavelengths are provided between the sample and the detector and are generated from the sample. An optical element that selectively reflects or transmits at least one wavelength of at least one of the electromagnetic waves between the sample and the detector and from the sample.
Of the electromagnetic waves directly entering the detector
Adjust, do not adjust the intensity of electromagnetic waves entering the optical element
An intensity adjusting mechanism installed at a position to adjust the intensity of the electromagnetic wave, wherein 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. Electromagnetic wave detection device. 2. The electromagnetic wave detection device according to claim 1, wherein the wavelength of the electromagnetic wave is in an X-ray region. 3. The electromagnetic wave detection device according to claim 1, 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 the above. 5. The strength adjusting mechanism changes an aperture ratio.
5. The electromagnetic wave detecting device according to claim 1, wherein the slit is a slit for adjusting the intensity of the electromagnetic wave. 6. The electromagnetic wave detecting device according to claim 1, wherein said optical element is an optical element utilizing a total reflection phenomenon. 7. The electromagnetic wave detecting device according to claim 1, wherein the optical element is an optical element utilizing 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 disposed between the substrate being processed and the detector, for selectively reflecting or transmitting at least one or more wavelengths of the electromagnetic waves having the plurality of wavelengths, Between the substrate and the detector , and
Of the electromagnetic waves generated from the substrate, directly enter the detector
Adjusting only the intensity of electromagnetic waves, electromagnetic waves entering the optical element
An intensity adjustment mechanism that is installed at a position where the intensity of the electromagnetic wave is not adjusted and adjusts the intensity of the electromagnetic wave while the substrate is being processed by the processing mechanism. A substrate processing apparatus, wherein the detector detects the adjusted electromagnetic wave. 9. 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 an electromagnetic wave emitted by the element excited by the excitation source Detector, an optical element installed between the target material and the detector for transmitting or reflecting the electromagnetic wave , and between the target material and the detector , and the target
Electromagnetic waves directly entering the above detector among electromagnetic waves generated from materials
Only the intensity of the electromagnetic wave entering the optical element
A substrate processing apparatus comprising: an intensity adjustment mechanism that is installed at a position where adjustment is not performed and adjusts the intensity of electromagnetic waves. Wavelength of claim 10 wherein said electromagnetic radiation, a substrate processing apparatus according to claim 8 or 9, characterized in that the X-ray region. 11. The detector substrate processing apparatus according to any one of claims 8 to 10, characterized in that an energy dispersive detector. 12. 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.
12. The substrate processing apparatus according to any one of items 11 . 13. The strength adjusting mechanism changes an aperture ratio.
The substrate processing apparatus according to any one of claims 8 to 12 , wherein the slit is a slit for adjusting the intensity of the electromagnetic wave by causing the slit to adjust . 14. The optical element, to claims 8, characterized in that an optical element that utilizes total reflection phenomenon 13
The substrate processing apparatus according to any one of the above. 15. The optical device includes a substrate processing apparatus according to any one of claims 8 to 13, characterized in that an optical element utilizing a diffraction phenomenon.