JPH1048165A - Method and apparatus for surface analysis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method and an apparatus, for a surface analysis, in which the scale of the apparatus is not large, in which an operation is simple, the time for the analysis is short and a sample is not damaged by the analysis. SOLUTION: In this apparatus, a beam of visible light or vacuum ultraviolet rays which are radiated from a light source 1 are spectrally diffracted by a spectroscope 3 so as to irradiate a very small region 8' on the face of a sample 9, electrons which are emitted by the irradiation are detected by a detector 13, a detection signal is analyzed by a computer 14 so as to be compared with, and referred to, a peak wavelength 22, a peak intensity 21 or a threshold value 23, and information about the element or the chemical state of the sample 9 and an adsorbed substance and about its change with the passage of time is obtained. In addition, incident light 8 is scanned on the face of the sample 9, and information about the two-dimensional distribution of the element of the sample 9 is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for analyzing a surface and an adsorbed substance, in particular, a surface analysis method for obtaining information on elements or chemical states in a minute region in a nondestructive manner under a low vacuum or atmospheric pressure.

[0002]

2. Description of the Related Art With the miniaturization, high precision and high performance of products, various surface analysis techniques are indispensable. In particular, there is a strong demand for an analytical method for obtaining information on the element or chemical state in the surface and in the minute region of the adsorbate. To meet these demands, XPS (X-ray photoelectron spectroscopy), UP
Surface analysis methods using S (vacuum ultraviolet photoelectron spectroscopy), AES (Auger electron spectroscopy), TOF-SlMS (time-of-flight secondary ion mass spectrometry), and the like have been proposed.

In these methods, a micro-beam such as an electron, an ion, a vacuum ultraviolet ray, or an X-ray is irradiated on a minute area of a sample, and electrons and secondary ions emitted from the sample surface are observed. The analysis is performed under a high vacuum, the equipment is generally large and expensive, the operation is complicated, and has a depth resolution on the order of nanometers and a surface resolution on the order of micrometers. In addition, the surface of the sample is often damaged by the irradiation of the beam, and the chemical state at the beginning of analysis is impaired.

[0004] JP-A-2-114159, JP-A-6-16-1
No. 60314 and JP-A-7-110311 disclose a method and an apparatus for observing electrons emitted from a sample surface by irradiating soft X-rays or vacuum ultraviolet rays on a minute area and analyzing elements constituting the minute area. It has been disclosed. The analysis is performed under ultra-high vacuum for the convenience of the equipment components such as the energy analyzer, and also requires complicated data processing such as integral conversion and inverse conversion. On the other hand, JP-A-1-295145 discloses a method of observing electrons emitted from a sample surface by irradiation of visible light or vacuum ultraviolet light and quantifying the thickness of a relatively thick thin film of the order of micrometers at atmospheric pressure. It has been disclosed.

[0005]

The first problem with the conventional method is that many surface analyzers, such as the one disclosed in Japanese Patent Application Laid-Open No. Hei 7-11031, perform analysis under high vacuum. Therefore, high-vacuum detectors such as energy detectors require complicated data conversion and data analysis of detection signals, which makes the equipment large and expensive, maintenance and operation complicated, and running costs. And the analysis time is long.

A second problem is that in a device for irradiating a sample with electrons or ions such as XPS or AES, the surface of the sample is often damaged by the irradiation of the electron and ion beams. Therefore, not only can analysis not be repeated, but also when focusing on changes over time in the sample or when observing changes in the sample caused by applying a stimulus to the sample, the damage caused by beam irradiation affects the analysis results. Effect. Particularly, in a process such as a material acceptance inspection or a product sampling inspection, in which high-precision and quick analysis of the surface state of a material or a product is regularly or frequently required, Japanese Patent Laid-Open No. 7-11 / 1995
According to the method of JP-A No. 0311, the apparatus becomes too large, and no practical detection sensitivity can be obtained by the method of JP-A-1-295145.

In view of the above-mentioned conventional problems, the present invention irradiates a micro-region of a sample with a visible light or vacuum ultraviolet ray which does not damage the sample, and emits relatively low energy of relatively low energy emitted from the sample surface. An object of the present invention is to provide a surface analysis method and an apparatus for detecting and analyzing electrons under low vacuum or atmospheric pressure.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems without lowering the analysis accuracy, and performs a quick, simple and inexpensive non-destructive surface analysis. A means for detecting, with sufficient sensitivity, a relatively low-energy electron emitted from the sample surface by irradiation in a surface analyzer that generates, disperses, and irradiates a minute area of the sample with vacuum ultraviolet light. Data analysis means that does not require complicated calculations; means for observing a change over time in a sample; means for applying a stimulus to a sample; and means for observing a change when a stimulus is applied to a sample.

That is, in the surface analysis method of the present invention, in the surface analysis for observing electrons emitted from the sample surface by irradiation with visible light or vacuum ultraviolet rays, the fineness of the sample is changed while changing the wavelength of the visible light or vacuum ultraviolet rays. Irradiate the region and compare the peak wavelength, peak intensity, or threshold value of the detection signal of the electrons emitted from the sample surface by irradiation to determine the element or chemical state of the sample and adsorbate in the irradiated region under low vacuum. Is obtained.

Another surface analysis method according to the present invention is directed to a surface analysis for observing electrons emitted from a sample surface by irradiation of visible light or vacuum ultraviolet light. While moving the sample stage provided with the moving mechanism to scan the incident light converging point on the sample surface, while detecting the peak wavelength, peak intensity or peak of the detection signal of the electrons emitted from the sample surface by the irradiation. It is characterized in that a two-dimensional distribution of elements or chemical states of a sample and an adsorbate in an irradiation region is obtained under a low vacuum by comparing and comparing threshold values.

Further, in the surface analysis method of the present invention, in a surface analysis for observing electrons emitted from a sample surface by irradiation of visible light or ultraviolet light, a minute region of the sample is irradiated with visible light or ultraviolet light fixed at a fixed wavelength. Then, by comparing the peak wavelength, peak intensity or threshold value of the detection signal of electrons emitted from the sample surface by irradiation, information on the element or chemical state of the sample and the adsorbate in the irradiation area under atmospheric pressure is obtained. It is characterized by obtaining.

The method of detecting emitted electrons is performed by a microammeter, and a practical sensitivity can be obtained even under atmospheric pressure.

Further, the above-mentioned surface analysis method is characterized in that electrons emitted from the sample surface are detected while applying a stimulus to the sample.

Further, the method for applying a stimulus to the sample is characterized by heat or gas.

Further, the above-mentioned surface analysis method is characterized by observing a change with time of the element or the chemical state of the sample and the adsorbate.

The above-mentioned surface analysis method is characterized by observing a change with time in the element or the chemical state of the sample and the adsorbate while applying a stimulus to the sample.

The surface analyzer of the present invention detects electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light, and obtains information on the element or chemical state of the sample and the adsorbate. , Means for generating visible light or vacuum ultraviolet light, means for improving spectral characteristics, means for changing or fixing the wavelength of visible light or vacuum ultraviolet light to be incident, and changing the shape and area of the incident light focusing point Means, means for focusing visible light or vacuum ultraviolet light on a small area of the sample, means for detecting electrons emitted from the sample surface, and means for analyzing the peak wavelength, peak intensity or threshold value of the detection signal. And obtaining information on the element or chemical state of the sample and the adsorbate under a low vacuum.

Another surface analyzer of the present invention detects electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light, and obtains information on the element or chemical state of the sample and the adsorbate. In the analyzer, means for generating visible light or vacuum ultraviolet light, means for improving spectral characteristics, means for fixing the wavelength of visible light or vacuum ultraviolet light to be incident, and changing the shape and area of the incident light focusing point Means, means for condensing visible light or vacuum ultraviolet light on a small area of the sample, means for aligning the incident light converging point with respect to the sample and scanning the incident light converging point on the sample surface, Means for visually recognizing the sample and the incident light converging point for alignment with the converging point; means for detecting electrons emitted from the sample surface; And means for analyzing the intensity or threshold value, and obtaining a two-dimensional distribution of elements or chemical state of the sample and the adsorbate in a low vacuum.

Further, the surface analyzer of the present invention detects electrons emitted by irradiating a minute region of the sample with visible light or ultraviolet light, and obtains information on the element or chemical state of the sample and the adsorbate. In the analyzer, means for generating visible light or ultraviolet light, means for improving spectral characteristics, means for fixing the wavelength of visible light or ultraviolet light to be incident, and means for changing the shape and area of the incident light focus point Means for condensing visible light or ultraviolet light on a minute area of the sample, means for moving the sample stage provided with a moving mechanism to adjust the position of the incident light converging point with respect to the sample, and Means for visually recognizing the sample and the incident light converging point to align with the light spot, means for detecting electrons emitted from the sample surface, peak wavelength and peak intensity of the detection signal Is characterized by obtaining information element or chemical state of the sample and adsorbate in which means and a atmospheric pressure for analyzing the threshold.

The means for detecting the emitted electrons is a minute ammeter, and practical sensitivity can be obtained even under atmospheric pressure.

The above-mentioned surface analyzing apparatus is characterized in that it comprises means for stimulating a sample.

[0022] The means for stimulating the sample is heat or gas.

The above-mentioned surface analyzer is characterized in that it is provided with a means for observing a change over time in the element or the chemical state of the sample and the adsorbate.

The above-mentioned surface analyzing apparatus is characterized in that it comprises means for observing a change with time in the element or the chemical state of the sample and the adsorbed substance while applying a stimulus to the sample.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Visible light or vacuum ultraviolet light emitted from a light source is adjusted by a slit in order to improve spectral characteristics in a subsequent spectroscope, and is split by the spectroscope. The split light beam is narrowed down to the shape and area of the incident light condensing point according to the sample and the purpose by a pinhole, and becomes a micro beam. The micro beam is guided onto a sample via a lens and, in some cases, a reflecting mirror, and irradiates a minute area of the sample. Relatively low-energy electrons emitted by the irradiation of the sample with the microbeam are detected by a detector capable of detecting with sufficient sensitivity under low vacuum or atmospheric pressure. The detection signal is analyzed by a computer, and information on the element or the chemical state of the sample and the adsorbate can be obtained. If necessary, stimulate the sample or observe changes over time.

An embodiment of the present invention will be described below with reference to FIGS. FIG. 1 is a diagram showing a configuration example of a surface analyzer, and FIG. 2 is a diagram showing a detection signal analysis method.

One example of the surface analysis method of the present invention is a surface analysis for observing electrons (e ⁻ ) emitted from the surface of the sample 9 by irradiation with visible light or vacuum ultraviolet rays. Irradiating the micro region 8 ′ of the sample 9 while changing the peak wavelength 22 and the peak intensity 2 of the detection signal of the electron (e ⁻ ) emitted from the surface of the sample 9 by the irradiation.
This is a method of obtaining information on the element or the chemical state of the sample 9 and the adsorbed substance of the sample 9 in the irradiation area under a low vacuum by comparing 1 or the threshold 23.

An example of the surface analyzer of the present invention detects the electrons (e ⁻ ) emitted by irradiating a minute area of the sample 9 with visible light or ultraviolet light, and detects the sample 9 and the sample 9.
A light source 1 which is a means for generating visible light or ultraviolet light, a slit 2 which is a means for improving spectral characteristics, and a visible light to be incident A spectroscope 3 as a means for fixing the wavelength of the ultraviolet light, a pinhole 4 as a means for changing the shape and area of the incident light converging point 8 ', and condensing visible light or ultraviolet light on a minute area of the sample 9. By moving the collimating lens 5, the reflecting mirror 6, the condensing lens 7, and the sample stage 10 provided with the moving mechanism 11, the position of the incident light converging point 8 ′ of the incident light 8 with respect to the sample 9 is included. Means for performing the measurement, and the sample 9 and the incident light condensing point 8 ′ for aligning the sample 9 with the incident light condensing point 8 ′.
And the electron (e) emitted from the surface of the sample 9.
^- ) And a computer 14 which is a means for analyzing a peak wavelength 22, a peak intensity 21 or a threshold value 23 of a detection signal. It is a device that obtains information on element or chemical state.

Examples of means for visually recognizing the sample 9 and the incident light converging point 8 'in order to align the sample 9 with the incident light converging point 8' include a glass plate or a window having a lens or the like. Sample window 17. By adjusting the incident light into visible light by the sample window 17 as a means for visual recognition, the position of the incident light converging point 8 ′ can be visually recognized, so that the surface of the sample 9 can be accurately irradiated with the incident light 8. is there.

The present invention will be described in more detail with reference to FIGS. The visible light or vacuum ultraviolet light emitted from the light source 1 is adjusted by the slit 2 which is a means for improving the spectral characteristics in the subsequent spectroscope 3, and is split into a predetermined wavelength by the spectroscope 3 controlled by the computer 14. . The spectral characteristics refer to monochromaticity of light rays in the subsequent spectroscope 3, and improving the spectral characteristics means increasing monochromaticity of the incident light 8. As the monochromaticity of the incident light 8 is higher, a sharper peak is obtained, and a more accurate qualitative analysis can be performed. Since the light beam never converges on a focal point smaller than the diameter of the original light beam, the split light beam is
And a focusing point (incident light focusing point) 8 ′ according to the purpose and the shape and area of the focusing point 8 ′ to form a micro beam.

The luminous flux of the micro beam is made parallel by the collimating lens 5, and the reflecting mirror 6, the condensing lens 7
After that, the incident light 8 is condensed on a minute area on the surface of the sample 9 placed on the sample stage 10. Electrons emitted from the sample 9 by the irradiation of the incident light 8 are detected by the detector 13 controlled by the computer 14, and the obtained detection signal is analyzed by the computer 14, and the analysis result is processed by the monitor 15 and the recorder 16 as necessary. Etc. are output from an external output device.

The detector 13 includes a Geiger-Muller (Ge)
An igger-muler counter tube or a microammeter capable of detecting the above electrons with sufficient sensitivity under low vacuum or atmospheric pressure is used. Since the data processing of the detection signal of the detector is relatively easy, it is possible to use the computer 14 at the personal computer level. In the above configuration example, the components that need to be installed under a low vacuum at least are the sample 9 and the sample stage 10.
(Upper half), moving mechanism 11, stimulating mechanism 12, detector 13
The five. In order to minimize the attenuation of the incident light 8, all the components except for the computer 14, the monitor 15, and the recorder 16 can be installed under a low vacuum. The required degree of vacuum is about 10 ^-2 Torr, and the sample can be quickly introduced and exchanged.

The data is usually the peak wavelength 22 of the raw data.
Alternatively, as shown in FIG. 2B, the peak intensity 21 and the threshold value 23 obtained by converting the wavelength into energy and the intensity into the square root of the intensity, respectively, are obtained by focusing on the above three values. From the three values, information on the element or chemical state of the surface of the sample 9 and the adsorbate can be known. Here, the information on the chemical state includes information based on qualitative analysis or quantitative analysis of the sample 9. Since complicated calculations are not required to obtain these values, data analysis can be easily performed at a practical speed even with a computer at the personal computer level. If necessary, the analysis can be performed while variously changing the wavelength to be separated by the spectroscope 3. When the analysis is performed while changing the wavelength, analysis of a sample whose peak wavelength 22 is unknown and analysis focusing on a plurality of peaks can be performed as compared with a case where the wavelength is not changed.

Here, as shown in FIG. 2A, the peak intensity 21 is the maximum value of the electron detection signal at the wavelength corresponding to the element or chemical state of interest, and the peak wavelength 2
Reference numeral 2 denotes a wavelength at which an electron detection signal at a wavelength corresponding to an element or a chemical state of interest has a maximum value.
3, as shown in FIG. 2B, the wavelength is converted to energy,
When the intensity is converted into the square root of the intensity and the tangent line between the base line and the peak rise curve is drawn, the energy at the intersection is shown. That is, the threshold value 23
Means the wavelength (energy) at which electrons begin to be emitted. The threshold value 23 and the peak wavelength 22 have values specific to the substance. Therefore, qualitative analysis of the sample can be performed from these values. In addition, when focusing on a known substance, quantitative analysis can be performed by fixing the wavelength of the incident light 8 to the peak wavelength 22 of the substance and comparing the peak intensity 21 with another sample. This is because the peak intensity 21 is proportional to the number of emitted electrons and means the absolute amount of the substance.

However, like many other analysis data, it is not always necessary to pay attention only to the intensity or wavelength at which the detection signal becomes maximum, such as when a plurality of peaks overlap or when the peaks shift with time. Therefore, in principle, the peak intensity 21, the peak wavelength 22, or the threshold 2
3 is defined as described above, but it is also possible to appropriately define these values as needed. Further, it is also possible to observe a change with time of the detection signal under the control of the computer 14. By such a method, for example, the surface dispersion speed of the oil film can be measured.

Next, a method for obtaining a two-dimensional distribution in the above embodiment will be described. The sample stage 10 is operated by the moving mechanism 11 controlled by the computer 14 so that the region to be analyzed on the surface of the sample 9 is shifted to the converging point of the incident light 8 which is separated into the wavelength corresponding to the element or chemical state of interest. The detector 13 is moved to detect electrons emitted from the surface of the sample 9 by irradiation of the incident light 8 and having energy corresponding to a chemical state or an element of interest. These series of operations are performed while controlling the computer 14 to scan the focal point of the incident light 8 on the surface of the sample 9, and the obtained detection signal is analyzed by the computer 14 to obtain the surface of the sample 9 and the adsorption. The two-dimensional distribution of the element or chemical state of an object can be known.

Next, a method of observing a change in the sample caused by various stimuli in the above embodiment will be described. Using the sample stage 10 provided with the stimulating mechanism 12, various stimuli are applied to the sample 9 singly, intermittently or continuously while controlling the computer 14, and a change in a detection signal corresponding to the various stimuli is obtained. Can be observed. The stimulus applied to the sample 9 by the stimulus mechanism 12 includes heat, gas, and the like. By such a method of giving a stimulus, it is possible to know, for example, information on the adsorption or reaction behavior of the organic gas to the noble metal material, and the temperature dependency such as the denaturation or desorption behavior of the adsorbed substance on the sample surface.

Next, a method of performing an analysis under the atmospheric pressure in the above embodiment will be described. In order to perform the analysis under the atmospheric pressure, it is necessary that the relatively low energy electrons emitted from the sample 9 can be detected with sufficient sensitivity. An example of the detector 13 that satisfies the above conditions is a minute ammeter.

It should be noted that combinations of the above embodiments are also included in the present invention. Further, in the above-described embodiment, the means for condensing the incident light 8 is exemplified as the configuration of the collimating lens 5, the reflecting mirror 6, and the condensing lens 7, but other device configurations, for example, the reflecting mirror 6
A configuration having a geometrical difference such that all the components from the light source 1 to the sample stage 10 are linearly arranged without passing through, or using an aromatic lens as a means for condensing the incident light 8 In principle, the principle is the same, such as reducing the aberration of the incident light converging point 8 'due to the difference in wavelength, but there is a functional difference in which the component (optical system) is replaced by another component (optical system). It is needless to say that the same can be applied similarly.

[0040]

[Examples] Examples of specific experimental results will be described below with reference to examples. (Example 1) A Cu specimen in which a Cu oxide film having a thickness of about 5 nm (nanometer) was formed on the left half was prepared. The two-dimensional distribution of the copper oxide of this specimen was measured using the apparatus shown in FIG. 1 as follows. The wavelength of the incident light 8 is fixed at 260 nm, which is the peak wavelength of Cu, the incident light converging point 8 'is a circle having a diameter of 100 μm, and the Cu specimen has a diameter of 9 mm.
Two-dimensional mapping was performed at a surface resolution of 100 μm over a range of × 7 mm. The experiment was performed at 5.5 × 10 ^-2 Torr.
I went in. A Geiger-Muller counter tube is used for the detector 13, and a PC 8800 (manufactured by NEC Corporation) is used for the computer.
Were used.

[0041] Sokuchi a surface analyzer used is, as shown in FIG. 1, the ultraviolet electrons emitted by irradiating (260 nm) in the micro region 8 of Cu coupon 9 ^'- detects (e) A light source 1 for generating ultraviolet light, a slit 2 for improving spectral characteristics, a spectroscope 3 for fixing the wavelength of ultraviolet light to 260 nm, and an incident light. A pinhole 4 for changing the shape or area of the focal point 8 ', a collimating lens 5, a reflecting mirror 6 and a condensing lens 7 for condensing ultraviolet rays on a minute region 8' (a circle having a diameter of 100 μm) of the sample 9. Sample stage 1 for aligning incident light converging point 8 'with sample 9 and scanning incident light converging point 8' on sample 9 surface
0, a moving mechanism 11, a sample window 17 for visually recognizing the sample 9 and the incident light converging point 8 ′ in order to position the sample 9 at the incident light converging point 8 ′, and from the surface of the sample 9. A Geiger-Muller counter 13 for detecting emitted electrons (e ⁻ );
A computer 14 for analyzing the peak wavelength 22, peak intensity 21, and threshold value 23 of the detection signal was provided.

The surface analysis is performed under a low vacuum (5.
This is a surface analysis method for observing electrons (e ⁻ ) emitted from the surface of a sample 9 by irradiation of ultraviolet rays (260 nm) at 5 × 10 ⁻² Torr, and a vacuum ultraviolet ray 8 fixed at a constant wavelength (260 nm) is used as a sample. (Cu sample) 9 is irradiated on a small area (circle having a diameter of 100 μm) and the sample stage 10 provided with the moving mechanism 11 is moved to scan the incident light focusing point 8 ′ on the surface of the sample 9. Sample 9 by irradiation
Electrons (e ⁻ ) emitted from the surface are detected by a Geiger-Muller counter tube 13 and the detection signal is sent to a computer 14.
, A peak wavelength 22, a peak intensity 21, and a threshold value 23 are obtained, and the magnitude of the peak intensity 21 is recorded by a recorder (recorder) 16 in shades. At 5 × 10 ^-2 Torr), a two-dimensional distribution of the element (copper oxide) of Sample 9 in the irradiation region was obtained.

FIG. 3 shows the two-dimensional distribution of copper oxide on the surface of the test piece 9 obtained as described above. As shown in FIG. 3, the peak intensity of the copper oxide film portion on the left side (in the range of (3 to 5) mm × (0 to 7) mm) is small, and the Cu portion on the right side ((6
-9) mm × (0-7) mm) peak intensity was large. That is, the two-dimensional distribution of the copper oxide (oxide film) of the test piece could be displayed by shading.

The thickness of the copper oxide film was determined by ESCA depth profile measurement. Here, the peak intensity 2
1 is proportional to the absolute amount of the copper oxide film, that is, the film thickness. Therefore, the density of the two-dimensional distribution of the peak intensities 21 indicates the distribution of the absolute amount of the copper oxide film. In this embodiment, the peak intensities 21 were determined for each of the analysis points, and the quantitative analysis of the copper oxide was performed. It is nothing but doing.

(Embodiment 2) The wavelength of the incident light 8 is
Irradiating the Cu specimen 9 of Example 1 while changing it within the range of 140 nm, the peak wavelength 22 and the peak intensity 21 of the detection signal of the electron (e ⁻ ) emitted from the surface of the sample 9 by the irradiation.
And the threshold value 23 are obtained, and thus under a low vacuum (5.
Specimen 9 in the irradiation area at 5 × 10 ⁻² Torr)
The peak wavelength 22 and threshold value 23 of Cu were determined. As a result, values of 260 nm and 400 nm were obtained as the peak wavelength 22 and the threshold value 23 of Cu, respectively.

As is clear from FIG. 3, in this embodiment, a two-dimensional mapping of a thin film of the order of nanometers is possible with a surface resolution of the order of micrometers.
The present invention provides high-precision non-destructive surface analysis at low vacuum or atmospheric pressure as compared to conventional analysis methods without lowering the analysis accuracy than conventional analysis methods.
In particular, material acceptance inspection of contact materials and terminal materials, relays,
Such as a sampling inspection of a product such as a connector, etc., exhibits its true value in a process where a highly accurate and quick analysis of the surface state of a material or a product is regularly or frequently required. Furthermore, by incorporating the present surface analyzer online, it is also possible to apply it to a micro-dirt sensor on the outermost surface of a product.

[0047]

As described above, the present invention irradiates a micro-area of a sample with a visible or vacuum ultraviolet ray micro beam which does not damage the sample, and emits relatively low-energy electrons emitted by the irradiation in a low vacuum. Alternatively, detection can be performed with sufficient sensitivity under atmospheric pressure, and the apparatus configuration is simple, so that rapid, simple, and inexpensive nondestructive surface analysis can be performed with high accuracy. Further, since there is no damage to the sample due to the irradiation of the microbeam, it is effective for observing a change with time of the sample or a change due to a stimulus given from outside.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration of a surface analyzer according to an embodiment of the present invention.

FIGS. 2A and 2B are diagrams illustrating a method of analyzing a detection signal based on a peak wavelength, a peak intensity, and a threshold, wherein FIG. 2A illustrates a peak wavelength and a peak intensity, and FIG.

FIG. 3 is a diagram showing a two-dimensional distribution of copper oxide of a test piece.

[Explanation of symbols]

1. light source, 2. slit, 3. spectroscope, 4. pinhole, 5. collimating lens, 6. reflecting mirror, 7.
..Condensed lens, 8..incident light, 8 '.. condensing point of incident light, 9..sample, 10..sample stage, 11..moving mechanism, 12..stimulating mechanism, 13..detector, 14. Computer, 15 Monitor, 16 Recorder, 17
Sample window, 21 peak intensity, 22 peak wavelength,
23 ... threshold

Claims (16)

[Claims] In a surface analysis for observing electrons emitted from a sample surface by irradiation of visible light or vacuum ultraviolet light, a small area of the sample is irradiated while changing the wavelength of visible light or vacuum ultraviolet light, and the sample surface is irradiated by the irradiation. By comparing and comparing the peak wavelength, peak intensity, or threshold value of the detection signal of the electrons emitted from the sample, information on the element or chemical state of the sample and the adsorbate in the irradiation area under a low vacuum is obtained. Surface analysis method. 2. A surface analysis for observing electrons emitted from a sample surface by irradiation of visible light or vacuum ultraviolet light, wherein a visible light or vacuum ultraviolet light fixed at a fixed wavelength is irradiated to a small area of the sample, and a moving mechanism is provided. By moving the sample stage, the incident light focus point is scanned on the sample surface while comparing the peak wavelength, peak intensity or threshold value of the detection signal of the electrons emitted from the sample surface by irradiation. A method for obtaining a two-dimensional distribution of elements or chemical states of a sample and an adsorbate in an irradiation area under a low vacuum. 3. In a surface analysis for observing electrons emitted from a sample surface by irradiation with visible light or ultraviolet light, a small region of the sample is irradiated with visible light or ultraviolet light fixed at a fixed wavelength and emitted from the sample surface by irradiation. Surface analysis characterized by obtaining information on the element or chemical state of the sample and adsorbate in the irradiation area under atmospheric pressure by comparing and referring to the peak wavelength, peak intensity, or threshold value of the detected electron detection signal. Law. 4. The surface analysis method according to claim 3, wherein said method for detecting emitted electrons is performed by a microammeter, and practical sensitivity can be obtained even under atmospheric pressure. 5. A surface analysis for observing electrons emitted from a sample surface by irradiation with visible light or vacuum ultraviolet rays, wherein electrons emitted from the sample surface are detected while applying a stimulus to the sample. 5. The surface analysis method according to any one of items 1 to 4. 6. The surface analysis method according to claim 5, wherein the method of applying a stimulus to the sample is heat or gas. 7. A surface analysis for observing electrons emitted from a sample surface by irradiation with visible light or vacuum ultraviolet light, wherein a change with time of an element or a chemical state of a sample or an adsorbate is observed. 5. The surface analysis method according to any one of items 1 to 4. 8. A surface analysis for observing electrons emitted from a sample surface by irradiation with visible light or vacuum ultraviolet light, and observing a change with time of an element or a chemical state of a sample and an adsorbate while applying a stimulus to the sample. The surface analysis method according to claim 5 or 6, wherein: 9. A surface analysis apparatus for detecting electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light and obtaining information on the element or chemical state of the sample and the adsorbed substance. Means for generating ultraviolet light, means for improving the spectral characteristics, means for changing or fixing the wavelength of visible light or vacuum ultraviolet light to be incident, means for changing the shape and area of the incident light converging point, A low vacuum, comprising: means for concentrating vacuum ultraviolet light on a minute area of the sample; means for detecting electrons emitted from the sample surface; and means for analyzing the peak wavelength, peak intensity or threshold value of the detection signal. A surface analysis apparatus characterized by obtaining information on elements or chemical states of a sample and an adsorbate underneath. 10. Detecting electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light,
Means for generating visible light or vacuum ultraviolet light, means for improving spectral characteristics, and means for fixing the wavelength of visible light or vacuum ultraviolet light to be incident on a surface analyzer for obtaining information on elements or chemical states of a sample and an adsorbate. Means for changing the shape and area of the incident light converging point; means for condensing visible light or vacuum ultraviolet light on a small area of the sample; positioning of the incident light converging point with respect to the sample; Means for scanning on the sample surface,
Means for visually recognizing the sample and the incident light focal point to align the sample with the incident light focal point; means for detecting electrons emitted from the sample surface; A means for analyzing the threshold value of the element or the chemical state of the sample and adsorbate under a low vacuum.
A surface analysis device for obtaining a dimensional distribution. 11. A surface analyzer for detecting electrons emitted by irradiating a minute region of a sample with visible light or ultraviolet light and obtaining information on the element or chemical state of the sample and adsorbate. Means for improving the spectral characteristics, means for fixing the wavelength of visible light or ultraviolet light to be incident, means for changing the shape and area of the incident light condensing point, and means for applying visible light or ultraviolet light to the sample. Means for focusing on a minute area, means for moving the sample stage provided with a moving mechanism to adjust the position of the incident light focusing point with respect to the sample, and means for aligning the sample with the incident light focusing point Means for visually recognizing the sample and the incident light converging point; means for detecting electrons emitted from the sample surface; means for analyzing the peak wavelength, peak intensity or threshold value of the detection signal A surface analysis apparatus comprising: obtaining information on elements or chemical states of a sample and an adsorbed substance under atmospheric pressure, comprising: 12. The surface analyzer according to claim 11, wherein the means for detecting the emitted electrons is a minute ammeter and practical sensitivity can be obtained even under atmospheric pressure. 13. Detecting electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light,
The surface analyzer according to any one of claims 9 to 12, further comprising means for stimulating the sample, wherein the surface analyzer obtains information on an element or a chemical state of the sample and the adsorbate. 14. The surface analyzer according to claim 13, wherein the means for stimulating the sample is heat or gas. 15. Detecting electrons emitted by irradiating a minute region of the sample with visible light or vacuum ultraviolet light,
10. A surface analyzer for obtaining information on the element or chemical state of a sample and an adsorbate, comprising means for observing a change over time of the element or chemical state of the sample and the adsorbate.
13. The surface analyzer according to any one of items 1 to 12. 16. Detecting electrons emitted by irradiating a minute region of a sample with visible light or vacuum ultraviolet light,
15. The surface analysis apparatus for obtaining information on the element or chemical state of a sample and an adsorbate, comprising means for observing a change with time of the element or the chemical state of the sample and the adsorbate while applying a stimulus to the sample. Surface analyzer.