Analysis device, processing unit of analysis device, analysis method, analysis program, and computer-readable storage medium storing the analysis program

Abstract

To improve analysis precision without upsizing a device.SOLUTION: An analysis device stores a wavelength list as a combination of multiple wavelengths used for a constituent analysis for each analysis object element, successively calculates similarly between a reference strength value that is a strength value acquired from reference spectra and is a strength value of a wavelength included in the wavelength list, and an object strength value that is a strength value acquired from light emitting spectra and is a strength value of a wavelength included in the wavelength list for each analysis object element, and performs a constituent analysis for estimating a type of an element included in a sample on the basis of the calculated similarity.SELECTED DRAWING: Figure 7

Description

Technical Field

[0001] The technology disclosed herein relates to an analyzer for analyzing components of a measurement object, a processing unit of the analyzer, an analysis method, an analysis program, and a computer-readable storage medium storing the analysis program.

Background Art

[0002] For example, Patent Document 1 discloses a component analyzer for a sample using laser light. Specifically, the component analyzer described in Patent Document 1 includes a light source that irradiates laser light and an analyzer that acquires an emission spectrum of light generated by the irradiation of the laser light in order to perform component analysis using laser-induced breakdown spectroscopy (LIBS). With this analyzer, the light generated by the irradiation of the laser light is spectroscopically analyzed for each wavelength, and an emission spectrum is generated. In laser-induced breakdown spectroscopy, based on the emission spectrum, the composition of the sample and the content of the sample can be analyzed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It is known that the emission spectrum of light generated by the irradiation of laser light has a very large number of peaks in a wide wavelength range. By accurately identifying the peaks of the sample to be analyzed, the accuracy of component analysis can be improved. In order to improve the accuracy of component analysis, there is a method of using a spectroscope with high wavelength resolution. It is considered that if a spectroscope with high wavelength resolution is used, it becomes possible to accurately identify the peaks of the sample to be analyzed. However, in this case, the size of the apparatus increases and the usability deteriorates.

Means for Solving the Problem

[0005] In order to solve the above problems, a first disclosure of the present invention irradiates a surface of a sample with laser light, and based on an emission spectrum of plasma light generated by the irradiation and reference spectra of a plurality of elements to be analyzed, among the plurality of elements to be analyzed, a laser-induced breakdown spectroscopic apparatus (analysis apparatus) for performing component analysis of the sample can be premised.

[0006] The laser-induced breakdown spectroscopic apparatus includes a storage unit that stores, for each element to be analyzed, a wavelength list that is a combination of a plurality of wavelengths used during component analysis, a reference intensity value that is an intensity value obtained from a reference spectrum and corresponds to a wavelength included in the wavelength list, and a target intensity value that is an intensity value obtained from an emission spectrum and corresponds to a wavelength included in the wavelength list, and a similarity calculation unit that sequentially calculates, for each element to be analyzed, a similarity between the reference intensity value and the target intensity value, and a component analysis unit that estimates the type of element contained in the sample based on the similarity calculated by the similarity calculation unit.

[0007] According to this configuration, the storage unit can store, for each element to be analyzed, a unique wavelength list suitable for analysis of the element to be analyzed. The similarity calculation unit can calculate the similarity based on the reference intensity values obtained for a plurality of wavelengths included in the wavelength list and the target intensity values obtained for a plurality of wavelengths included in the wavelength list using this wavelength list. That is, the similarity calculation unit can calculate the similarity by regarding each of the plurality of reference intensity values and the plurality of target intensity values as one set (vector) instead of the similarity between the reference intensity value and the target intensity value corresponding to each individual wavelength. Thereby, even when the wavelength of the peak cannot be accurately specified, misjudgment of the elements contained in the sample can be suppressed, and the component analysis accuracy can be improved.

[0008] In another disclosure of the present invention, the laser-induced breakdown spectroscopy apparatus includes an intensity ratio calculation unit that calculates an intensity ratio between a reference intensity value and a target intensity value of a wavelength included in a wavelength list. Then, the component analysis unit estimates the content of an element contained in the sample based on the intensity ratio calculated by the intensity ratio calculation unit.

[0009] According to this configuration, the content of an element can be estimated using a unique wavelength list suitable for the analysis of the element to be analyzed, and even when the wavelength of the peak cannot be accurately specified, the content of the element contained in the sample can be estimated more accurately.

[0010] In another disclosure of the present invention, the storage unit stores, in association with the element to be analyzed, the wavelengths of a plurality of peaks included in the reference spectrum as a wavelength list. According to this configuration, for each element to be analyzed, since the wavelength at which a peak is estimated to appear is included in the wavelength list, the element contained in the sample can be estimated more accurately.

[0011] In another disclosure of the present invention, when the wavelength of one peak included in the reference spectrum of one element to be analyzed and the wavelength of another peak included in the reference spectrum of another element to be analyzed exist within a predetermined wavelength range, the storage unit stores, as a wavelength list corresponding to the one element to be analyzed, a wavelength list in which the wavelength of one peak among the plurality of peaks included in the reference spectrum of the one element to be analyzed is excluded. According to this configuration, when peaks are close to each other, it is possible to store an optimized wavelength list for each element to be analyzed, such as excluding the wavelength corresponding to the peak from the wavelength list.

[0012] In addition, each of the above-described configurations, functions, etc. may be realized in part or in whole by hardware, or may be realized by software by a processing unit interpreting and executing a program for realizing each function. Information such as a program for realizing each function can be stored in a recording device such as a memory or a hard disk, or a recording medium such as a memory card.

Advantages of the Invention

[0013] According to the present disclosure, without causing the apparatus to be enlarged, it is possible to more accurately estimate the elements contained in the sample and the content of the elements.

Brief Description of the Drawings

[0014]

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DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. Note that the following description is illustrative.

[0016] <Overall Configuration of Analysis Observation Apparatus A> FIG. 1 is a schematic diagram exemplifying the overall configuration of an analysis observation apparatus A as an analysis apparatus according to an embodiment of the present disclosure. The analysis observation apparatus A illustrated in FIG. 1 can perform magnified observation of a sample SP as an object to be observed and an object to be analyzed, and can perform component analysis of the sample SP. The analysis apparatus is also referred to as a laser-induced breakdown spectroscopy apparatus.

[0017] Specifically, the analysis observation apparatus A according to the present embodiment can search for a site where component analysis is to be performed in the sample SP by magnifying and imaging a sample SP composed of, for example, a sample such as a minute object, an electronic component, a workpiece, etc., and can perform inspection, measurement, etc. of the appearance thereof. When focusing on the observation function of the analysis observation apparatus A, it can be referred to as a magnifying observation apparatus, simply as a microscope, or as a digital microscope.

[0018] When performing component analysis of the sample SP, the analysis and observation apparatus A can also implement techniques such as Laser Induced Breakdown Spectroscopy (LIBS) and Laser Induced Plasma Spectroscopy (LIPS). When focusing on its analysis function, the analysis and observation apparatus A can also be referred to as a component analysis apparatus, simply as an analysis apparatus, or as a spectroscopic apparatus.

[0019] As shown in FIG. 1, the analysis and observation apparatus A according to the present embodiment includes, as main components, an optical system assembly (optical system main body) 1, a controller main body 2, and an operation unit 3.

[0020] Among these, the optical system assembly 1 can image and analyze the sample SP and output an electrical signal corresponding to the imaging result and the analysis result to the outside.

[0021] The controller main body 2 has a control unit 21 for controlling various components constituting the optical system assembly 1, such as a first camera 81. The controller main body 2 can cause the optical system assembly 1 to observe and analyze the sample SP via the control unit 21. The controller main body 2 also has a display unit 22 capable of displaying various information. Images captured by the optical system assembly 1, data indicating the analysis results of the sample SP, etc. can be displayed on this display unit 22.

[0022] The operation unit 3 includes a mouse 31, a console 32, etc. for receiving operation inputs from the user. By operating buttons, adjustment knobs, etc. on the console 32, the controller main body 2 can be instructed to capture image data, adjust brightness, focus the first camera 81, etc.

[0023] <Details of the optical system assembly 1> As shown in FIG. 1, the optical system assembly 1 includes a stage 4 that supports various devices and on which a sample SP is placed, and a head unit 6 attached to the stage 4. Here, the head unit 6 is formed by mounting an observation housing 90 in which an observation optical system 9 is housed on an analysis housing 70 in which an analysis optical system 7 is housed. Here, the analysis optical system 7 is an optical system for performing component analysis of the sample SP. The observation optical system 9 is an optical system for performing magnified observation of the sample SP. The head unit 6 is configured as a group of devices having both an analysis function and a magnified observation function of the sample SP.

[0024] In the following description, as shown in FIG. 1, the front-rear direction and the left-right direction of the optical system assembly 1 are defined. That is, the side facing the user is the front side of the optical system assembly 1, the opposite side is the rear side of the optical system assembly 1, and when the user and the optical system assembly 1 face each other, the right side as seen from the user is the right side of the optical system assembly 1, and the left side as seen from the user is the left side of the optical system assembly 1. Note that the definitions of the front-rear direction and the left-right direction are for assisting in understanding the description and do not limit the actual usage state. Any direction can be used as the front.

[0025] Although details will be described later, the head unit 6 can move along the central axis Ac shown in FIG. 1 or swing around this central axis Ac. As shown in FIG. 1 and the like, this central axis Ac is configured to extend along the aforementioned front-rear direction.

[0026] (Stage 4) The stage 4 has a base 41 installed on a workbench or the like, a stand 42 connected to the base 41, and a mounting table 5 supported by the base 41 or the stand 42. This stage 4 is a member for defining the relative positional relationship between the mounting table 5 and the head unit 6, and is configured to be able to attach at least the observation optical system 9 and the analysis optical system 7 of the head unit 6.

[0027] (Head unit 6) The head unit 6 includes a head attachment member 61, an analysis unit formed by housing an analysis optical system 7 in an analysis housing 70, an observation unit formed by housing an observation optical system 9 in an observation housing 90, a housing connector 64, and a slide mechanism (horizontal drive mechanism) 65. The head attachment member 61 is a member for connecting the analysis housing 70 to the stand 42. The analysis unit is a device for performing component analysis of the sample SP by the analysis optical system 7. The observation unit 63 is a device for observing the sample SP by the observation optical system 9. The housing connector 64 is a member for connecting the observation housing 90 to the analysis housing 70. The slide mechanism 65 is a mechanism for sliding the analysis housing 70 relative to the stand 42.

[0028] Hereinafter, the configurations of the analysis unit, the observation unit, and the slide mechanism 65 will be described in order.

[0029] - Analysis unit - FIG. 3 is a schematic diagram illustrating the configuration of the analysis optical system 7.

[0030] The analysis unit includes an analysis optical system 7 and an analysis housing 70 in which the analysis optical system 7 is housed. The analysis optical system 7 is a collection of components for analyzing the sample SP as an analysis object, and each component is housed in the analysis housing 70. The analysis housing 70 houses a first camera 81 and first and second detectors 77A and 77B as detectors. Also included in the elements for analyzing the sample SP is the control unit 21 of the controller main body 2.

[0031] The analysis optical system 7 can perform analysis using, for example, the LIBS method. A communication cable C1 for transmitting and receiving electrical signals between the analysis optical system 7 and the controller main body 2 is connected to the analysis optical system 7. This communication cable C1 is not essential, and the analysis optical system 7 and the controller main body 2 may be connected by wireless communication.

[0032] As shown in FIG. 3, the analytical optical system 7 according to the present embodiment includes an emission unit 71, an output adjustment unit 72, a deflection element 73, a reflective objective lens 74 as a collection head, a spectroscopic element 75, a first parabolic mirror 76A, a first detector 77A, a first beam splitter 78A, a second parabolic mirror 76B, a second detector 77B, a second beam splitter 78B, a coaxial illumination 79, an imaging lens 80, and a first camera 81. Some of the components of the analytical optical system 7 are also shown in FIG. 2.

[0033] The emission unit 71 emits laser light to the sample SP. In particular, the emission unit 71 according to the present embodiment is composed of a laser light source that emits laser light to the sample SP. Note that the emission unit 71 according to the present embodiment can output laser light composed of ultraviolet rays.

[0034] The output adjustment unit 72 is disposed on the optical path connecting the emission unit 71 and the deflection element 73, and can adjust the output of the laser light.

[0035] The laser light whose output is adjusted by the output adjustment unit 72 is reflected by a mirror (not shown) and enters the deflection element 73.

[0036] Specifically, the deflection element 73 reflects the laser light output from the emission unit 71 and passing through the output adjustment unit 72, and guides it to the sample SP via the reflective objective lens 74. On the other hand, the light generated in the sample SP corresponding to this laser light (the light emitted along with the plasma generation on the surface of the sample SP, hereinafter referred to as "plasma light") is passed through, and is laid out so as to be guided to the first detector 77A and the second detector 77B. The deflection element 73 is also laid out so as to pass the visible light condensed for imaging and guide most of it to the first camera 81.

[0037] The ultraviolet laser light reflected by the deflection element 73 propagates along the analytical optical axis Aa as parallel light and reaches the reflective objective lens 74.

[0038] The reflective objective lens 74 as a collection head is configured to collect plasma light, which is an electromagnetic wave generated in the sample SP when the laser light emitted from the emission unit 71 irradiates the sample SP. In particular, the reflective objective lens 74 according to the present embodiment is configured to condense the laser light and irradiate the sample SP, and to collect the plasma light generated in the sample SP corresponding to the laser light irradiated to the sample SP.

[0039] The reflective objective lens 74 has an analysis optical axis Aa extending along the substantially vertical direction described above. The analysis optical axis Aa is provided to be parallel to the observation optical axis Ao of the objective lens 92 of the observation optical system 9.

[0040] Specifically, the reflective objective lens 74 according to the present embodiment is a Schwarzschild type objective lens composed of two mirrors. As shown in FIG. 3, this reflective objective lens 74 has a first mirror 74a that is semi-annular and relatively large in diameter, and a second mirror 74b that is disc-shaped and relatively small in diameter.

[0041] The first mirror 74a allows the laser light to pass through an opening provided in its central portion, while reflecting the plasma light generated at the sample SP by a mirror surface provided around it. The latter plasma light is reflected again by the mirror surface of the second mirror 74b and passes through the opening of the first mirror 74a in a state coaxial with the laser light.

[0042] The second mirror 74b is configured to transmit the laser light that has passed through the opening of the first mirror 74a, while condensing and reflecting the plasma light reflected by the first mirror 74a. The former laser light irradiates the sample SP, while the latter plasma light passes through the opening of the first mirror 74a and reaches the deflection element 73 as described above.

[0043] The spectroscopic element 75 is disposed between the deflection element 73 and the first beam splitter 78A in the optical axis direction of the reflective objective lens 74 (the direction along the analysis optical axis Aa), guiding a part of the plasma light generated by the sample SP to the first detector 77A, and guiding the other part to the second detector 77B and the like. Most of the latter plasma light is guided to the second detector 77B, and the rest reaches the first camera 81.

[0044] The first parabolic mirror 76A is a so-called parabolic mirror and is disposed between the spectroscopic element 75 and the first detector 77A. The first parabolic mirror 76A condenses the plasma light reflected by the spectroscopic element 75 and makes the condensed plasma light incident on the first detector 77A.

[0045] The first detector 77A receives the plasma light generated in the sample SP and collected by the reflective objective lens 74, and generates a spectrum which is the intensity distribution for each wavelength of the plasma light.

[0046] In particular, when the emitting unit 71 is constituted by a laser light source and the reflective objective lens 74 is configured to condense the plasma light generated corresponding to the irradiation of the laser light, the first detector 77A separates the light by reflecting the light at different angles for each wavelength, and makes each of the separated lights incident on an image sensor having a plurality of pixels. Thereby, the wavelength of the light received by each pixel can be made different, and the received light intensity can be acquired for each wavelength. In this case, the spectrum corresponds to the intensity distribution for each wavelength of the light.

[0047] Note that the spectrum may be constituted by the received light intensity acquired for each wave number. Since the wavelength and the wave number uniquely correspond to each other, even when the received light intensity acquired for each wave number is used, the spectrum can be regarded as the intensity distribution for each wavelength. The same applies to the second detector 77B described later.

[0048] The first beam splitter 78A reflects a part of the light that has passed through the spectroscopic element 75 (infrared plasma light including the visible light band) and guides it to the second detector 77B, while transmitting the other part (a part of the visible light band) and guiding it to the second beam splitter 78B. Among the plasma light belonging to the visible light band, a relatively large amount of plasma light is guided to the second detector 77B, and a relatively small amount of plasma light is guided to the first camera 81 via the second beam splitter 78B.

[0049] The second parabolic mirror 76B is a so-called parabolic mirror similar to the first parabolic mirror 76A, and is disposed between the first beam splitter 78A and the second detector 77B. The second parabolic mirror 76B condenses the plasma light reflected by the first beam splitter 78A and makes the condensed plasma light incident on the second detector 77B.

[0050] Similar to the first detector 77A, the second detector 77B receives the plasma light generated in the sample SP when the laser light emitted from the emission unit 71 irradiates the sample SP, and generates a spectrum that is the intensity distribution for each wavelength of the plasma light.

[0051] The ultraviolet spectrum generated by the first detector 77A and the infrared spectrum generated by the second detector 77B are input to the control unit 21. Based on these spectra, the control unit 21 performs component analysis of the sample SP using the basic principle described later. The control unit 21 can perform component analysis using a wider frequency range by combining and using the ultraviolet spectrum and the infrared spectrum.

[0052] The second beam splitter 78B reflects the illumination light (visible light) emitted from the LED light source 79a and passing through the optical element 79b, and irradiates the sample SP through the first beam splitter 78A, the spectroscopic element 75, the deflection element 73, and the reflective objective lens 74. The reflected light (visible light) reflected by the sample SP returns to the analysis optical system 7 through the reflective objective lens 74.

[0053] The coaxial illumination 79 includes an LED light source 79a that emits illumination light, and an optical element 79b through which the illumination light emitted from the LED light source 79a passes. The coaxial illumination 79 functions as so-called "coaxial epi-illumination". The illumination light emitted from the LED light source 79a propagates coaxially with the laser light (primary electromagnetic wave) output from the output unit 71 and irradiated onto the sample SP, and the light (secondary electromagnetic wave) returning from the sample SP.

[0054] The second beam splitter 78B also further transmits the reflected light that has returned to the analysis optical system 7 and passed through the first beam splitter 78A, and the plasma light that has passed through the first beam splitter 78A without reaching the first and second detectors 77A and 77B, and makes it incident on the first camera 81 via the imaging lens 80.

[0055] In the example shown in FIG. 3, the coaxial illumination 79 is built into the analysis housing 70, but the present disclosure is not limited to such a configuration. For example, a light source may be laid out outside the analysis housing 70, and the light source and the analysis optical system 7 may be optically coupled to the optical system via an optical fiber cable.

[0056] The first camera 81 receives the reflected light reflected by the sample SP via the reflective objective lens 74. The first camera 81 images the sample SP by detecting the amount of received light of the received reflected light.

[0057] Specifically, the first camera 81 according to the present embodiment photoelectrically converts the light incident through the imaging lens 80 by a plurality of pixels arranged on its light receiving surface, and converts it into an electrical signal corresponding to the optical image of the subject (sample SP).

[0058] Then, the first camera 81 inputs the electrical signal generated by detecting the amount of received light at each light receiving element to the control unit 21 of the controller main body 2. The control unit 21 generates image data corresponding to the optical image of the subject based on the input electrical signal. The control unit 21 can display the image data thus generated on the display unit 22 or the like as an image obtained by imaging the subject.

[0059] The optical components described so far are housed in the aforementioned analysis housing 70. A through-hole 70a is provided in the lower surface of the analysis housing 70. The reflective objective lens 74 faces the placement surface 51a through this through-hole 70a.

[0060] -Basic principle of analysis by the analysis optical system 7- The control unit 21 performs component analysis of the sample SP based on the spectra input from the first detector 77A and the second detector 77B serving as detectors. As a specific analysis method, the LIBS method can be used as described above. The LIBS method is a method for analyzing the components contained in the sample SP at the elemental level (so-called elemental analysis method).

[0061] According to the LIBS method, evacuation is not required, and component analysis can be performed in an open-air state. Also, although it is a destructive test of the sample SP, processes such as dissolving the entire sample SP are not required, and the position information of the sample SP remains (it is only a local destructive test).

[0062] -Observation unit- The observation unit includes an observation optical system 9 and an observation housing 90 that houses the observation optical system 9. The observation optical system 9 is a collection of components for observing the sample SP as an observation object, and each component is housed in the observation housing 90. The observation housing 90 is configured separately from the aforementioned analysis housing 70 and houses the second camera 93 as the second imaging unit. Also, the control unit 21 of the controller main body 2 is included in the elements for observing the sample SP.

[0063] The observation optical system 9 includes a lens unit 9a having an objective lens 92. This lens unit 9a corresponds to a cylindrical lens barrel disposed on the lower end side of the observation housing 90. The lens unit 9a is held by the analysis housing 70.

[0064] The observation housing 90 is connected to a communication cable C2 for transmitting and receiving electrical signals to and from the controller main body 2, and an optical fiber cable C3 for guiding illumination light from the outside. Note that the communication cable C2 is not essential, and the observation optical system 9 and the controller main body 2 may be connected by wireless communication.

[0065] Specifically, as shown in FIG. 2, the observation optical system 9 includes a mirror group 91, an objective lens 92, a second camera 93 as a second imaging unit, a second coaxial illumination 94, a second side illumination 95, and a magnifying optical system 96.

[0066] The objective lens 92 has an observation optical axis Ao extending substantially in the vertical direction, condenses illumination light and irradiates a sample SP placed on the mounting table main body 51, and condenses light (reflected light) from the sample SP. The observation optical axis Ao is provided to be parallel to the analysis optical axis Aa of the reflection type objective lens 74 of the analysis optical system 7. The reflected light collected by the objective lens 92 is received by the second camera 93.

[0067] The mirror group 91 transmits the reflected light collected by the objective lens 92 and guides this to the second camera 93. The mirror group 91 according to the present embodiment can be configured using a total reflection mirror, a beam splitter, etc., as illustrated in FIG. 2. The mirror group 91 also reflects the illumination light irradiated from the second coaxial illumination 94 and guides this to the objective lens 92.

[0068] The second camera 93 receives the reflected light reflected by the sample SP via the objective lens 92. The second camera 93 images the sample SP by detecting the amount of received light of the received reflected light. The second camera 93 according to the present embodiment is configured by an image sensor made of CMOS, like the first camera 81, but an image sensor made of CCD may also be used.

[0069] Then, the second camera 93 inputs an electrical signal generated by detecting the amount of light received by each light-receiving element to the control unit 21 of the controller main body 2. Based on the input electrical signal, the control unit 21 generates image data corresponding to the optical image of the subject. The control unit 21 can display the thus-generated image data on the display unit 22 or the like as an image obtained by imaging the subject.

[0070] The second coaxial illumination 94 emits illumination light guided from the optical fiber cable C3. The second coaxial illumination 94 irradiates the illumination light through the same optical path as the reflected light condensed through the objective lens 92. That is, the second coaxial illumination 94 functions as "coaxial epi-illumination" coaxial with the observation optical axis Ao of the objective lens 92. Instead of guiding illumination light from the outside through the optical fiber cable C3, a light source may be built into the lens unit 9a. In that case, the optical fiber cable C3 becomes unnecessary.

[0071] The second side illumination 95 is constituted by a ring illumination arranged so as to surround the objective lens 92 as schematically illustrated in FIG. 2. Similar to the side illumination 84 in the analytical optical system 7, the second side illumination 95 irradiates illumination light from obliquely above the sample SP.

[0072] The magnifying optical system 96 is arranged between the mirror group 91 and the second camera 93 and is configured to be able to change the magnification of the sample SP by the second camera 93.

[0073] - Slide mechanism 65 - FIG. 4 is a diagram for explaining the horizontal movement of the head portion 6 by the slide mechanism 65.

[0074] The slide mechanism 65 is configured to move the relative positions of the observation optical system 9 and the analysis optical system 7 with respect to the mounting table main body 51 along the horizontal direction so that imaging of the sample SP by the observation optical system 9 and irradiation of laser light (in other words, irradiation of laser light by the emission unit 71 of the analysis optical system 7) when generating a spectrum by the analysis optical system 7 can be performed on the same location of the sample SP as the observation object.

[0075] The moving direction of the relative position by the slide mechanism 65 can be the arrangement direction of the observation optical axis Ao and the analysis optical axis Aa. As shown in FIG. 4, the slide mechanism 65 according to the present embodiment moves the relative positions of the observation optical system 9 and the analysis optical system 7 with respect to the mounting table main body 51 along the front-rear direction.

[0076] The slide mechanism 65 according to the present embodiment relatively displaces the analysis housing 70 with respect to the stand 42 and the head attachment member 61. Since the analysis housing 70 and the lens unit 9a are connected by the housing coupler 64, the lens unit 9a is also displaced integrally by displacing the analysis housing 70.

[0077] Specifically, the slide mechanism 65 according to the present embodiment includes a guide rail 65a and an actuator 65b. Among them, the guide rail 65a is configured to protrude forward from the front surface of the head attachment member 61.

[0078] As shown in FIG. 4, when the slide mechanism 65 operates, the head unit 6 slides along the horizontal direction, and the relative positions of the observation optical system 9 and the analysis optical system 7 with respect to the mounting table 5 move (horizontal movement). By this horizontal movement, the head unit 6 switches between a first mode in which the reflective objective lens 74 faces the sample SP and a second mode in which the objective lens 92 faces the sample SP. The slide mechanism 65 can slide the analysis housing 70 and the observation housing 90 between the first mode and the second mode.

[0079] By configuring as described above, it becomes possible to execute, from the same direction, the generation of an image of the sample SP by the observation optical system 9 and the generation of a spectrum by the analysis optical system 7 (specifically, the irradiation of laser light by the analysis optical system 7 when the spectrum is generated by the analysis optical system 7) at the timings before and after switching between the first mode and the second mode, with respect to the same location in the sample SP.

[0080] <Details of the detector> FIG. 5 is a diagram illustrating the configurations of the first detector 77A and the second detector 77B as detectors. The detector includes a slit 101 that narrows the incident plasma light, a first concave mirror 102 that condenses and reflects the plasma light that has passed through the slit 101, a diffraction element 103 that receives and diffracts the plasma light reflected by the first concave mirror 102, a second concave mirror 104 that receives and further reflects the plasma light diffracted by the diffraction element 103, and a light receiving element 105 that receives the plasma light reflected by the second concave mirror 104, and has a Czerny-Turner type configuration. When the plasma light is diffracted by the diffraction element 103, each pixel column of the light receiving element receives plasma light with different wavelengths. That is, the spectrum generated by this detector is a multi-dimensional quantity (multi-dimensional vector) having a dimension corresponding to the number of pixel columns.

[0081] <Details of the controller main body> FIG. 6 is a block diagram illustrating the configuration of the control unit 21 of the controller main body 2. In the present embodiment, the controller main body 2 and the optical system assembly 1 are configured separately, but the present disclosure is not limited to such a configuration. At least a part of the controller main body 2 may be provided in the optical system assembly 1. For example, at least a part of the processing unit 21a that constitutes the control unit 21 can be incorporated in the optical system assembly 1.

[0082] As described above, the controller main body 2 according to the present embodiment includes a control unit 21 that performs various processes, and a display unit 22 that displays information related to the processes performed by the control unit 21.

[0083] The emission unit 71, the first detector 77A, and the second detector 77B are electrically controlled by the control unit 21.

[0084] Also, the output signals of the first detector 77A and the second detector 77B are input to the control unit 21. The control unit 21 executes operations and the like based on the input output signals, and executes processing based on the operation results. As hardware for performing such processing, the control unit 21 according to the present embodiment includes a processing unit 21a that executes various processes, and a primary storage unit 21b and a secondary storage unit 21c that store data related to the processes performed by the processing unit 21a.

[0085] The processing unit 21a is composed of a CPU, a system LSI, a DSP, etc. The processing unit 21a executes various programs to analyze the sample SP or control each part of the analysis observation apparatus A such as the display unit 22. In particular, the processing unit 21a according to the present embodiment can control the display screen on the display unit 22 based on information indicating the analysis result of the sample SP.

[0086] Note that the display unit as a control target by the processing unit 21a is not limited to the display unit 22 included in the controller main body 2. The "display unit" according to the present disclosure also includes a display unit not provided in the analysis observation apparatus A. For example, a display of a computer, a tablet terminal, etc. connected to the analysis observation apparatus A by wire or wirelessly may be regarded as a display unit, and information indicating the analysis result of the sample SP and various image data may be displayed on the display unit. Thus, the present disclosure can also be applied to an analysis system including the analysis observation apparatus A and a display unit connected to the analysis observation apparatus A by wire or wirelessly.

[0087] As shown in FIG. 6, the processing unit 21a according to the present embodiment includes, as functional elements, an emission control unit 211, a spectrum acquisition unit 212, a user interface control unit (hereinafter simply referred to as "UI control unit") 221, an analysis processing unit 230, a wavelength selection unit 241, and a coefficient setting unit 242. These elements may be realized by a logic circuit or may be realized by executing software. Further, at least a part of these elements may be provided in the optical system assembly 1 such as the head unit 6.

[0088] Note that the classification such as the spectrum acquisition unit 212 and the analysis processing unit 230 is merely for convenience and can be freely changed. For example, the analysis processing unit 230 may also serve as the spectrum acquisition unit 212, or the spectrum acquisition unit 212 may also serve as the analysis processing unit 230.

[0089] -Emission control unit 211- The emission control unit 211 shown in FIG. 6 controls the emission unit 71 in response to an input operation of the operation unit 3 by the user. That is, when the input reception unit 221b receives an analysis start operation by the user, the emission control unit 211 causes the emission unit 71 to emit laser light.

[0090] -Spectrum acquisition unit 212- The spectrum acquisition unit 212 shown in FIG. 6 acquires the spectra generated by the first and second detectors 77A and 77B as detectors.

[0091] Specifically, when laser light is emitted from the emission unit 71 in the first mode, plasma light, which is an electromagnetic wave, is generated. This plasma light reaches the first detector 77A and the second detector 77B.

[0092] The first and second detectors 77A and 77B as detectors generate the emission spectra of the plasma light that has reached each of them. The spectra thus generated are acquired by the spectrum acquisition unit 212. The spectra acquired by the spectrum acquisition unit 212 show the relationship between wavelength and intensity, and there are a plurality of peaks corresponding to the elements contained in the sample SP.

[0093] The spectra thus acquired by the spectrum acquisition unit 212 are output to the analysis processing unit 230 in order to perform component analysis of the sample SP.

[0094] The UI control unit 221 includes a display control unit 221a and an input reception unit 221b. The display control unit 221a causes the display unit 22 to display the component analysis result by the analysis processing unit 230 on the display unit 22. The input reception unit 221b receives operation inputs by the user through the operation unit 3.

[0095] -Analysis Processing Unit 230- The analysis processing unit 230 shown in FIG. 6 can determine that the element corresponding to the peak position is a component contained in the sample SP based on the peaks included in the emission spectrum acquired by the spectrum acquisition unit 212. Further, the analysis processing unit 230 estimates the component ratio of each element by comparing the magnitudes (peak intensities) of the peaks with each other.

[0096] The analysis processing unit 230 includes a preprocessing unit 231, a determination target specifying unit 232, an intensity acquisition unit 233, a similarity threshold setting unit 234, a similarity calculation unit 235, an intensity ratio calculation unit 236, and a component analysis unit 237. Details of the analysis processing unit 230 will be described later.

[0097] -Wavelength Selection Unit 241- The wavelength selection unit 241 shown in FIG. 6 can select the peak wavelengths that make up the wavelength list WL from among the plurality of peaks included in the reference spectrum Sr stored in the secondary storage unit 21c.

[0098] -Coefficient Setting Unit 242- The coefficient setting unit 242 shown in FIG. 6 can set weighting coefficients for a plurality of wavelengths included in the reference spectrum Sr stored in the secondary storage unit 21c.

[0099] -Primary storage unit 21b- The primary storage unit 21b is composed of a volatile memory. The primary storage unit 21b according to the present embodiment can primarily store parameters related to component analysis by the analysis processing unit 230. Also, a computer program executed by the processing unit 21a can be stored in the primary storage unit 21b. In this case, a computer program acquired from a recording medium such as a communication interface (not shown) or a memory card is stored in the primary storage unit 21b.

[0100] -Secondary storage unit 21c- The secondary storage unit 21c is composed of a non-volatile memory such as a hard disk drive or a solid state drive. The secondary storage unit 21c can continuously store a reference spectrum Sr, which is a spectrum acquired in advance for a plurality of predetermined elements, and a wavelength list WL in which a plurality of wavelengths constituting the reference spectrum Sr are associated with the elements. Note that the reference spectrum Sr and the wavelength list WL may be stored in a storage medium such as an optical disk instead of being stored in the secondary storage unit 21c, or may be stored in a computer, a tablet terminal, etc. that is connected to the analysis observation device A by wire or wirelessly.

[0101] <Component analysis of sample SP> FIG. 7A in FIG. 7 is a diagram showing an example of the reference spectrum Sr stored in the secondary storage unit 21c. This reference spectrum Sr is an example of the reference spectrum Sr of Fe, which is one of the elements to be analyzed. Although there are a very large number of peaks in the actual reference spectrum Sr, a simplified reference spectrum Sr is shown for the purpose of explanation.

[0102] FIG. 7B and FIG. 7C of FIG. 7 are diagrams showing an example of the wavelength list WL stored in the secondary storage unit 21c. In the example shown in FIG. 7B, the wavelength list WL is constituted by wavelengths corresponding to a plurality of peaks included in the reference spectrum Sr of Fe. This wavelength list WL is a combination of a plurality of wavelengths to be focused on during component analysis, that is, a plurality of wavelengths used during component analysis. Also, in the example shown in FIG. 7C, the wavelength list WL is constituted by setting a weighting coefficient applied to the intensity values corresponding to a plurality of wavelengths included in the reference spectrum Sr of Fe for each wavelength. In the example shown in FIG. 7C, a larger weighting coefficient is set around (in the vicinity of) the wavelength corresponding to the peak included in the reference spectrum Sr of Fe, and a smaller weighting coefficient is set as the distance from the wavelength corresponding to the peak increases. Also, in the example shown in FIG. 7C of FIG. 7, the weighting coefficient is set in the range from 0 to 1, but it may be appropriately optimized, such as setting the weighting coefficient in the range from 0 to 100 or in the range from -1 to 1. Furthermore, the wavelengths included in the wavelength list WL do not necessarily have to be wavelengths corresponding to the peaks included in the reference spectrum Sr. The wavelength list WL may exclude wavelengths corresponding to the peaks included in the reference spectrum Sr, or may include wavelengths other than the wavelengths corresponding to the peaks. Similarly, it is not always necessary to set a large coefficient for the wavelength corresponding to the peak in the weighting coefficient set in the wavelength list WL, and a small weighting coefficient may be set for the wavelength corresponding to the peak, or a large weighting coefficient may be set for wavelengths other than the wavelength corresponding to the peak.

[0103] FIG.8A in Fig. 8 shows an example of the reference spectrum Sr stored in the secondary storage unit 21c. This reference spectrum Sr is an example of the reference spectrum Sr of Cr, which is one of the elements to be analyzed. FIG.8B and FIG.8C in Fig. 8 show an example of the wavelength list WL stored in the secondary storage unit 21c. Similar to FIG.7B and FIG.7C in Fig. 7, the wavelength list WL is configured by the wavelengths corresponding to the plurality of peaks included in the reference spectrum Sr, or by setting the weighting coefficients applied to the intensity values corresponding to the plurality of wavelengths included in the reference spectrum Sr for each wavelength.

[0104] As shown in FIG.7B of Fig. 7 and FIG.8B of Fig. 8, when the wavelength list WL is configured by the wavelengths corresponding to the peaks included in the reference spectrum Sr, the wavelength list WL is composed of a combination of a plurality of different wavelengths for each element. That is, the wavelength list WL corresponding to Fe is composed of a plurality of wavelengths specified in advance to determine whether Fe is present. Also, the wavelength list WL corresponding to Cr is composed of a plurality of wavelengths specified in advance to determine whether Cr is present. In this way, for each element, a unique wavelength list WL is configured by combining the specific wavelengths to be focused on during component analysis.

[0105] As shown in FIG.7C of Fig. 7 and FIG.8C of Fig. 8, when the wavelength list WL is configured by setting the weighting coefficients applied to the intensity values corresponding to the plurality of wavelengths included in the reference spectrum Sr, the wavelength list WL is created by setting different weighting coefficients for each wavelength for each element. That is, for the wavelength list WL corresponding to Fe, a relatively large weighting coefficient is set for a predetermined wavelength suitable for determining whether Fe is present. In this way, different weighting coefficients are set for each element for the plurality of wavelengths constituting the reference spectrum Sr, thereby defining the wavelength list WL for each element.

[0106] FIG. 9 is a diagram illustrating a target spectrum St which is an emission spectrum of plasma light obtained by actually measuring a sample SP. That is, the target spectrum St shown in FIG. 9 is an emission spectrum of plasma light generated by the first detector 77A and the second detector 77B and acquired by the spectrum acquisition unit 212. Based on FIGS. 7 to 9, the type of element and the estimation of the element content rate by the analysis processing unit 230 will be described.

[0107] -Wavelength list WL- The wavelength list WL can be created for each element to be analyzed by theoretically estimating the wavelengths corresponding to the transitions between energy levels based on, for example, the spectral information of atoms published by the National Institute of Standards and Technology (NIST) in the United States. Also, a reference spectrum Sr which is actually a spectrum of a pure element is obtained, and a wavelength list can be created for each element to be analyzed based on the actually obtained reference spectrum Sr, such as regarding the maximum value appearing in the reference spectrum Sr as a peak. In this case, among the maximum values, the one with the largest absolute value can be regarded as a peak, or the one with a large difference between the maximum value and the minimum value can be regarded as a peak, or the one with a steep change in the intensity values before and after can be regarded as a peak. When the wavelength list WL is composed of wavelengths corresponding to a plurality of peaks, the wavelengths theoretically estimated, the wavelengths corresponding to the peaks included in the actually obtained reference spectrum Sr, specific wavelengths reflecting the characteristics of the element, etc. are included in the wavelength list WL. Also, when the wavelength list WL is composed by setting a weighting coefficient, a larger coefficient is set as the weighting coefficient for the wavelengths theoretically estimated, the wavelengths corresponding to the peaks included in the actually obtained reference spectrum Sr, specific wavelengths reflecting the characteristics of the element, etc. Here, when it is a characteristic of an element that the reference intensity value of a certain specific wavelength is low, that specific wavelength is an example of a "specific wavelength reflecting the characteristics of the element".

[0108] -Preprocessing unit 231- The preprocessing unit 231 estimates the abnormal wavelengths of the target spectrum St. As a method for estimating the abnormal wavelengths, for example, for each wavelength included in the wavelength list WL, the intensity similarity, which is the similarity between the reference intensity value, which is the intensity value obtained from the reference spectrum Sr, and the target intensity value, which is the intensity value obtained from the target spectrum St, is calculated, and a wavelength with a small intensity similarity can be regarded as an abnormal wavelength. In the examples shown in FIGS. 10A and 10B of FIG. 10, the target intensity values of wavelengths 301 nm, 303 nm, and 305 nm are 0.7 times the reference intensity value, while the target intensity value of wavelength 306.5 nm is 1.5 times the reference intensity value. Thus, the target intensity value of wavelength 306.5 nm is likely to be affected by other elements, and the intensity similarity is low. Therefore, the preprocessing unit 231 can estimate wavelength 306.5 nm as an abnormal wavelength. That is, the preprocessing unit 231 can regard a wavelength whose wavelength-intensity ratio is significantly different from other wavelengths as an abnormal wavelength.

[0109] -Determination target specifying unit 232- The determination target specifying unit 232 shown in FIG. 6 specifies which element among the plurality of elements to be analyzed is the determination target this time. That is, the determination target specifying unit 232 outputs each element specified as the determination target element to the intensity acquisition unit 233 one by one. The determination target specifying unit 232 may specify the elements to be determined one by one in order based on the list of elements to be analyzed, or may specify the elements to be determined by accepting the selection of any element by the user.

[0110] -Intensity acquisition unit 233- The intensity acquisition unit 233 shown in FIG. 6 sequentially acquires the intensity values at a predetermined wavelength in the target spectrum St, which is the emission spectrum of the plasma light acquired by the spectrum acquisition unit 212, and the reference spectrum Sr stored in the secondary storage unit 21c, for each analysis target element. When there are a plurality of wavelength lists WL for one analysis target element, they may be sequentially acquired for each wavelength list WL. The intensity acquisition unit 233 first acquires a plurality of wavelengths included in the wavelength list WL stored in the secondary storage unit 21c. Then, the intensity acquisition unit 233 calculates the intensity value of the reference spectrum Sr corresponding to each of the acquired wavelengths as a reference intensity value. By calculating the reference intensity value in this way by the intensity acquisition unit 233, the intensity value of the reference spectrum Sr at each wavelength included in the wavelength list WL is acquired. Then, the intensity acquisition unit 233 creates a set of reference intensity values with the plurality of reference intensity values acquired for each wavelength as one set. This set of reference intensity values can be represented in a multi-dimensional space where each wavelength included in the wavelength list WL corresponds to a coordinate axis on the spatial coordinates. That is, the set of reference intensity values is a multi-dimensional vector with the number of wavelengths included in the wavelength list WL as the number of dimensions. An example of the set of reference intensity values is shown in FIG. 10A of FIG. 10. In the example shown in FIG. 10A of FIG. 10, the plurality of wavelengths shown in FIG. 7B of FIG. 7 and the reference intensity values corresponding to each wavelength are held in tabular form as one dataset. Here, although it is described in tabular form for the sake of explanation, the present embodiment is not limited to this. For example, the set of reference intensity values may hold the plurality of wavelengths included in the wavelength list WL and the reference intensity values corresponding to each wavelength in graph form or spectrum form. Also, since the set of reference intensity values is expressed as a multi-dimensional vector, it may be held in vector form having a direction and a magnitude.

[0111] Next, the intensity acquisition unit 233 sequentially calculates, for each element to be analyzed, the intensity value of the target spectrum St corresponding to each of the acquired wavelengths as the target intensity value. By calculating the target intensity value in this way by the intensity acquisition unit 233, the intensity value of the target spectrum St at each wavelength included in the wavelength list WL is acquired. Then, the intensity acquisition unit 233 creates a set of target intensity values with the plurality of target intensity values acquired for each wavelength as one set. This set of target intensity values is a multi-dimensional vector having the number of wavelengths included in the wavelength list WL as the number of dimensions, similar to the set of reference intensity values. An example of the set of target intensity values is shown in FIG. 10B of FIG. 10. In the example shown in FIG. 10B of FIG. 10, the plurality of wavelengths shown in FIG. 7B of FIG. 7 and the target intensity values corresponding to each wavelength are held in tabular form as one dataset. Note that, similar to the above-mentioned "set of reference intensity values", the set of target intensity values may be held in other forms such as a graph form, a spectrum form, or a vector form.

[0112] In this way, the intensity acquisition unit 233 sequentially creates a set of reference intensity values and a set of target intensity values for each element to be analyzed, and outputs the created set of reference intensity values and the set of target intensity values to the similarity calculation unit 235.

[0113] Note that, in the set of reference intensity values and the set of target intensity values, the wavelengths estimated as abnormal wavelengths by the preprocessing unit 231 and the intensity values corresponding to the wavelengths may be excluded. By selectively extracting wavelengths with high similarity to the reference spectrum in this way and creating the set of reference intensity values and the set of target intensity values, the accuracy of component analysis can be improved.

[0114] Also, here, the case where the intensity acquisition unit 233 calculates the reference intensity value from the reference spectrum Sr stored in the secondary storage unit 21c has been described, but the present embodiment is not limited to this. For example, instead of or in addition to the reference spectrum Sr, the secondary storage unit 21c may store in advance a set of reference intensity values in which the wavelengths included in the wavelength list WL and the reference intensity values corresponding to each of the wavelengths are listed. In this case, the intensity acquisition unit 233 acquires the set of reference intensity values from the secondary storage unit 21c and outputs the acquired set of reference intensity values to the similarity calculation unit 235.

[0115] -Similarity calculation unit 235- The similarity calculation unit 235 shown in FIG. 6 sequentially calculates the similarity between the reference intensity value of the wavelength included in the wavelength list WL and the target intensity value of the wavelength included in the wavelength list WL for each element to be analyzed. This similarity can be calculated from the degree of coincidence (distance) between the normalized intensity values. Here, normalization may be realized by dividing each reference intensity value by the average value of the plurality of reference intensity values included in the set of reference intensity values and dividing each target intensity value by the average value of the plurality of target intensity values included in the set of target intensity values. Alternatively, it may be realized by dividing the plurality of reference intensity values included in the set of reference intensity values by the reference intensity value of a predetermined wavelength and dividing the plurality of target intensity values included in the set of target intensity values by the target intensity value of the above predetermined wavelength. Note that the methods listed here are merely examples, and the intensity values of a plurality of wavelengths, their average values, the intensity values of a continuous spectrum, their average values, areas, etc. may be used for normalization.

[0116] Then, the similarity calculation unit 235 sequentially calculates the difference (distance) between the reference intensity value and the target intensity value for each wavelength included in the wavelength list WL. Then, the similarity calculation unit 235 sequentially calculates the similarity for each analysis target element based on the calculated differences. Here, the similarity is calculated based on the average value of the difference (distance) between the corresponding intensity values ​​of the reference intensity value set and the target intensity value set, the maximum value of the difference, the root mean square of the difference, the maximum value of the square of the difference, etc. That is, the similarity calculation unit 235 applies a predetermined mathematical process to the difference between the corresponding intensity values ​​of the reference intensity value set and the target intensity value set, and calculates a larger similarity as the degree of agreement (the distance) between the reference intensity value set and the target intensity value set increases.

[0117] Here, the similarity between the set of reference intensity values ​​and the set of target intensity values ​​is calculated based on the intensity values ​​at multiple wavelengths included in the wavelength list WL, not the intensity values ​​at individual wavelengths. When the component analysis of the sample SP is performed by the LIBS method, there are many peaks that occur in the emission spectrum of the plasma light, and the peak of one element to be determined whether it is included in the sample SP and the peak of another element often appear at close wavelengths. In particular, when a detector with a relatively low resolution is used to miniaturize the device, this tendency is more pronounced. Therefore, in a method for determining the presence or absence of a peak for each wavelength, there is a risk that the presence of the one element to be determined is erroneously determined to be present due to the peak of another element, even though the one element to be determined is not present. Therefore, in this embodiment, the intensity acquisition unit 233 acquires a reference intensity value calculated from the reference spectrum Sr and a target intensity value calculated from the target spectrum St for multiple wavelengths included in the wavelength list WL. Then, the similarity calculation unit 235 calculates the similarity based on multiple differences between the corresponding intensity values ​​of the "set of reference intensity values" and the "set of target intensity values". This makes it possible to improve the accuracy of the component analysis of the sample SP.

[0118] Note that the similarity calculation unit 235 can also calculate the similarity as the ratio of the difference or intensity ratio between the reference intensity value and the target intensity value at each wavelength falling within a predetermined threshold. Also, in the calculation of similarity and the normalization process, outliers such as abnormal wavelengths estimated by the preprocessing unit 231 may be excluded, or a small weighting coefficient may be set for the outliers.

[0119] The calculation of similarity by the similarity calculation unit 235 will be described in detail with reference to FIGS. 9 and 10. As described above, the similarity calculation unit 235 acquires the set of reference intensity values and the set of target intensity values generated by the intensity acquisition unit 233. The set of reference intensity values acquired here corresponds to FIG. 10A in FIG. 10, and the set of target intensity values corresponds to FIG. 10B in FIG. 10. In this case, the similarity calculation unit 235 can regard each of the set of reference intensity values and the set of target intensity values as a vector and calculate the similarity based on the degree of coincidence of the unit vectors. That is, in a multi-dimensional space with each wavelength as a coordinate axis, the vectors corresponding to the set of wavelength and intensity values are uniquely determined for each of the set of reference intensity values and the set of target intensity values. The similarity calculation unit 235 calculates the vector corresponding to the set of reference intensity values and the vector corresponding to the set of target intensity values, and calculates the similarity based on the degree of coincidence of these vectors. Here, the degree of coincidence of the vectors can be calculated based on, for example, the direction of the unit vectors. When the directions of the unit vectors of the vector corresponding to the set of reference intensity values and the vector corresponding to the set of target intensity values are the same, the similarity calculation unit 235 can calculate a large value as the similarity. Also, when the directions of the respective unit vectors are different, the similarity calculation unit 235 can calculate the similarity so that the similarity decreases as the difference between the unit vectors increases according to the difference in the directions of the unit vectors. Although the details are omitted, the cosine similarity between the vector corresponding to the set of reference intensity values and the vector corresponding to the set of target intensity values can also be used as the degree of coincidence of the vectors. Note that in the calculation of the degree of coincidence of the vectors, wavelengths excluding the abnormal wavelengths estimated by the preprocessing unit 231 among the plurality of wavelengths included in the wavelength list WL can be used.

[0120] As described above, the preprocessing unit 231 estimates the wavelength of 306.5 nm as an abnormal wavelength among the wavelengths included in the target spectrum St. Therefore, a method of qualitative analysis using wavelengths other than the wavelength estimated as the abnormal wavelength by the preprocessing unit 231 will be described. In the example shown in FIG. 10A of FIG. 10, the vector corresponding to the set of reference intensity values is represented as (301, 303, 305) = (8000, 11000, 6000). Also, in the example shown in FIG. 10B of FIG. 10, the vector corresponding to the set of target intensity values is represented as (301, 303, 305) = (5600, 7700, 4200). Since these vectors have substantially the same direction and only differ in magnitude, the degree of coincidence is high. Therefore, the similarity calculation unit 235 calculates a large value as the similarity between the set of reference intensity values and the set of target intensity values. Also, although not shown, when the vector corresponding to the set of target intensity values is represented as (301, 303, 305) = (7000, 7700, 4200), the direction of the vector corresponding to the set of reference intensity values and the vector corresponding to the set of target intensity values is different and the degree of coincidence is low. Therefore, the similarity calculation unit 235 calculates a relatively small value as the similarity between the set of reference intensity values and the set of target intensity values compared to the above case.

[0121] The method for calculating the similarity according to this embodiment can also be described as follows. The similarity calculation unit 235 can calculate the similarity based on the degree of coincidence between the ratios among a plurality of reference intensity values included in the set of reference intensity values and the ratios among a plurality of target intensity values included in the set of target intensity values. In the example shown in FIG. 10A of FIG. 10, the ratio among a plurality of reference intensity values included in the set of reference intensity values is (301:303:305) = (8:11:6). Also, in the example shown in FIG. 10B of FIG. 10, the ratio among a plurality of target intensity values included in the set of target intensity values is (301:303:305) = (8:11:6). Since these ratios are all substantially the same, the degree of coincidence between the ratio among a plurality of reference intensity values included in the set of reference intensity values and the ratio among a plurality of target intensity values included in the set of target intensity values is high. Therefore, the similarity calculation unit 235 calculates a large value as the similarity between the set of reference intensity values and the set of target intensity values. Also, although not shown in the figure, when the target intensity value at a wavelength of 301 nm fluctuates greatly, such as being 7000, the ratio among a plurality of target intensity values included in the set of target intensity values changes from the above value, and the degree of coincidence between the ratio among a plurality of reference intensity values included in the set of reference intensity values and the ratio among a plurality of target intensity values included in the set of target intensity values decreases. In such a case, for example, when looking at the wavelength of 303 nm individually, the similarity between the reference intensity value and the target intensity value is high. However, when the intensity values of a plurality of wavelengths (a plurality of wavelengths included in the wavelength list) serving as the determination criteria for one element (Fe) to be determined are grouped into a "set of reference intensity values" and a "set of target intensity values", the degree of coincidence decreases between the set of reference intensity values, which are a plurality of grouped reference intensity values, and the set of target intensity values, which are a plurality of grouped target intensity values. Therefore, the similarity calculation unit 235 calculates a relatively small value as the similarity between the set of reference intensity values and the set of target intensity values compared to the above case. In this case as well, the degree of coincidence can be calculated based on the distance between the "set of reference intensity values" and the "set of target intensity values".

[0122] Thus, in this embodiment, the similarity calculation unit 235 calculates the similarity between the ratio of a plurality of reference intensity values corresponding to each wavelength included in the wavelength list and the ratio of a plurality of target intensity values corresponding to each wavelength included in the wavelength list. As a result, it is possible to determine whether or not one element of the determination target exists based on the intensity values of a plurality of wavelengths, so that the presence or absence of the element can be estimated with higher accuracy.

[0123] Note that such a determination method is particularly effective when the above-mentioned Czerny-Turner type detector is used, that is, when a detector with a generally lower wavelength resolution than other detectors such as an Echelle type is used. The Czerny-Turner type detector has the advantage that the size of the entire apparatus can be reduced because it is smaller in size than other types of detectors. However, as the size of the detector decreases, the wavelength resolution decreases. Even in such a case where the wavelength resolution is low, instead of estimating the presence or absence of an element based on the intensity values of individual wavelengths, the accuracy in estimating the presence or absence of an element can be improved by estimating the presence or absence of an element based on a data set (vector) in which the intensity values of a plurality of wavelengths are regarded as one set.

[0124] -Intensity Ratio Calculation Unit 236- The intensity ratio calculation unit 236 shown in FIG. 6 calculates the intensity ratio between the reference intensity value and the target intensity value of the wavelengths included in the wavelength list WL. The intensity ratio calculation unit 236 calculates the intensity ratio between the reference intensity value and the target intensity value corresponding to at least one wavelength among the plurality of wavelengths included in the wavelength list WL. In the cases shown in FIGS. 10A and 10B of FIG. 10, among each wavelength included in the wavelength list WL, the target intensity values at wavelengths other than the wavelengths estimated as abnormal wavelengths by the preprocessing unit 231 are all approximately 0.7 times the reference intensity value, and are calculated as 0.7 as the intensity ratio. Also, when the intensity ratio varies slightly for each wavelength, the intensity ratio calculation unit 236 can calculate the intensity ratio by averaging the intensity values at each wavelength, setting a large weight for wavelengths with large intensity values, or optimizing appropriately. Note that the intensity ratio calculation unit 236 may calculate the intensity ratio between the reference intensity value and the target intensity value after removing outliers such as wavelengths estimated as abnormal wavelengths by the preprocessing unit 231, or may perform a predetermined mathematical process on the intensity ratio.

[0125] -Component analysis unit 237- The component analysis unit 237 shown in FIG. 6 determines whether or not one element of the determination target specified by the determination target specifying unit 232 exists based on the similarity calculated by the similarity calculation unit 235 and the similarity threshold value stored in the primary storage unit 21b. Here, the similarity threshold value is a threshold value for determining whether or not a predetermined element exists, and the component analysis unit 237 determines that the element exists when the calculated similarity exceeds the similarity threshold value. Note that the similarity threshold value may be a predetermined fixed value, or may be dynamically changed by a similarity threshold value setting unit 234 described later.

[0126] In addition, the component analysis unit 237 estimates the content of the elements estimated to be included in the sample SP. Here, the estimation of the content of the elements is calculated based on the intensity ratio calculated by the intensity ratio calculation unit 236. In the cases shown in FIGS. 10A and 10B of FIG. 10, among the wavelengths included in the wavelength list WL, the target intensity values at wavelengths other than the wavelengths estimated to be abnormal wavelengths by the preprocessing unit 231 are all approximately 0.7 times the reference intensity value. Since the component analysis unit 237 estimates that one element exists when the relationship between the intensity values at each wavelength included in the wavelength list WL is similar between the set of reference intensity values and the set of target intensity values, the intensity ratio of the target intensity value to the reference intensity value is approximately constant at any wavelength. Based on this intensity ratio and the content when the reference spectrum Sr was obtained, the component analysis unit 237 can estimate the content of the elements included in the sample SP. In the case shown in FIG. 10A of FIG. 10, the set of reference intensity values is obtained from a reference sample with a Fe content of 100 wt%. By multiplying this content by the intensity ratio of the target intensity value to the above reference intensity value, the content of the elements included in the sample SP can be estimated. Furthermore, the component analysis unit 237 may re-estimate the content of the elements so that the estimated content for each element totals 100 wt%.

[0127] (Another embodiment of the wavelength list WL) In the description so far, the case of performing component analysis based on the wavelength list WL including the wavelengths corresponding to the plurality of peaks included in the reference spectrum Sr has been described. Here, the case of performing component analysis based on the wavelength list WL in which a plurality of wavelengths constituting the reference spectrum are associated with the weighting coefficients applied to the intensity values corresponding to each wavelength will be described.

[0128] The intensity acquisition unit 233 shown in FIG. 6 acquires a reference intensity value, which is the intensity value of the reference spectrum Sr at each wavelength included in the wavelength list WL, based on the wavelength list WL stored in the secondary storage unit 21c and the reference spectrum Sr. Then, the intensity acquisition unit 233 creates a set of reference intensity values by taking a plurality of reference intensity values acquired for each wavelength as one set. This set of reference intensity values is a multi-dimensional vector having the number of wavelengths included in the wavelength list WL as the number of dimensions. Although illustration is omitted, an example of the set of reference intensity values created here is that a plurality of wavelengths shown in FIG. 7C of FIG. 7 and the reference intensity values corresponding to the respective wavelengths are held in tabular form as one data set.

[0129] Next, the intensity acquisition unit 233 calculates a target intensity value, which is the intensity value of the target spectrum St at each wavelength included in the wavelength list WL, based on the wavelength list WL stored in the secondary storage unit 21c and the target spectrum St. Then, the intensity acquisition unit 233 creates a set of target intensity values by taking a plurality of target intensity values calculated for each wavelength as one set. This set of target intensity values is a multi-dimensional vector having the number of wavelengths included in the wavelength list WL as the number of dimensions. Although illustration is omitted, an example of the set of target intensity values created here is that a plurality of wavelengths shown in FIG. 7C of FIG. 7 and the target intensity values corresponding to the respective wavelengths are held in tabular form as one data set. The intensity acquisition unit 233 sequentially creates a set of reference intensity values and a set of target intensity values for each element to be determined, and outputs these to the similarity calculation unit 235.

[0130] When using a wavelength list WL that associates a plurality of wavelengths constituting a reference spectrum with weighting coefficients applied to the intensity values corresponding to each wavelength, the wavelengths included in the wavelength list WL may include not only the wavelengths corresponding to the peaks of the reference spectrum Sr but also other wavelengths such as wavelengths that do not appear as peaks. Note that the wavelength list WL may include all the wavelengths constituting the reference spectrum Sr regardless of the presence or absence of peaks, and weighting coefficients may be set for each wavelength. In this case, the weighting coefficients associated with a plurality of wavelengths of interest during component analysis, such as the wavelengths corresponding to the peaks, may be set to be larger than the weighting coefficients associated with other wavelengths (wavelengths not of interest) constituting the reference spectrum. Thereby, it is possible to more accurately estimate whether or not the element to be determined exists.

[0131] The similarity calculation unit 235 shown in FIG. 6 calculates the similarity between the reference intensity value and the target intensity value using the weighting coefficients set in the wavelength list WL. This similarity may be calculated, for example, based on the degree of coincidence (distance) between the weighted reference intensity value and the weighted target intensity value by multiplying each of the reference intensity value and the target intensity value by the weighting coefficient set for the corresponding wavelength. Also, when calculating the degree of coincidence (distance) between the reference intensity value and the target intensity value, the similarity may be calculated by multiplying the distance between the reference intensity value and the target intensity value calculated for each wavelength by the weighting coefficient associated with that wavelength. That is, the above similarity is calculated by applying the weighting coefficients set in the wavelength list WL for each wavelength to the reference intensity values corresponding to a plurality of wavelengths included in the reference spectrum Sr and the target intensity values corresponding to a plurality of wavelengths included in the target spectrum Sr. Then, the component analysis unit 237 shown in FIG. 6 estimates the type of element included in the sample SP based on the similarity calculated by the similarity calculation unit 235 and the similarity threshold value stored in the primary storage unit 21b.

[0132] Further, the component analysis unit 237 estimates the content of an element based on the intensity ratio between the reference intensity value and the target intensity value corresponding to at least one wavelength among the plurality of wavelengths included in the wavelength list WL. Note that the wavelength used for estimating the content rate may be a wavelength with a larger weighting coefficient set in the wavelength list WL, or a wavelength with a large intensity similarity described later. Specifically, in the wavelength list of Fe shown in FIG. 7C of FIG. 7, a larger weighting coefficient is set for the wavelength of 301 nm. Therefore, the component analysis unit 237 can estimate the content of the element based on the intensity ratio between the reference intensity value and the target intensity value at this wavelength of 301 nm.

[0133] Furthermore, the component analysis unit 237 can also estimate the content of an element based on the intensity ratio between the reference intensity values of the plurality of wavelengths included in the wavelength list WL and the target intensity values of the plurality of wavelengths included in the wavelength list WL. In particular, the secondary storage unit 21c may store the wavelength list WL separately as a wavelength list WL used for qualitative analysis and a wavelength list WL used for quantitative analysis. In this case, the component analysis unit 237 estimates the content of the element based on the intensity ratio between the reference intensity value and the target intensity value of all the wavelengths included in the wavelength list WL used for quantitative analysis and the weighting coefficient set for each wavelength in the wavelength list WL. In this way, by separating the wavelength to be focused on for qualitative use and the wavelength to be focused on for quantitative use, component analysis can be performed with higher accuracy. In this way, by estimating the content of the element based on the intensity ratio between the set of reference intensity values with a plurality of reference intensity values as one data set and the set of target intensity values with a plurality of target intensity values as one data set, the influence caused by the variation of each target intensity value can be suppressed, and the estimation accuracy of the content can be improved.

[0134] Note that the method for estimating the content of the element is not limited to the above method. The component analysis unit 237 may estimate the content of the element based on the intensity ratio between the reference intensity value and the target intensity value at a plurality of wavelengths with relatively large weighting coefficients set, or may estimate the content of the element based on the intensity ratio between the average of the reference intensity values and the average of the target intensity values.

[0135] -Details of Wavelength List WL When performing component analysis of sample SP by the LIBS method, there are very many peaks in the emission spectrum of the plasma light, and the peaks of one element to be analyzed often appear at wavelengths close to the peaks of other elements. Even in such a case, a wavelength list WL may be created so that the elements contained in the sample SP can be estimated more accurately. Note that the wavelength list WL is created by the wavelength selection unit 241 or the coefficient setting unit 242 shown in FIG. 6.

[0136] Wavelength list WL of peak wavelengths considering the positional relationship between peaks The wavelength selection unit 241 shown in FIG. 6 can create a wavelength list WL in consideration of the positional relationship between the peaks included in the reference spectrum Sr of one element to be analyzed and the peaks included in the reference spectrum Sr of other elements to be analyzed. That is, the wavelength selection unit 241 determines whether one peak included in the reference spectrum Sr of one element to be analyzed and another peak included in the reference spectrum Sr of other elements to be analyzed exist within a predetermined wavelength range and whether the peaks are close to each other. When the peaks are close to each other, a wavelength list WL in which the wavelength corresponding to one peak is excluded from the wavelengths corresponding to a plurality of peaks included in the reference spectrum Sr of one element to be analyzed is created as the wavelength list WL corresponding to one element to be analyzed. For example, as shown in FIG. 7B of FIG. 7 and FIG. 8B of FIG. 8, a peak of Fe exists at a wavelength of 306.5 nm, and a peak of Cr exists at a wavelength of 306.7 nm. If it is known in advance that peaks are likely to appear around a wavelength of 306.5 nm by obtaining a reference spectrum Sr for each element to be analyzed, the wavelength selection unit 241 can create a wavelength list WL excluding the wavelength of 306.5 nm as the wavelength list WL corresponding to Fe. That is, a wavelength list WL consisting of wavelengths of 301 nm, 303 nm, and 305 nm is created as the wavelength list WL corresponding to Fe. Similarly, the wavelength selection unit 241 can create a wavelength list WL excluding the wavelength of 306.7 nm as the wavelength list WL corresponding to Cr.

[0137] Here, the positional relationship (resolution) between peaks can be determined based on parameters when each peak included in the reference spectrum Sr is approximated by a function. For example, when each peak is approximated by a Gaussian function, it is possible to determine whether the peaks are close to each other based on the distance between peak wavelengths and the full width at half maximum of the peaks. By creating a wavelength list WL excluding wavelengths corresponding to such close peaks, false detection of elements included in the sample SP can be suppressed.

[0138] Wavelength list WL with a weighting coefficient set considering the resolution The coefficient setting unit 242 shown in FIG. 6 can set weighting coefficients for a plurality of wavelengths included in the reference spectrum Sr in consideration of the positional relationship between a peak included in the reference spectrum Sr of one analysis target element and another peak included in the reference spectrum Sr of another analysis target element. Similar to the description of the "wavelength list considering the positional relationship between peaks", the coefficient setting unit 242 can set a weighting coefficient for each wavelength based on the resolution between one peak included in the reference spectrum Sr of one analysis target element and another peak included in the reference spectrum Sr of another analysis target element. That is, the coefficient setting unit 242 can create a wavelength list WL corresponding to one analysis target element by setting a relatively large weighting coefficient for wavelengths corresponding to peaks with a large resolution and a relatively small weighting coefficient for wavelengths corresponding to peaks with a small resolution. Although not shown, the coefficient setting unit 242 can create a wavelength list WL with a relatively small weighting for the wavelength 306.5 nm as the wavelength list WL corresponding to Fe.

[0139] Wavelength list WL of peak wavelengths considering the correlation with the intensity value The secondary storage unit 21c can store, as the wavelength list WL, a first wavelength list for qualitative analysis and a second wavelength list for quantitative analysis. In this case, the component analysis unit 237 estimates the types of elements contained in the sample SP based on the similarity calculated using the weighting coefficients set in the first wavelength list, and estimates the content of the elements contained in the sample SP based on the intensity ratio calculated using the weighting coefficients set in the second wavelength list.

[0140] As shown in FIG. 11, the reference intensity value of the reference spectrum Sr of the element to be analyzed varies according to the content of the element to be analyzed. Among the variations in this reference intensity value, there are those that are in a proportional relationship with the content of the element to be analyzed and those that are not. In FIG. 11, the case of containing 100 wt% of Fe is shown by a solid line, and the case of containing 50 wt% of Fe is shown by a dashed line. The reference intensity values at wavelengths 301 nm and 303 nm are in a proportional relationship with the content of Fe. On the other hand, although the reference intensity values at wavelengths 305 nm and 306.5 nm increase as the content of Fe increases, there is no proportional relationship between the content of Fe and the reference intensity value. That is, for the wavelengths of 301 nm, 303 nm, 305 nm, and 306.5 nm, the value indicating the correlation between the content of the element and the reference intensity value is equal to or greater than the first value. And for the wavelengths of 301 nm and 303 nm, the value indicating the correlation between the content of the element and the reference intensity value is equal to or greater than a second value that is larger than the first value. By using, for quantitative analysis, a wavelength with a larger value indicating the correlation between the content of the element to be analyzed and the reference intensity value, the content of the elements contained in the sample SP can be accurately estimated. On the other hand, for estimating whether or not the element to be analyzed exists, any wavelength whose reference intensity value changes as the content of the element to be analyzed changes is sufficient, and a large correlation is not necessarily required. Therefore, the secondary storage unit 21c can store, as the wavelength list WL, a first wavelength list composed of a plurality of wavelengths whose value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than the first value, and a second wavelength list composed of a plurality of wavelengths whose value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than the second value.

[0141] In the case shown in FIG. 11, the four wavelengths at which the value indicating the correlation between the Fe content and the reference intensity value is equal to or greater than the first value are wavelengths that can be used for the qualitative analysis of Fe. Therefore, the first wavelength list includes the above four wavelengths. Further, the two wavelengths at which the value indicating the correlation between the Fe content and the reference intensity value is equal to or greater than the second value are wavelengths suitable for the quantitative analysis of Fe. Therefore, the second wavelength list includes these two wavelengths having a large correlation between the element to be analyzed and the reference intensity value.

[0142] In this way, by separately storing in the secondary storage unit 21c the wavelength list WL (the first wavelength list) used for qualitative analysis and the wavelength list WL (the second wavelength list) used for quantitative analysis, it is possible to more accurately estimate the content of the element estimated to be included in the sample SP while suppressing misjudgment of the elements included in the sample SP.

[0143] The wavelength list WL in which the weighting coefficient is set in consideration of the correlation with the intensity value In the above "wavelength list WL of peak wavelengths considering the correlation with intensity values", the case where the wavelength list is constituted by the wavelengths corresponding to the peaks was explained. Here, the case where the wavelength list WL is defined by setting weighting coefficients corresponding to a plurality of wavelengths included in the reference spectrum Sr in consideration of the correlation with intensity values will be explained. In this case, among the plurality of wavelengths included in the reference spectrum Sr, the weighting coefficients corresponding to the plurality of wavelengths whose values indicating the correlation between the content of the element to be analyzed and the reference intensity value are equal to or greater than the first value are relatively larger than the weighting coefficients corresponding to the wavelengths whose values indicating the correlation are less than the first value, whereby a first wavelength list for qualitative analysis is created. Further, the second wavelength list for quantitative analysis is created by setting, for a plurality of wavelengths among the plurality of wavelengths included in the reference spectrum Sr, whose values indicating the correlation between the content of the element to be analyzed and the reference intensity value are equal to or greater than a second value greater than the first value, the weighting coefficients to be relatively larger than the weighting coefficients corresponding to the wavelengths whose values indicating the correlation are less than the second value. Although illustration is omitted, in the case shown in FIG. 11, the first wavelength list is created by the coefficient setting unit 242 setting relatively larger weighting coefficients for wavelengths 301 nm, 303 nm, 305 nm, and 306.5 nm than for other wavelengths. Further, the second wavelength list is created by the coefficient setting unit 242 setting relatively larger weighting coefficients for wavelengths 301 nm and 303 nm than for other wavelengths.

[0144] Wavelength list WL corresponding to the valence number of the element in the plasma state When the element in the excited state returns to the ground state by irradiating the sample SP with laser light, plasma light is generated. The elements in the plasma state exist in different valence states such as neutral atoms, monovalent ions, divalent ions, etc. In this case, since there are low energy levels corresponding to the valence of the element in the plasma state, such as the low energy level of the monovalent ion and the low energy level of the divalent ion, the wavelength corresponding to the peak of the emission spectrum varies according to the valence of the element. Therefore, a plurality of wavelength lists WL may be stored in the secondary storage unit 21c corresponding to the valence of the element in the plasma state in which energy is emitted as plasma light. This case will be described with reference to FIG. 12.

[0145] FIG. 12 is a diagram illustrating the reference spectrum Sr of Zn. This reference spectrum Sr has a plurality of peak groups, such as a peak group corresponding to the energy transition within Zn(2+), a peak group corresponding to the energy transition within Zn(1+), and a peak group corresponding to the energy transition within Zn(0). Among these multiple peak groups, the peaks at wavelengths 300.7 nm, 301 nm, and 301.2 nm correspond to the energy transition within Zn(2+), the peaks at wavelengths 302.8 nm and 303 nm correspond to the energy transition within Zn(1+), and the peaks at wavelengths 305.7 nm, 306 nm, 306.2 nm, and 306.5 nm are known to correspond to the energy transition within Zn(0). Note that the reference spectrum Sr shown in FIG. 12 is for illustrative purposes and does not necessarily match the spectrum actually obtained by measuring Zn.

[0146] As shown in FIG. 12, when the correspondence between a plurality of peak groups included in the reference spectrum Sr and the valence of an element is known in advance, the secondary storage unit 21c may store a first wavelength list including three wavelengths of 300.7 nm, 301 nm, and 301.2 nm, a second wavelength list including two wavelengths of 300.7 nm, 301 nm, and 301.2 nm, and a third wavelength list including four wavelengths of 305.7 nm, 306 nm, 306.2 nm, and 306.5 nm. That is, the secondary storage unit 21c can store different wavelength lists WL for each ion valence of an element in a plasma state in which energy is emitted as plasma light. In the present embodiment, instead of a method of determining the presence or absence of a peak at a specific wavelength, it is determined whether or not an element to be determined exists based on the ratio between intensity values at a plurality of wavelengths (degree of coincidence as a vector). Due to differences in the intensity of the laser light emitted by the emission unit 71, differences in the plasma temperature, which is the temperature of the plasma-formed element, etc., the ratio of the amount of energy transition within divalence to the amount of energy transition within monovalence may be different. Therefore, if wavelengths corresponding to energy transitions within divalence and wavelengths corresponding to energy transitions within monovalence are stored in a mixed manner, the degree of coincidence between the ratio of reference intensity values at each wavelength and the ratio of target intensity values may decrease. Due to the decrease in the degree of coincidence, there is a possibility that an element that actually exists may be erroneously determined not to exist even though it exists. By storing a plurality of wavelength lists corresponding to the ion valence of an element in a plasma state in which energy is emitted as plasma light in this way, the possibility of overlooking the presence of an element can be reduced, and the elements present in the sample SP can be estimated more accurately. Although not shown in the figure, similarly, when the wavelength list WL is created by setting a weighting coefficient for a plurality of peaks included in the reference spectrum Sr, a plurality of wavelength lists WL with weighting coefficients set corresponding to the ion valence of the element in the plasma state can be stored. Further, when there are a plurality of wavelength lists WL for one element to be analyzed, the similarity calculation unit 235 may calculate the similarity by extracting the maximum value among the similarities calculated for each of the wavelength lists WL or by calculating the average of the plurality of similarities.

[0147] -Details of the reference spectrum Sr- In the analysis using the LIBS method, a phenomenon called the so-called "matrix effect" may occur. That is, when an element to be determined and an element not to be determined are mixed, the intensity value of the peak that appeared at a predetermined wavelength may vary from the reference intensity value, or a peak that existed in the reference spectrum Sr may disappear or split. Therefore, not only the reference spectrum Sr obtained for the element to be determined alone, but also the mixed spectrum obtained from a sample in which the element to be determined and an element not to be determined are mixed, and the wavelength list WL obtained from that spectrum may be stored in the secondary storage unit 21c. This case will be described with reference to FIG. 13. Here, the element to be determined is referred to as the first element. The secondary storage unit 21c stores, as the wavelength list WL, a first wavelength list created based on a spectrum obtained from a sample containing the first element and a second element different from the first element, and a second wavelength list created based on a spectrum obtained from a sample containing the first element and a third element different from the first element and the second element.

[0148] FIG. 13A in FIG. 13 is a diagram illustrating a first mixed spectrum obtained from a sample containing Fe as the first element and Mg as the second element. In the reference spectrum Sr of Fe alone, which is the first element, a peak appears at the wavelength position shown in FIG. 7B of FIG. 7. However, as shown in FIG. 13A of FIG. 13, in the mixed spectrum containing Fe and Mg, there is no peak at the position corresponding to a wavelength of 305 nm. This is because there is a peak of Mg at the position corresponding to a wavelength of 304.8 nm, and due to the influence of this peak, the intensity value corresponding to a wavelength of 305 nm has decreased or the peak itself has disappeared.

[0149] Further, FIG. 13B in FIG. 13 shows a second mixed spectrum obtained from a sample containing Fe as the first element and Mn as the third element. In the reference spectrum Sr of pure Fe as the first element, a peak appears at the wavelength position shown in FIG. 7B of FIG. 7. However, as shown in FIG. 13B of FIG. 13, in the mixed spectrum containing Fe and Mn, the intensity value of the peak corresponding to a wavelength of 301 nm has decreased. This is due to being affected by the peak of Mn existing near a wavelength of 301 nm. In the present embodiment, instead of a method for determining the presence or absence of a peak at a specific wavelength, it is estimated whether an element to be determined exists based on the ratio (degree of coincidence as a vector) between intensity values at a plurality of wavelengths. Therefore, with only the reference spectrum Sr of the first element, the degree of coincidence between the ratio of reference intensity values at each wavelength and the ratio of target intensity values decreases, and there is a risk of being erroneously determined as not existing even though it actually exists. Therefore, by storing in advance a mixed spectrum obtained from a sample in which the first element and other elements (second element, third element) that often coexist with the first element are mixed, the risk of overlooking the presence of an element can be reduced, and the elements present in the sample SP can be estimated more accurately. That is, the intensity acquisition unit 233 acquires a reference intensity value that is the intensity value of a wavelength included in the wavelength list WL from the reference spectrum Sr, acquires the intensity value of a wavelength included in the wavelength list WL from the first mixed spectrum, or acquires the intensity value of a wavelength included in the wavelength list WL from the second mixed spectrum. Then, the similarity calculation unit 235 calculates a similarity based on the distance between the reference intensity value and the target intensity value. Similarly, the similarity calculation unit 235 calculates the similarity between the intensity value obtained from the first mixed spectrum and the target intensity value. Further, the similarity calculation unit 235 calculates the similarity between the intensity value obtained from the second mixed spectrum and the target intensity value. Thereby, since the elements contained in the sample SP can be estimated not only based on the reference spectrum Sr but also based on the first mixed spectrum and the second mixed spectrum, erroneous determination caused by the influence of other elements can be suppressed.

[0150] - Similarity threshold setting unit 234 - The similarity threshold setting unit 234 shown in FIG. 6 can dynamically change the similarity threshold for each target spectrum St according to the degree of change in the intensity values within the target spectrum St acquired by the spectrum acquisition unit 212. Here, as an example of the degree of change in the intensity values, the variance of the intensity values within the target spectrum St, the number of peaks, the intensity values of the peaks, etc. can be mentioned.

[0151] For example, the similarity threshold setting unit 234 calculates the variance of the target spectrum acquired by the intensity acquisition unit 233. When the calculated variance is large, there are many noise components in the target spectrum St due to elements other than the element to be determined or the measurement environment. In this case, if the similarity threshold is small, by detecting peaks other than the element to be determined, there is a high risk of misjudging that the element to be determined exists even though the element to be determined actually does not exist. Therefore, when the variance of the target spectrum St is large, the similarity threshold setting unit 234 increases the similarity threshold required for the component analysis unit 237 to determine that the element to be determined exists. That is, when the degree of change in the intensity values within the target spectrum St is large, the similarity threshold setting unit 234 dynamically changes the similarity threshold so that it is less likely to be determined that the element to be determined exists, and when the degree of change in the intensity values within the target spectrum St is small, the similarity threshold setting unit 234 dynamically changes the similarity threshold so that it is more likely to be determined that the element to be determined exists. When the number of peaks is used as the degree of change in the intensity values, the similarity threshold setting unit 234 dynamically changes the similarity threshold so that it is less likely to be determined that the element to be determined exists as the number of peaks included in the target spectrum St increases. Note that the similarity threshold setting unit 234 can also dynamically change the noise determination level based on the degree of change in the intensity values within the target spectrum St instead of or in addition to the similarity threshold. That is, when the degree of change in the intensity values within the target spectrum St is large, the similarity threshold setting unit 234 increases the noise determination level so that only peaks with large target intensity values are the detection targets, and when the degree of change in the intensity values is small, the similarity threshold setting unit 234 can decrease the noise determination level so that relatively small peaks are also the detection targets.

[0152] Generally, typical elements have a small degree of change in intensity values (few peaks), while transition elements have a large degree of change in intensity values (many peaks). Therefore, there is little risk of misestimating one typical element as another typical element or misestimating one typical element as a transition element. When a transition element is not detected, the similarity threshold setting unit 234 can dynamically change the similarity threshold (relax the similarity threshold) so that it is easier to determine that the element to be determined exists, thereby enhancing the detection ability of the element to be determined. On the other hand, since transition elements have many peaks, there is a risk of misestimating that a typical element with few peaks is included. In such a case, the similarity threshold setting unit 234 can dynamically change the similarity threshold (tighten the similarity threshold) so that it is more difficult to determine that the element to be determined exists. Although the detection ability of typical elements will decrease, false detection of typical elements can be suppressed. In this way, since the similarity threshold can be dynamically changed for each measurement according to the obtained target spectrum St, qualitative analysis can be performed more accurately. Here, false detection is suppressed by changing the similarity threshold according to the degree of change in intensity values, but false detection may also be suppressed by decreasing the similarity itself according to the degree of change in intensity values.

[0153] -Details of the preprocessing unit 231- The preprocessing unit 231 shown in FIG. 6 can determine to what extent the shape of the peak included in the target spectrum St acquired by the spectrum acquisition unit 212 matches the ideal shape of the peak. That is, the preprocessing unit 231 calculates a peak matching degree that represents the degree of match between the shape of the peak included in the target spectrum St and a predetermined peak model that is the ideal shape of the peak. Here, the predetermined peak model is a model representing a peak shape represented by a predetermined non-linear function such as a parabola or a Gaussian function, or a predetermined linear function such as a piecewise linear function. When a non-linear function is used as the peak model, the preprocessing unit 231 approximates a plurality of peaks included in the target spectrum St with a predetermined non-linear function. The preprocessing unit 231 can calculate the peak matching degree by calculating the distance between the ideal non-linear function and the approximated non-linear function by a known method such as the least squares method. Note that the peak matching degree can also be calculated based on the matching degree as the vector described above. Then, the preprocessing unit 231 outputs the calculated peak matching degree to the similarity calculation unit 235. The higher this peak matching degree, the closer it is to the ideal peak model. Therefore, a peak with a high peak matching degree is likely to more accurately reflect the elements included in the sample SP. Therefore, by calculating the similarity in consideration of this peak matching degree, it is possible to more accurately estimate whether or not the element to be determined exists.

[0154] Also, as the predetermined peak model, the peak shape included in the reference spectrum Sr can be used. In this case, the preprocessing unit 231 can calculate the peak matching degree based on the distance between the peak shape included in the reference spectrum Sr and the target spectrum St acquired by the spectrum acquisition unit 212. Here, since the smaller the distance between the peak shape of the reference spectrum Sr and the peak shape of the target spectrum St, the more the peaks match, the preprocessing unit 231 calculates the peak matching degree so that the smaller the above distance, the larger the peak matching degree.

[0155] -Calculation of the overall similarity by the similarity calculation unit 235- The similarity calculation unit 235 shown in FIG. 6 calculates the similarity between the set of reference intensity values and the set of target intensity values. The similarity calculation unit 235 may calculate the comprehensive similarity instead of or in addition to the similarity. Here, the case where the similarity calculation unit 235 calculates the comprehensive similarity in consideration of the peak matching degree calculated by the preprocessing unit 231 will be described. Peaks with a large peak matching degree are likely to more accurately reflect the elements contained in the sample SP. Therefore, when there is a peak with a large peak matching degree, the similarity calculation unit 235 increases the value of the calculated comprehensive similarity. On the other hand, a peak with a small peak matching degree is likely not to accurately reflect the elements contained in the sample SP, such as a peak formed by a plurality of different peaks. If the presence of an element is determined based on such a peak, there is a risk of misjudging that an element that actually does not exist exists. Therefore, when there is a peak with a small peak matching degree, the similarity calculation unit 235 decreases the value of the calculated comprehensive similarity. Specifically, the similarity calculation unit 235 first calculates the similarity between the set of reference intensity values and the set of target intensity values. Then, the similarity calculation unit 235 calculates the product of the similarity calculated here and the peak matching degree as the comprehensive similarity. Note that the above method of calculating the comprehensive similarity is only an example, and other mathematical methods such as arithmetic operations can be used. By changing the comprehensive similarity according to the peak shape of the target spectrum St actually obtained during measurement by the spectrum acquisition unit 212 in this way, the elements contained in the sample SP can be estimated more accurately.

[0156] In addition, when calculating the similarity, the similarity calculation unit 235 shown in FIG. 6 can consider the intensity similarity instead of or in addition to the peak matching degree. Specifically, the similarity calculation unit 235 obtains the intensity similarity, which is the similarity between the reference intensity value and the target intensity value calculated by the preprocessing unit 231. Then, the similarity calculation unit 235 calculates the comprehensive similarity by applying a predetermined mathematical process to the similarity between the set of reference intensity values and the set of target intensity values, the peak matching degree, and the intensity similarity. When the primary storage unit 21b holds the intensity similarity threshold, the comprehensive similarity may be calculated by calculating the intensity similarity for each wavelength and multiplying the ratio of the calculated intensity similarity exceeding the intensity similarity threshold by the above similarity.

[0157] When the comprehensive similarity is calculated by the similarity calculation unit 235, the component analysis unit 237 can estimate the types of elements contained in the sample SP based on the calculated comprehensive similarity and the similarity threshold stored in the primary storage unit 21b.

[0158] -Details of the component analysis unit 237- The component analysis unit 237 shown in FIG. 6 can consider the peak matching degree calculated by the preprocessing unit 231 when estimating the content. Generally, there are a plurality of peaks in the target spectrum St. Therefore, the component analysis unit 237 calculates the intensity ratio between the reference intensity value and the target intensity value for the wavelengths corresponding to the plurality of peaks, and estimates the content based on the calculated plurality of intensity values. However, among the plurality of peaks, there may be both a peak with a large peak matching degree and a peak with a small peak matching degree. Therefore, when estimating the element content based on the intensity ratio between the reference intensity value and the target intensity value calculated for the plurality of wavelengths, the component analysis unit 237 can set a weighting coefficient to be applied to the intensity ratio according to the peak matching degree. That is, the component analysis unit 237 can increase the weighting coefficient as the peak matching degree increases and decrease the weighting coefficient as the peak matching degree decreases among the peak matching degrees calculated for each wavelength.

[0159] In addition, the component analysis unit 237 shown in FIG. 6 can consider the intensity similarity calculated for each wavelength instead of or in addition to the peak matching degree when estimating the element content. Specifically, the component analysis unit 237 acquires the intensity similarity, which is the similarity between the reference intensity value and the target intensity value calculated by the preprocessing unit 231. Then, among the intensity similarities calculated for each wavelength, the component analysis unit 237 can set a large value as the weighting coefficient applied to the intensity ratio for the wavelength with a relatively large intensity similarity. Also, for the wavelength with a relatively small intensity similarity, the component analysis unit 237 can set a small value as the weighting coefficient applied to the intensity ratio. In this way, since the weighting coefficient applied to the intensity ratio can be changed when estimating the element content based on the similarity between the reference intensity value and the target intensity value at each wavelength, the element content can be estimated with higher accuracy.

[0160] <Component analysis flow> FIG. 14 is a flowchart illustrating the analysis procedure of the sample SP by the processing unit 21a.

[0161] First, in step S1001, the emission control unit 211 controls the emission unit 71 to emit laser light.

[0162] Next, in step S1002, the spectrum acquisition unit 212 acquires the target spectrum St, which is the emission spectrum of the plasma light generated by the first detector 77A and the second detector 77B. Step S1002 is an example of the "spectrum acquisition step" in the present embodiment.

[0163] Next, in step S1003, the component analysis unit 237 performs qualitative analysis of the sample SP. The details of step S1003 will be described based on the flowchart of FIG. 15.

[0164] Subsequently, in step S1004, the component analysis unit 237 performs a quantitative analysis to estimate the content of the element estimated to be present in the sample in step S1003. Steps S1003 and S1004 are examples of the "component analysis step" in the present embodiment.

[0165] <Qualitative analysis flow> Next, based on the flowchart of FIG. 15, the qualitative analysis procedure shown in step S1003 of FIG. 14 will be described.

[0166] First, in step S1101, the determination target specifying unit 232 specifies one element among the analysis target elements as the determination target element.

[0167] Next, in step S1102, the determination target specifying unit 232 acquires at least one of the number of wavelength lists WL of the determination target element and the number of reference spectra Sr. This step is realized by referring to the data table shown in FIG. 18.

[0168] Next, in step S1103, the determination target specifying unit 232 selects one reference spectrum Sr for which the calculation of similarity has not been completed from among the reference spectra Sr associated with the determination target element.

[0169] Next, in step S1104, the determination target specifying unit 232 selects one wavelength list WL for which the calculation of similarity has not been completed from among the wavelength lists WL associated with the one reference spectrum Sr selected in step S1103.

[0170] Next, in step S1105, the intensity acquisition unit 233 acquires the one wavelength list WL selected in step S1104 from the secondary storage unit 21c. Step S1105 is an example of the "reading step" in the present embodiment.

[0171] Next, in step S1106, the intensity acquisition unit 233 acquires a reference intensity value and a target intensity value corresponding to the wavelengths included in the one wavelength list WL acquired in step S1105. Here, as the reference intensity value, a value stored in advance in the secondary storage unit 21c may be acquired, or it may be acquired by calculating from the reference spectrum Sr stored in the secondary storage unit 21c.

[0172] Next, in step S1107, the similarity calculation unit 235 calculates a similarity (overall similarity) based on the reference intensity value and the target intensity value acquired in step S1106. Details of this step will be described according to the flowchart of FIG. 16. Step S1109 is an example of the "similarity calculation step" in the present embodiment.

[0173] Next, in step S1108, the determination target specifying unit 232 determines whether the calculation of the similarity has been completed for the wavelength list WL associated with the one reference spectrum Sr selected in step S1103. If this determination is YES, the process proceeds to step S1109, and if this determination is NO, the process returns to step S1104.

[0174] Next, in step S1109, the determination target specifying unit 232 determines whether the calculation of the similarity has been completed for all the reference spectra Sr associated with the elements to be determined. If this determination result is YES, the process proceeds to step S1110, and if this determination result is NO, the process returns to step S1103.

[0175] In step S1110, the component analysis unit 237 acquires a similarity threshold value from the primary storage unit 21b. Note that this step may be omitted if the similarity threshold value has already been acquired. Also, if the similarity threshold value is set to change dynamically, the similarity threshold value may be acquired every time the similarity is calculated.

[0176] Next, in step S1111, the component analysis unit 237 determines whether a similarity equal to or greater than the similarity threshold has been calculated. If this determination is YES, the process proceeds to step S1112, and the component analysis unit 237 determines that the element to be determined exists. If this determination is NO, the process proceeds to step S1113, and the component analysis unit 237 determines that the element to be determined does not exist.

[0177] Then, in step S1114, the determination target specifying unit 232 determines whether qualitative analysis has been completed for all elements to be analyzed. If this determination is YES, the qualitative analysis is terminated. If this determination is NO, the process returns to step S1101. <Similarity calculation flow> Next, based on the flowchart of FIG. 16, the procedure for calculating the similarity shown in step S1109 of FIG. 15 is shown.

[0178] First, in step S1201, the similarity calculation unit 235 calculates the similarity between the reference intensity value and the target intensity value of the wavelengths included in the wavelength list WL. This similarity may be calculated based on the degree of coincidence between vectors in a multi-dimensional space having the wavelengths included in the wavelength list WL as coordinate axes, or may be calculated based on, for example, the sum of the differences between the reference intensity value and the target intensity value at each wavelength.

[0179] Next, in step S1202, the similarity calculation unit 235 determines whether to calculate the overall similarity in consideration of the peak coincidence degree. This determination is realized, for example, by referring to the item "peak determination" in the analysis setting table shown in FIG. 19. If this determination is YES, the process proceeds to step S1203. If this determination is NO, step S1203 is skipped and the process proceeds to step S1204.

[0180] In step S1203, the similarity calculation unit 235 acquires the peak coincidence degree calculated by the preprocessing unit 231.

[0181] Subsequently, in step S1204, the similarity calculation unit 235 determines whether to calculate the comprehensive similarity in consideration of the intensity similarity. This determination is realized, for example, by referring to the "intensity similarity" item in the analysis setting table shown in FIG. 19. If this determination is YES, the process proceeds to step S1205. If this determination is NO, step S1205 is skipped and the process proceeds to step S1206.

[0182] In step S1205, the similarity calculation unit 235 acquires the intensity similarity calculated by the preprocessing unit 231. Subsequently, in step S1206, the similarity calculation unit 235 calculates the comprehensive similarity based on the similarity calculated in step S1201, the peak matching degree, and the intensity similarity. Here, the comprehensive similarity may be calculated by mathematical processing such as multiplying the similarity, the peak matching degree, and the intensity similarity. Here, steps S1201 to S1206 are examples of the "similarity calculation step" in the present embodiment.

[0183] <Similarity threshold setting flow> FIG. 17 is a flowchart illustrating the procedure for setting the similarity threshold by the similarity threshold setting unit 234.

[0184] First, in step S1301, the similarity threshold setting unit 234 acquires the standard threshold stored in the primary storage unit 21b or the secondary storage unit 21c. The standard threshold is a default value predetermined, for example, at the time of factory shipment of the device.

[0185] Next, in step S1302, the similarity threshold setting unit 234 calculates the degree of change in the intensity values within the target spectrum St acquired by the spectrum acquisition unit 212. Here, the degree of change in the intensity values within the target spectrum St is calculated based on, for example, the variance or the number of peaks of the target spectrum St.

[0186] Next, in step S1303, the similarity threshold setting unit 234 acquires the peak matching degree calculated by the preprocessing unit 231.

[0187] Subsequently, in step S1304, the similarity threshold setting unit 234 calculates a similarity threshold based on the standard threshold, the degree of change in the intensity value, and the peak matching degree. Here, the similarity threshold may be calculated, for example, by multiplying the reciprocal of the degree of change in the intensity value with respect to the standard threshold, or further by multiplying the peak matching degree.

[0188] Subsequently, in step S1305, the similarity threshold setting unit registers the similarity threshold calculated in step S1304 in the primary storage unit 21b.

[0189] <Example of display screen> An example of the display screen displayed on the display unit 22 will be described using the target spectrum St in FIG. 9. In the target spectrum St shown in FIG. 9, there are a plurality of peaks corresponding to Fe and a plurality of peaks corresponding to Cr. In order to be able to identify whether these peaks belong to the peaks of Fe or the peaks of Cr, an icon indicating Fe and an icon indicating Cr are displayed together with the target spectrum St in association with each peak. Note that these icons can be made non-display for the wavelengths estimated as abnormal wavelengths by the preprocessing unit 231. That is, the display control unit 221a can display these icons for the wavelengths used in the calculation of the similarity, and can vary the wavelengths at which the icons are displayed for each target spectrum St. As a result, since the wavelengths at which the icons are displayed change dynamically for each target spectrum St, the user can easily grasp which wavelengths were used to calculate the similarity, making it easier to interpret the results of the component analysis.

[0190] Here, the case where an icon is displayed in association with each peak has been described. However, other methods such as assigning a straight line or a broken line to the peak can also be used. That is, the display control unit 221a identifies the wavelengths used for calculating the similarity for each target spectrum St. Then, the display control unit 221a may display the display screen on the display unit 22 so that the wavelengths used for calculating the similarity among the wavelengths of the plurality of peaks included in the target spectrum St can be identified.

Industrial Applicability

[0191] As described above, the analyzer according to the present invention can be used when performing component analysis of various samples.

Explanation of Signs

[0192] A Analysis and Observation Device SP Sample (Object to be Analyzed) 1 Optical System Assembly 5 Mounting Table 6 Head Unit 7 Analysis Optical System 71 Emission Unit 74 Reflective Objective Lens (Collection Head) 77A First Detection Unit (Detection Unit) 77B Second Detection Unit (Detection Unit) 81 First Camera (Imaging Unit) 9 Observation Optical System 93 Second Camera (Imaging Unit) 2 Controller Main Body 21a Processing Unit 211 Emission Control Unit 212 Spectrum Acquisition Unit 221 UI Control Unit 230 Component Analysis Unit 231 Intensity Acquisition Unit 234 Similarity Threshold Setting Unit 21b Primary Storage Unit 21c Secondary Storage Unit

Claims

1. An analyzer that irradiates the surface of a sample with a laser beam and performs component analysis of the sample based on the emission spectrum of the plasma light generated by the irradiation and the reference spectra of a plurality of elements to be analyzed, a storage unit that stores, for each element to be analyzed, a wavelength list that is a combination of a plurality of wavelengths of a plurality of peaks included in the reference spectrum and is used during component analysis, a similarity calculation unit that sequentially calculates, for each element to be analyzed, the similarity between a reference intensity value that is an intensity value obtained from the reference spectrum and corresponds to a wavelength included in the wavelength list, and a target intensity value that is an intensity value obtained from the emission spectrum and corresponds to a wavelength included in the wavelength list, an intensity ratio calculation unit that calculates an intensity ratio between a reference intensity value corresponding to a predetermined wavelength included in the wavelength list and a target intensity value corresponding to the predetermined wavelength included in the wavelength list, a component analysis unit that estimates the types of elements contained in the sample based on the similarity calculated by the similarity calculation unit and estimates the content of the elements contained in the sample based on the intensity ratio calculated by the intensity ratio calculation unit, wherein the storage unit stores, as the wavelength list, a first wavelength list including a plurality of wavelengths at which a value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than a first value, a second wavelength list including a plurality of wavelengths at which a value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than a second value that is greater than the first value, the similarity calculation unit sequentially calculates, for each element to be analyzed, the similarity between the reference intensity value and the target intensity value corresponding to the wavelengths included in the first wavelength list as the similarity, the intensity ratio calculation unit calculates the intensity ratio between the reference intensity value and the target intensity value corresponding to the wavelengths included in the second wavelength list as the intensity ratio, and the component analysis unit estimates the types of elements contained in the sample based on the similarity calculated by the similarity calculation unit, and estimates the content of the elements contained in the sample based on the intensity ratio calculated by the intensity ratio calculation unit. An analyzer characterized by the above.

2. The analyzer according to claim 1, The similarity calculation unit sequentially calculates the difference between the reference intensity value and the target intensity value for each of the plurality of wavelengths included in the wavelength list for each of the analysis target elements, and calculates the similarity based on the plurality of calculated differences. An analyzer characterized by that.

3. The analyzer according to claim 1 or 2, When the wavelength of one peak included in the reference spectrum of one analysis target element and the wavelength of another peak included in the reference spectrum of another analysis target element exist within a predetermined wavelength range, among the plurality of peaks included in the reference spectrum of the one analysis target element, A wavelength list excluding the wavelength of the one peak is stored as a wavelength list corresponding to the one analysis target element. An analyzer characterized by that.

4. An analyzer that irradiates the surface of a sample with laser light and performs component analysis of the sample among the plurality of analysis target elements based on the emission spectrum of the plasma light generated by the irradiation and the reference spectra of the plurality of analysis target elements, A storage unit that stores, for each analysis target element, a wavelength list associating a plurality of wavelengths constituting the reference spectrum with a weighting coefficient applied to the intensity value corresponding to each wavelength, A similarity calculation unit that sequentially calculates, for each analysis target element, the similarity between a reference intensity value that is an intensity value obtained from the reference spectrum and corresponds to a wavelength included in the wavelength list, and a target intensity value that is an intensity value obtained from the emission spectrum and corresponds to a wavelength included in the wavelength list, using the weighting coefficient set in the wavelength list, An intensity ratio calculation unit that calculates the intensity ratio between the reference intensity value and the target intensity value corresponding to the wavelength included in the wavelength list, Based on the similarity calculated by the similarity calculation unit, the type of element contained in the sample is estimated, and based on the intensity ratio calculated by the intensity ratio calculation unit, a component analysis unit that estimates the content of the element contained in the sample is provided, In the wavelength list, a large weighting coefficient is associated with the wavelength corresponding to the peak included in the reference spectrum among the plurality of wavelengths constituting the reference spectrum, The memory unit stores, as a wavelength list corresponding to the one analysis target element, a wavelength list in which a larger weighting coefficient is set as the separation degree between one peak included in the reference spectrum of the one analysis target element and another peak included in the reference spectrum of another analysis target element is larger. The analyzer is characterized by this.

5. An analyzer that irradiates the surface of a sample with laser light and performs component analysis of the sample among the plurality of analysis target elements based on the emission spectrum of the plasma light generated by the irradiation and the reference spectra of the plurality of analysis target elements, A memory unit that stores, for each analysis target element, a wavelength list associating a plurality of wavelengths constituting the reference spectrum with a weighting coefficient applied to the intensity value corresponding to each wavelength, A similarity calculation unit that sequentially calculates, for each analysis target element, the similarity between a reference intensity value that is an intensity value obtained from the reference spectrum and corresponds to a wavelength included in the wavelength list, and a target intensity value that is an intensity value obtained from the emission spectrum and corresponds to a wavelength included in the wavelength list, using the weighting coefficient set in the wavelength list, An intensity ratio calculation unit that calculates the intensity ratio between the reference intensity value and the target intensity value corresponding to the wavelength included in the wavelength list, A component analysis unit that estimates the type of element contained in the sample based on the similarity calculated by the similarity calculation unit, and estimates the content of the element contained in the sample based on the intensity ratio calculated by the intensity ratio calculation unit, The wavelength list has a large weighting coefficient associated with the wavelength corresponding to the peak included in the reference spectrum among the plurality of wavelengths constituting the reference spectrum, The memory unit stores, as the wavelength list, A first wavelength list in which the weighting coefficient corresponding to the wavelength at which the value indicating the correlation between the content of the analysis target element and the reference intensity value is equal to or greater than the first value is set to be larger than the weighting coefficient corresponding to the wavelength at which the value indicating the correlation is less than the first value, A second wavelength list in which the weighting coefficient corresponding to the wavelength at which the value indicating the correlation between the content of the analysis target element and the reference intensity value is greater than the first value and equal to or greater than the second value is set to be larger than the weighting coefficient corresponding to the wavelength at which the value indicating the correlation is less than the second value, The similarity calculation unit sequentially calculates the similarity for each of the elements to be analyzed using the weighting coefficient set in the first wavelength list. The intensity ratio calculation unit calculates the intensity ratio using the weighting coefficient set in the second wavelength list. The component analysis unit estimates the types of elements contained in the sample based on the similarity calculated using the weighting coefficient set in the first wavelength list. An analyzer characterized by estimating the content of elements contained in the sample based on the intensity ratio calculated using the weighting coefficient set in the second wavelength list.

6. The analyzer according to any one of claims 1 to 5, further comprising: a similarity threshold setting unit that sets a similarity threshold for estimating elements contained in the sample based on the degree of change between intensity values corresponding to a plurality of wavelengths within one of the emission spectra; The component analysis unit estimates the elements contained in the sample based on the similarity calculated by the similarity calculation unit and the similarity threshold set by the similarity threshold setting unit. An analyzer characterized by this.

7. The analyzer according to any one of claims 1 to 5, further comprising: a similarity threshold setting unit that sets a similarity threshold for estimating elements contained in the sample based on the number of peaks included in one of the emission spectra; The component analysis unit estimates the elements contained in the sample based on the similarity calculated by the similarity calculation unit and the similarity threshold set by the similarity threshold setting unit. An analyzer characterized by this.

8. The analyzer according to any one of claims 1 to 7, further comprising: a preprocessing unit that calculates a peak matching degree, which is the degree of coincidence between the peak shape included in the emission spectrum and the ideal shape of the peak; The similarity calculation unit calculates a smaller value as the comprehensive similarity based on the similarity and the peak matching degree, with the peak matching degree being lower. The component analysis unit estimates the types of elements contained in the sample based on the comprehensive similarity calculated by the similarity calculation unit. An analyzer characterized by this.

9. The analyzer according to claim 5, further comprising: a preprocessing unit that calculates a peak matching degree, which is the degree of coincidence between the peak shape included in the emission spectrum and the ideal shape of the peak; The component analysis unit is an analyzer characterized in that the smaller the peak matching degree is, the lower the weighting coefficient applied to the intensity ratio during the estimation of the content is.

10. The analyzer according to claim 5, further comprising: a preprocessing unit that calculates the intensity similarity between the reference intensity value and the target intensity value for each wavelength; The component analysis unit is an analyzer characterized in that the smaller the intensity similarity is, the lower the weighting coefficient applied to the intensity ratio during the estimation of the content is.

11. The analyzer according to any one of claims 1 to 10, wherein the storage unit stores a plurality of wavelength lists corresponding to the ionic valence numbers of the plasma states of the elements to be analyzed as the wavelength list; the similarity calculation unit sequentially calculates the difference between the reference intensity value and the target intensity value for each wavelength included in one wavelength list for each of the plurality of wavelength lists, and calculates the similarity based on the plurality of calculated differences. An analyzer characterized by the above.

12. The analyzer according to any one of claims 1 to 11, wherein the storage unit further stores a first mixed spectrum obtained from a substance containing a first element and a second element different from the first element; the similarity calculation unit calculates the similarity based on the difference between the target intensity value and the reference intensity value, and sequentially calculates the similarity based on the difference between the target intensity value and the intensity value obtained from the first mixed spectrum and corresponding to the wavelength included in the wavelength list. The component analysis unit is an analyzer characterized in that it estimates the types of elements contained in the sample based on the similarities sequentially calculated by the similarity calculation unit.

13. A processing unit configured to execute a computer program stored in a memory and used in an analyzer, wherein the processing unit a spectrum acquisition step of acquiring an emission spectrum of plasma light generated by irradiating a sample with a laser beam; a reading step of reading out the wavelength list from a storage unit that stores a wavelength list stored for each element to be analyzed and that is a combination of a plurality of wavelengths used during component analysis; A similarity calculation step of sequentially calculating the similarity between a reference intensity value, which is an intensity value obtained from the reference spectra of a plurality of elements to be analyzed and corresponds to the wavelengths included in the wavelength list, and a target intensity value, which is an intensity value obtained from the emission spectrum and corresponds to the wavelengths included in the wavelength list, for each element to be analyzed; An intensity ratio calculation step of calculating an intensity ratio between the reference intensity value and the target intensity value corresponding to the wavelengths included in the wavelength list; A component analysis step of estimating the types of elements contained in the sample based on the calculated similarity and estimating the content of the elements contained in the sample based on the calculated intensity ratio, and is configured to perform; In the reading step, a first wavelength list including a plurality of wavelengths in which a value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than a first value, and a second wavelength list including a plurality of wavelengths in which a value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than a second value greater than the first value are read from a storage unit that stores the first wavelength list and the second wavelength list; In the similarity calculation step, the similarity between the reference intensity value and the target intensity value corresponding to the wavelengths included in the first wavelength list is sequentially calculated for each element to be analyzed; A processing unit configured to calculate an intensity ratio between the reference intensity value and the target intensity value corresponding to the wavelengths included in the second wavelength list in the intensity ratio calculation step.

14. An analysis method used in an analyzer for estimating the types of elements contained in a sample based on the emission spectrum of plasma light generated from the sample by irradiating the surface of the sample with laser light and the reference spectra of a plurality of elements to be analyzed, comprising: A reading step of reading the wavelength list from a storage unit that stores the wavelength list, which is a wavelength list stored for each element to be analyzed and is a combination of a plurality of wavelengths used during component analysis; A similarity calculation step of sequentially calculating the similarity between a reference intensity value, which is an intensity value obtained from the reference spectrum and corresponds to the wavelengths included in the wavelength list, and a target intensity value, which is an intensity value obtained from the emission spectrum and corresponds to the wavelengths included in the wavelength list, for each element to be analyzed; An intensity ratio calculation step of calculating an intensity ratio between a reference intensity value and a target intensity value corresponding to a wavelength included in the wavelength list; Based on the calculated similarity, estimating the type of element contained in the sample, and based on the calculated intensity ratio, a component analysis step of estimating the content of the element contained in the sample; In the reading step, a first wavelength list including a plurality of wavelengths in which a value indicating the correlation between the content of the analysis target element and the reference intensity value is equal to or greater than a first value, and the content of the analysis target element and the reference intensity value are included. Reading the first wavelength list and the second wavelength list from a storage unit that stores a second wavelength list including a plurality of wavelengths in which a value indicating the correlation is greater than the first value and equal to or greater than a second value; In the similarity calculation step, the similarity between the reference intensity value and the target intensity value corresponding to the wavelength included in the first wavelength list is sequentially calculated for each analysis target element; The analysis method is characterized in that in the intensity ratio calculation step, an intensity ratio between a reference intensity value and a target intensity value corresponding to a wavelength included in the second wavelength list is calculated.

15. An analysis program used in an analyzer that estimates the type of element contained in a sample based on the emission spectrum of plasma light generated from the sample by irradiating the surface of the sample with laser light and the reference spectra of a plurality of analysis target elements, A reading step of reading the wavelength list from a storage unit that stores the wavelength list, which is a wavelength list stored for each analysis target element and is a combination of a plurality of wavelengths used in component analysis; A similarity calculation step of sequentially calculating, for each analysis target element, the similarity between a reference intensity value, which is an intensity value obtained from the reference spectrum and corresponds to a wavelength included in the wavelength list, and a target intensity value, which is an intensity value obtained from the emission spectrum and corresponds to a wavelength included in the wavelength list; An intensity ratio calculation step of calculating an intensity ratio between a reference intensity value and a target intensity value corresponding to a wavelength included in the wavelength list; Based on the calculated similarity, estimating the type of element contained in the sample, and based on the calculated intensity ratio, causing a computer to execute a component analysis step of estimating the content of the element contained in the sample; In the reading step, the first wavelength list including a plurality of wavelengths at which a value indicating the correlation between the content of the element to be analyzed and the reference intensity value is equal to or greater than a first value, and the correlation between the content of the element to be analyzed and the reference intensity value are read from a storage unit storing a second wavelength list including a plurality of wavelengths at which the value is equal to or greater than a second value greater than the first value, In the similarity calculation step, the similarity between the reference intensity value and the target intensity value corresponding to the wavelength included in the first wavelength list is sequentially calculated for each element to be analyzed. An analysis program that calculates an intensity ratio between a reference intensity value and a target intensity value corresponding to a wavelength included in the second wavelength list in the intensity ratio calculation step.

16. A computer-readable storage medium storing the analysis program according to claim 15.

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