Analytical method and composite analysis apparatus

Abstract

To provide a system capable of comprehensively analyzing organic materials through inorganic materials.SOLUTION: An analytical method is performed for a composite analysis apparatus capable of performing on a sample infrared spectroscopic analysis by infrared spectroscopic analysis method and LIBS analysis by laser-induced breakdown spectroscopy. The analytical method includes: steps ST02-ST06 of irradiating the sample with infrared to perform infrared spectroscopic analysis; steps ST08-ST12 of irradiating the sample with laser beam to perform LIBS analysis; and a step ST14 of identifying components of the sample on the basis of first analytical data obtained by the infrared spectroscopic analysis and second analytical data obtained by the LIBS analysis. The step of performing infrared spectroscopic analysis is performed before the step of performing LIBS analysis.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present disclosure relates to an analytical method and a multiplex analytical device. [Background technology]

[0002] Infrared spectroscopy is an analytical method in which a sample is irradiated with infrared light and the components in the sample are analyzed by detecting the transmitted or reflected light. Infrared spectroscopy is performed using an infrared spectrophotometer.

[0003] As described in JP 2019-32214 A (Patent Document 1), infrared spectroscopic analysis is suitable for analyzing polymeric materials and organic substances. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-32214 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, infrared spectroscopy is not the best method for analyzing inorganic substances such as metals, for which it is known that laser-induced breakdown spectroscopy (LIBS) is more suitable.

[0006] Therefore, the user must estimate the components to be analyzed in the sample and consider which analytical method the analysis device should use, which is time-consuming for the user.

[0007] The present disclosure has been made to solve such problems, and its purpose is to provide a system capable of comprehensively analyzing everything from organic to inorganic substances. [Means for solving the problem]

[0008] A first aspect of the present invention is an analysis method performed in a combined analysis device capable of performing infrared spectroscopy by infrared spectroscopy and LIBS analysis by laser-induced breakdown spectroscopy on a sample. The analysis method includes a step of performing infrared spectroscopy by irradiating the sample with infrared light, a step of performing LIBS analysis by irradiating the sample with laser light, and a step of identifying components of the sample based on first analysis data obtained by the infrared spectroscopy and second analysis data obtained by the LIBS analysis. The step of performing infrared spectroscopy is performed before the step of performing LIBS analysis.

[0009] Another aspect of the present invention is a composite analytical device including a sample holder, an infrared light source, a detector, a laser light source, a spectroscope, and a control device. A sample is placed in the sample holder. The infrared light source generates infrared light to be irradiated onto the sample. The detector detects infrared light emitted from the sample by irradiation with the infrared light. The laser light source generates laser light to be irradiated onto the sample. The spectroscope separates emission lines generated in the sample by irradiation with the laser light. The control device acquires first analysis data obtained by infrared spectroscopy analysis of the infrared light emitted from the sample, and second analysis data obtained by LIBS analysis of the emission lines generated in the sample. The control device identifies components of the sample based on the first analysis data and the second analysis data. The control device irradiates the sample with infrared light before irradiating the sample with the laser light. Effect of the Invention

[0010] According to the present disclosure, it is possible to provide a system capable of comprehensively analyzing everything from organic to inorganic substances. [Brief description of the drawings]

[0011] [Figure 1]FIG. 2 is a diagram showing the configuration of a multiple analysis device and a first optical path during infrared spectroscopic analysis according to an embodiment. [Diagram 2] FIG. 13 is a diagram showing a second optical path during LIBS analysis. [Diagram 3] 10 is a diagram showing the configuration of an analysis device and a first optical path during infrared spectroscopic analysis according to Modification 1. FIG. [Figure 4] 4 is a flowchart showing a process relating to an analysis method according to the embodiment. [Diagram 5] 13 is a flowchart showing a process relating to an analysis method according to Modification 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference characters and their description will not be repeated.

[0013] [1. Configuration of the combined analysis device according to the embodiment] Fig. 1 is a diagram showing the configuration of a combined analytical device 100 according to an embodiment, and a first optical path 15 during infrared spectroscopic analysis. Fig. 2 is a diagram showing a second optical path 25 during LIBS analysis. Hereinafter, the configuration of the combined analytical device 100, the first optical path 15, and the second optical path 25 will be described with reference to Figs. 1 and 2.

[0014] The multiple analysis device 100 includes a control device 90 and an analysis device 101 .

[0015] The analysis device 101 is a device that performs analysis of a sample S. The analysis device 101 is capable of performing infrared spectroscopic analysis by infrared spectroscopic analysis and LIBS analysis by laser-induced breakdown spectroscopy. The analysis device 101 usually performs LIBS analysis after infrared spectroscopic analysis.

[0016] The analysis device 101 includes a sample holder 5, an infrared light source 10, a detector 11, a laser light source 20, a spectroscope 21, and a plurality of mirrors 31-37.

[0017] The sample S is placed on the sample holder 5. In one embodiment, the sample S is a solid sample. However, as described later, the sample S may be a liquid sample or a gas sample stored in a container. In the example of FIG. 1, the sample holder 5 is a sample stage. In one embodiment, the direction perpendicular to the sample stage is the Z axis, and the plane parallel to the sample stage is the XY plane. In one embodiment, the sample stage is used in a state where it is placed so that the Z axis is approximately parallel to the direction of gravity (vertical direction). The sample S is placed on the upper surface of the sample stage. The sample stage is formed, for example, of a material (for example, metal) that has low transmittance of infrared light. The sample holder 5 may be any mechanism that can fix the position of the sample S during analysis, and may be, for example, a gripping mechanism that grips the sample S.

[0018] The infrared light source 10 generates infrared light to be irradiated onto the sample S. In one embodiment, the infrared light source 10 includes an interferometer (not shown) and a light source unit (not shown) and generates coherent infrared light for performing spectrum measurement. In one embodiment, the infrared light generated from the infrared light source 10 is incident on a specific position S0 of the sample S. The specific position S0 is, for example, a position to be analyzed of the sample S. In one embodiment, the specific position S0 is a position where LIBS analysis is possible, and more specifically, a position on the surface of the sample S or a position near the surface of the sample S. The infrared light irradiated onto the sample S is, for example, an infrared beam having a predetermined beam diameter and power density. The beam diameter and power density are set to have a beam intensity sufficient for infrared spectroscopic analysis.

[0019] The detector 11 is a photodetector that detects infrared light emitted from the sample S when irradiated with infrared light. A light reception signal of the detector 11 is transmitted to the control device 90.

[0020] The laser light source 20 generates a laser light to be irradiated onto the sample S. In one embodiment, the laser light source 20 includes a laser oscillator (not shown) and a condenser lens (not shown), and the laser pulse emitted by the laser oscillator is condensed by the condenser lens and irradiated onto the sample S. In one embodiment, the infrared light generated from the laser light source 20 is incident on a specific position S0 of the sample S. The laser light to be irradiated onto the sample S is set to have, for example, a predetermined beam diameter and power density. The beam diameter and power density are set to have a beam intensity sufficient for LIBS analysis.

[0021] The spectrometer 21 is an ultraviolet-visible spectrometer that separates emission lines generated in the sample S by irradiation with laser light. The emission lines are atomic beams and / or ion beams that are generated when sample components are atomized and excited (plasmaized) on the sample surface and / or near the surface by irradiation with laser light. A signal indicating the result of the spectrometry of the emission lines by the spectrometer 21 is transmitted to the control device 90.

[0022] The positions of the mirrors 31 to 37 can be a first position shown in FIG. 1 and a second position shown in FIG. 2. In the example of FIG. 1 to FIG. 2, the positions of the mirrors 31 and 32 indicated by the arrows AR1 and AR2, respectively, are different between the first position and the second position. The mirrors 31 and 32 are movable mirrors configured to be able to change their positions by a mirror drive mechanism (not shown). The mirror drive mechanism can move the locations of the mirrors 31 and 32 from the position shown in FIG. 1 (first position) to the position shown in FIG. 2 (second position), or from the position shown in FIG. 2 (second position) to the position shown in FIG. 1 (first position). An example of the mirror drive mechanism is, but is not limited to, a rail that slides the positions of the mirrors 31 and 32.

[0023] Mirrors 33 to 37 are fixed mirrors whose positions are fixed. Mirrors 35 to 37 are parabolic mirrors arranged at positions that form a focal point at specific position S0 (described later). Meanwhile, mirrors 31, 32, 33, and 34 are each arranged at a position that causes light to be incident on the parabolic mirror, or at a position that introduces light generated from the parabolic mirror into detector 11 or spectroscope 21.

[0024] When the positions of the multiple mirrors 31 to 37 are set to the first position, a first optical path 15 is formed. The first optical path 15 includes an optical path 151 and an optical path 152. In the optical path 151, the infrared light generated from the infrared light source 10 is reflected in order by the mirrors 33, 36, and 35, and then incident on a specific position S0 of the sample S. In the optical path 152, the infrared light emitted from the specific position S0 is reflected in order by the mirrors 37, 36, and 34, and then incident on the detector 11.

[0025] When the positions of the mirrors 31 to 37 are set to the second positions, a second optical path 25 is formed. The second optical path 25 includes an optical path 251 and an optical path 252. In the optical path 251, the laser light generated from the laser light source 20 is reflected by the mirrors 31, 36, and 35 in this order, and then enters the specific position S0. In the optical path 252, the emission line generated from the specific position S0 is reflected by the mirrors 37, 36, 34, and 32 in this order, and then enters the spectroscope 21.

[0026] More specifically, the first positions of the multiple mirrors 31 to 37 are preferably set so that, during infrared spectroscopic analysis, the intersection (so-called focal point) between the center of the incident infrared light 1511 and the center of the outgoing infrared light 1521 at a specific position S0 of the sample S is located at the specific position S0 of the sample S.

[0027] In addition, it is preferable that the second positions of the multiple mirrors 31 to 37 are set so that, during LIBS analysis, the intersection (so-called focal point) between the center of the incident laser light 2511 and the center of the outgoing emission line 2521 at a specific position S0 of the sample S is located at the specific position S0 of the sample S.

[0028] In the example of Figs. 1 and 2, when light is incident on position 361 of mirror 36 at a predetermined first angle, it is configured to focus on a specific position S0 of the sample, and to emit light from position 362 of mirror 36 at a predetermined second angle. In the first position, mirror 33 is used so that infrared light 1512 is incident on position 361 of mirror 36 at the first angle, and mirror 34 is used so that infrared light 1522 emitted from position 362 of mirror 36 is incident on detector 11. In the second position, mirror 31 is used so that laser light 2512 is incident on position 361 of mirror 36 at the first angle, and mirrors 34 and 32 are used so that emission line 2522 emitted from position 362 of mirror 36 is incident on spectroscope 21.

[0029] As described above, in the analytical device 101, with a simple configuration and control of moving two mirrors to switch the optical path, it is possible to analyze the same position (specific position S0) of the sample S in infrared spectroscopic analysis and LIBS analysis.

[0030] The control device 90 can be configured by a personal computer or a microcomputer including a CPU (Central Processing Unit) and a memory (not shown).

[0031] The control device 90 controls the analysis device 101. The control device 90 controls the infrared light source 10 and the detector 11 to perform infrared spectroscopic analysis. The control device 90 controls the laser light source 20 and the spectrometer 21 to perform LIBS analysis. When performing infrared spectroscopic analysis, the control device 90 controls the mirror driving unit to place the positions of the multiple mirrors 31 to 37 at a first position. When performing LIBS analysis, the control device 90 controls the mirror driving unit to place the positions of the multiple mirrors 31 to 37 at a second position. Note that the movement of the mirrors 31 and 32 may be configured to be performed manually by a user. However, in order to move the mirrors 31 and 32 to accurate positions to perform an analysis with high accuracy, it is preferable that the positions of the mirrors 31 and 32 are controlled by the control device 90.

[0032] Before irradiating the sample S with laser light to perform LIBS analysis, the control device 90 performs infrared spectroscopic analysis by irradiating the sample S with infrared light. This makes it possible to perform infrared spectroscopic analysis on the components of the sample S before they are denatured by the LIBS analysis. Therefore, it is possible to accurately perform both infrared spectroscopic analysis and LIBS analysis on the same position (specific position S0) of the sample S.

[0033] The control device 90 further performs processing to identify the components of the sample S based on the signal received from the detector 11 in the infrared spectroscopic analysis and the signal received from the spectrometer 21 in the LIBS analysis.

[0034] Specifically, the control device 90 first obtains first analysis data obtained by infrared spectroscopic analysis of the infrared light emitted from the sample S, and second analysis data obtained by LIBS analysis of the emission lines generated in the sample S. The first analysis data is, for example, an infrared spectrum. The second analysis data is, for example, an emission line spectrum.

[0035] In one embodiment, the control device 90 performs processing such as Fourier transform on the light receiving signal received from the detector 11 to create an infrared spectrum. The control device 90 also creates an emission line spectrum based on a signal indicating the spectral result of the emission line received from the spectrometer 21. However, the infrared spectrum and the emission line spectrum may be sent to the control device 90 after being created by the detector 11 and the spectrometer 21, respectively.

[0036] Furthermore, the control device 90 identifies the components of the sample S based on the first analysis data and the second analysis data. Specifically, for example, the control device 90 identifies the components at the specific position S0 based on the peak wavelength of the infrared spectrum, and quantifies the components according to the intensity of the peak wavelength. Also, for example, the control device 90 identifies the components at the specific position S0 based on the peak wavelength of the emission line spectrum, and quantifies the components according to the intensity of the peak wavelength.

[0037] According to the combined analysis device 100 described above, it is possible to perform both infrared spectroscopy and LIBS analysis on the sample S. Therefore, when the component to be analyzed in the sample S is organic, the component can be accurately identified based on the first analysis data obtained by the infrared spectroscopy. On the other hand, even when the component to be analyzed in the sample S is inorganic, the component can be accurately identified based on the second analysis data obtained by the LIBS analysis. Therefore, the combined analysis device 100 can accurately identify the component to be analyzed in the sample S, whether it is organic or inorganic. This saves the user the trouble of estimating the component to be analyzed in the sample S before starting the analysis of the sample S and thinking about whether to provide the sample to an analysis device suitable for organic matter or an analysis device suitable for inorganic matter. In addition, when the user cannot estimate the component to be analyzed in the sample, the trouble of moving the sample can be saved compared to the case where the sample is moved to a LIBS analysis device after infrared spectroscopy is performed in an infrared spectroscopy analysis device and LIBS analysis is performed. Furthermore, it is possible to prevent an inappropriate analysis from being performed by performing LIBS analysis first and then performing infrared spectroscopy on a denatured sample. As described above, the multiple analytical device 100 can provide a system capable of comprehensively analyzing a range of substances from organic to inorganic.

[0038] In particular, the combined analysis device 100 is highly convenient in that infrared spectroscopy and LIBS analysis can be easily performed at the same position (specific position S0) of the sample S. For example, infrared spectroscopy and LIBS analysis are often used to identify the components of small foreign matter in a product. The size of the foreign matter is not limited to this, but may be, for example, a maximum dimension of 100 μm or less, more specifically, 10 μm square. For such a small foreign matter, it is a difficult task for a user to focus for infrared spectroscopy and then refocus for LIBS analysis at exactly the same position. In addition, there is a possibility that the user may mistakenly focus on a foreign matter different from the foreign matter analyzed by infrared spectroscopy. However, in the combined analysis device 100, after performing infrared spectroscopy, the positions of the mirrors 31 and 32 can be moved to perform LIBS analysis at the same position as the infrared spectroscopy. Therefore, the user can save the trouble of resetting the focus. In addition, infrared light analysis and LIBS analysis can be performed at exactly the same position.

[0039] In the above, the case where a solid sample is analyzed in the combined analysis device 100 has been mainly described. However, the combined analysis device 100 can also analyze liquid samples or gas samples in the same way. For example, in the LIBS analysis, high-speed analysis is possible for samples including any of gas, liquid, and solid without performing complicated pretreatment processes. In particular, since high-temperature plasma (for example, 15000K to 30000K) is generated by laser light, not only metal elements but also halogens and the like that are difficult to detect by other emission spectroscopic analyses can be measured on the order of 1 ppm. In other words, the combined analysis device 100 can perform high-precision LIBS analysis for all gases, liquids, and solids in a short time.

[0040] Furthermore, in the multiple analytical device 100, even for organic substances for which LIBS analysis is not suitable, it is possible to perform infrared spectroscopy, which is suitable for the analysis of organic substances, before modifying the organic substances by LIBS analysis.

[0041] Therefore, by using the multiple analytical device 100, a user can accurately identify components contained in a sample without having to consider whether the analysis target position in the sample is organic or inorganic.

[0042] In addition, since the combined analytical device 100 can perform both infrared spectroscopy and LIBS analysis in one device, the installation space of the device can be made smaller than when two devices, an infrared spectrophotometer specialized for infrared spectroscopy and a laser organic breakdown spectroscopy analyzer specialized for LIBS analysis, are installed. Furthermore, since the combined analytical device 100 can share parts (e.g., a control device) required for both infrared spectroscopy and LIBS analysis, the parts cost can be reduced compared to when two independent devices are manufactured.

[0043] [2. Configuration of the analysis device according to the first modification] The analytical device 101 according to the above embodiment is configured to perform infrared spectroscopic analysis of reflected light from the sample S, whereas the analytical device 101A according to the first modification is configured to perform infrared spectroscopic analysis of transmitted light from the sample S.

[0044] FIG. 3 is a diagram showing the configuration of an analysis device 101A according to the first modification and the first optical path during infrared spectroscopic analysis.

[0045] 3, an analysis device 101A according to the first modification differs from the analysis device 101 in the position of an infrared light source 10A and the structure of a sample holder 5A. In addition, mirrors 38 to 40 are added to the analysis device 101A. Due to the above structural changes, a first optical path 15A during infrared analysis of the analysis device 101A differs from the first optical path 15 of the analysis device 101.

[0046] The sample holder 5A is configured to be able to obtain infrared light transmitted through the sample S placed in the sample holder 5A. In the example of FIG. 3, the sample holder 5A is a sample stage in which a through hole 51A is formed. By using the sample holder 5A, it is possible to make infrared light 1511A, 1511A' that has passed through the through hole 51A enter the sample S from a predetermined direction (downward in FIG. 3). Then, infrared light 1521A, 1521A' that has passed through the sample S is emitted in the opposite direction to the predetermined direction (upward in FIG. 3).

[0047] The mirrors 38 to 40 are parabolic mirrors whose positions are fixed.

[0048] The infrared light source 10A is disposed on the opposite side to the sample holder 5A with respect to the mirrors 38 to 40 (the lower side in FIG. 3).

[0049] In one embodiment, the infrared light source 10A and the mirrors 38 to 40 are arranged so that the intersection (also called "focus") of the incident light is formed at a specific position S0A of the sample S. The specific position S0A is, for example, a position on the surface of the sample S or a position near the surface where LIBS analysis is possible. Hereinafter, a more detailed description will be given with reference to FIG. 3. The infrared light source 10A emits infrared light 1512A and infrared light 1512A', which are reflected by mirrors 39, 38 and mirrors 39, 40, respectively, to become infrared light 1511A and 1511A'. The infrared light 1511A and 1511A' are set to form an intersection at the specific position S0A. Each of the infrared light 1512A and 1512A' emitted from the infrared light source 10A is, for example, an infrared beam having a predetermined beam diameter and power density. The beam diameter and power density are set so as to have a beam intensity sufficient for analysis.

[0050] The transmitted light (infrared light 1521A, 1521A′) that has passed through the specific position S0 is reflected by the mirrors 37, 36, 34 and the mirrors 35, 36, 34, respectively, and then enters the detector 11.

[0051] The infrared light emitted from infrared light source 10A may be, for example, a single infrared beam having a diameter D. In this case, the beam is split into left and right beams and reflected by mirror 39. The two split beams are then reflected by mirrors 38 and 40, respectively, and then intersect at specific position S0A. The transmitted infrared light that passes through specific position S0A is then reflected by mirrors 37, 36, and 34 and mirrors 35, 36, and 34, respectively, and then enters detector 11.

[0052] As described above, by using the analytical device 101A according to the first modification, it is possible to perform infrared spectroscopic analysis of transmitted infrared light. Note that the analytical device 101A can also perform LIBS analysis by moving the positions of the mirrors 31 and 32 to the positions shown in Fig. 2. Therefore, the analytical device 101A according to the first modification can provide a system capable of comprehensively analyzing organic and inorganic substances, similar to the analytical device 101 according to the embodiment.

[0053] In particular, the analysis device 101A according to the first modification is suitable for analyzing a sample S having a high infrared light transmittance, and can accurately analyze the sample S having a high infrared light transmittance. On the other hand, the analysis device 101 according to the embodiment is suitable for analyzing a sample S having a high infrared light reflectance, and can accurately analyze the sample S having a high infrared light reflectance.

[0054] Moreover, the analysis device 101A according to the first modification has an advantage that the diameter of the infrared light irradiated on the sample S can be easily increased. In the LIBS analysis, an emission line generated from a component near the sample surface is detected, so that a configuration in which the laser light source 20 and the spectroscope 21 are installed on the same side (upper side in FIG. 2) of the XY plane passing through the specific position S0 of the sample S is simple and preferable (see FIG. 2). In addition, in order to perform infrared spectroscopic analysis of the reflected light of the infrared light at the same specific position S0 as in LIBS, a configuration in which the infrared light source 10 and the detector 11 are also installed on the same side (upper side in FIG. 1) as the laser light source 20 and the spectroscope 21 is simple and preferable (see FIG. 1). On the other hand, in order to detect the transmitted light of the infrared light and perform infrared spectroscopic analysis, a configuration in which the infrared light source 10 is installed on the opposite side (lower side in FIG. 3) of the detector 11, the laser light source 20, and the spectroscope 21 is simple and preferable (see FIG. 3). As a result, in the analysis device 101A, unlike the analysis device 101, there is no need to place any components (for example, mirrors 31, 33) other than the mirrors 38-40 for focusing on the specific position S0 in the space between the infrared light source 10A and the sample S. Therefore, the analysis device 101A can be easily configured so that infrared light with a large diameter is incident on the sample S. This makes it possible to increase the amount of infrared light irradiated on the sample S and detected by the detector 11, thereby improving the analysis accuracy.

[0055] On the other hand, the analytical device 101 according to the embodiment has the advantage that the parts required for LIBS analysis and / or infrared light detection (e.g., mirrors 35-36) can be used as parts required for the incidence of infrared light on the sample S, thereby reducing parts costs.

[0056] [3. Processing for Analysis Method According to the Embodiment] 4 is a flowchart showing a process related to the analysis method according to the embodiment. The process in FIG.

[0057] In steps (hereinafter referred to as "ST") 02 to ST06, the control device 90 irradiates the sample S with infrared light and performs infrared spectroscopic analysis.

[0058] In ST02, the control device 90 controls a mirror drive mechanism (not shown) to place the multiple mirrors 31 to 37 in the first positions shown in FIG.

[0059] In ST04, the control device 90 irradiates the infrared light generated from the infrared light source 10 to the specific position S0 of the sample S. In one embodiment, the control device 90 first controls the infrared light source 10 to generate infrared light. The infrared light generated by the infrared light source 10 passes through a first optical path 15 formed by a mirror arranged at a first position. More specifically, the infrared light generated by the infrared light source 10 is reflected by mirrors 33, 36, and 35 in order and is incident on the specific position S0 of the sample S. Then, the infrared light emitted from the specific position S0 is reflected by mirrors 37, 36, and 34 in order and is incident on the detector 11. The specific position S0 is a position to be analyzed. In one embodiment, the specific position S0 is a small foreign object in a product found by a user through visual observation or microscopic observation.

[0060] In ST06, the control device 90 performs infrared spectroscopic analysis on the infrared light emitted from the specific position S0 to obtain first analysis data. The first analysis data is, for example, an infrared spectrum.

[0061] In ST08 to ST12, the control device 90 irradiates the sample S with laser light to perform LIBS analysis.

[0062] In ST08, the control device 90 controls a mirror drive mechanism (not shown) to place the multiple mirrors at a second position different from the first position.

[0063] In ST10, the control device 90 irradiates the specific position S0 with the laser light generated from the laser light source 20. In one embodiment, the control device 90 first controls the laser light source 20 to generate the laser light. The laser light generated by the laser light source 20 passes through a second optical path 25 formed by a mirror disposed at a second position. More specifically, the laser light generated by the laser light source 20 is reflected in turn by mirrors 31, 36, and 35, and is incident on the specific position S0 of the sample S. Then, the emission line emitted from the specific position S0 is reflected in turn by mirrors 37, 36, 34, and 32, and is incident on the spectroscope 21.

[0064] In ST12, the control device 90 obtains second analysis data obtained by performing LIBS analysis on the emission lines generated at the specific position S0. The second analysis data is, for example, an emission line spectrum.

[0065] In ST14, the control device 90 identifies the component at the specific position S0 based on the first analysis data obtained by the infrared spectroscopy analysis and the second analysis data obtained by the LIBS analysis. This allows, for example, the component of a foreign substance in a product to be identified. For example, based on a peak in the infrared spectrum, an organic component corresponding to the peak can be accurately identified. On the other hand, based on a peak in the emission line spectrum, an inorganic component corresponding to the peak can be accurately identified.

[0066] As described above, in the process of FIG. 4, infrared spectroscopic analysis is performed before LIBS analysis. Therefore, infrared spectroscopic analysis can be performed on components before they are denatured by LIBS analysis. This makes it easy to accurately identify components even if the components to be analyzed are organic, inorganic, or contain both organic and inorganic substances. Therefore, it is possible to provide a system that can comprehensively analyze everything from organic to inorganic substances.

[0067] In addition, in ST02 to ST06 of Figure 4, the process in which the control device 90 performs infrared spectroscopic analysis of the reflected light emitted from the sample S has been described, but this process may be replaced by a process in which the control device 90 performs infrared spectroscopic analysis of the transmitted light emitted from the sample S.

[0068] [4. Processing for analysis method related to modification example 2] The analysis method according to the second modification includes a process in which, when the control device 90 has information about the components to be analyzed, the control device 90 determines whether to perform either infrared spectroscopic analysis or LIBS analysis, or both, based on the information.

[0069] 5 is a flowchart showing a process relating to the analysis method according to Modification 2. The process in FIG.

[0070] In ST010, the control device 90 acquires information about the components to be analyzed. The information about the components to be analyzed is, for example, the names of substances that are candidates for the components to be analyzed. For example, a user operates an input device (not shown) of the control device 90 to input information about the components to be analyzed, and the control device 90 acquires the information input by the input device.

[0071] In ST011, the control device 90 judges whether or not the components to be analyzed may contain organic matter based on the input information. Specifically, for example, the control device 90 judges whether or not a substance name corresponding to an organic matter is included in the substance names that are candidates for the components to be analyzed. The substance name corresponding to an organic matter is a substance name that indicates that the substance is an organic matter, for example, the name of the organic matter.

[0072] If there is a possibility that the components to be analyzed include organic matter (YES in ST011), the control device 90 advances the process to ST02. The processes in ST02 to ST06 in FIG.

[0073] Following the process of ST06, or if the component to be analyzed is unlikely to contain an organic substance (NO in ST011), in ST07, the control device 90 determines whether or not the component to be analyzed is likely to contain an inorganic substance based on the input information. Specifically, for example, the control device 90 determines whether or not a substance name corresponding to an inorganic substance is included in the substance names that are candidates for the component to be analyzed. A substance name corresponding to an inorganic substance is a substance name that indicates that the substance is an inorganic substance, for example, the name of an inorganic substance.

[0074] If there is a possibility that the components to be analyzed include inorganic substances (YES in ST07), the control device 90 advances the process to ST08. The processes in ST08 to ST12 in FIG.

[0075] Following processing in ST12, or if the component being analyzed is not likely to contain inorganic matter (NO in ST07), in ST14A, the controller 90 identifies the component at the specific location S0 based on the analytical data obtained in ST06 and / or ST12.

[0076] As described above, the process of Fig. 5 includes steps ST010, ST011, and ST07 for determining whether to perform either or both of steps ST02 to ST06 for performing infrared spectroscopy analysis and steps ST08 to ST12 for performing LIBS analysis based on information about the components to be analyzed in the sample. This allows the user to reduce the time spent performing obviously unnecessary analysis. Therefore, further efficiency of analysis can be expected in a system capable of comprehensively analyzing organic and inorganic substances.

[0077] In addition, in ST010, if the user does not input the name of a substance that is a candidate for the component to be analyzed, it may be determined that the component to be analyzed may include both organic and inorganic substances, and infrared spectroscopy analysis and LIBS spectroscopy analysis may be performed.

[0078] Alternatively, the user may more directly input information as to whether or not the components to be analyzed are likely to include organic matter or inorganic matter. Similarly, the user may input instructions as to whether or not to perform infrared spectroscopy or LIBS analysis. Furthermore, when the components to be analyzed are determined for each type of sample, the user may input the type of sample.

[0079] [Aspects] It will be appreciated by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0080] (Item 1) An analytical method according to one embodiment is an analytical method performed in a combined analytical device capable of performing infrared spectroscopic analysis by infrared spectroscopic analysis and LIBS analysis by laser-induced breakdown spectroscopy on a sample. The analytical method includes a step of performing infrared spectroscopic analysis by irradiating the sample with infrared light, a step of performing LIBS analysis by irradiating the sample with laser light, and a step of identifying components of the sample based on first analysis data obtained by the infrared spectroscopic analysis and second analysis data obtained by the LIBS analysis. The step of performing infrared spectroscopic analysis is performed before the step of performing LIBS analysis.

[0081] According to the analysis method described in paragraph 1, the infrared spectroscopic analysis is performed before the LIBS analysis. Therefore, the components before they are denatured by the LIBS analysis can be analyzed by infrared spectroscopic analysis. This makes it easy to accurately identify the components even if the components to be analyzed are organic, inorganic, or contain both organic and inorganic substances. Therefore, it is possible to provide a system that can comprehensively analyze everything from organic to inorganic substances.

[0082] (2) In the analysis method according to the first aspect, the step of performing infrared spectroscopic analysis includes a step of irradiating a specific position of the sample with infrared light generated from an infrared light source, and the step of performing LIBS analysis includes a step of irradiating the specific position with laser light generated from a laser light source.

[0083] According to the analytical method described in the second aspect, it is easy to analyze the same position (specific position) of a sample in the infrared spectroscopy analysis and the LIBS analysis.

[0084] (Item 3) In the analysis method described in Item 2, the combined analysis device further includes a plurality of mirrors. The step of performing infrared spectroscopic analysis further includes a step of arranging the plurality of mirrors at a first position. The step of performing LIBS analysis further includes a step of arranging the plurality of mirrors at a second position different from the first position. At the first position, a first optical path is formed. At the first optical path, infrared light generated from the infrared light source is incident on a specific position, and infrared light emitted from the specific position is incident on a detector. At the second position, a second optical path is formed. At the second optical path, laser light generated from the laser light source is incident on the specific position, and an emission line generated at the specific position is incident on a spectrometer.

[0085] According to the analysis method described in paragraph 3, it is possible to analyze the same position (specific position) of a sample in infrared spectroscopic analysis and LIBS analysis with a simple configuration and control of moving a mirror to switch the optical path.

[0086] (Item 4) In the analysis method described in any one of items 1 to 3, the step of performing infrared spectroscopic analysis includes a step of performing infrared spectroscopic analysis of reflected light from the sample, or a step of performing infrared spectroscopic analysis of transmitted light from the sample.

[0087] When the analysis method described in paragraph 4 includes a step of performing infrared spectroscopy of reflected light, samples with high infrared reflectance can be analyzed with high accuracy. In addition, the cost of parts can be reduced in that parts required for LIBS analysis and / or infrared detection can be used as parts required for infrared light incidence on the sample. On the other hand, when the analysis method described in paragraph 4 includes a step of performing infrared spectroscopy of transmitted light, samples with high infrared transmittance can be analyzed with high accuracy. In addition, it is easy to increase the diameter of the infrared light irradiated on the sample.

[0088] (Item 5) The analytical method according to any one of items 1 to 4 further comprises a step of determining to perform either or both of a step of performing infrared spectroscopic analysis and a step of performing LIBS analysis based on information about the components to be analyzed in the sample.

[0089] According to the analytical method described in item 5, it is possible to further improve the efficiency of analysis in a system capable of comprehensively analyzing organic and inorganic substances.

[0090] (Item 6) A composite analysis device according to another aspect is a composite analysis device including a sample holder, an infrared light source, a detector, a laser light source, a spectroscope, and a control device. A sample is placed in the sample holder. The infrared light source generates infrared light to be irradiated onto the sample. The detector detects infrared light emitted from the sample by irradiation with infrared light. The laser light source generates laser light to be irradiated onto the sample. The spectroscope separates emission lines generated in the sample by irradiation with the laser light. The control device acquires first analysis data obtained by infrared spectroscopic analysis of the infrared light emitted from the sample, and second analysis data obtained by LIBS analysis of the emission lines generated in the sample. The control device identifies components of the sample based on the first analysis data and the second analysis data. The control device irradiates the sample with infrared light before irradiating the sample with laser light.

[0091] According to the composite analyzer described in paragraph 6, when the component to be analyzed in the sample is organic, the component can be accurately identified based on the first analysis data obtained by infrared spectroscopy. On the other hand, when the component to be analyzed in the sample is inorganic, the component can be accurately identified based on the second analysis data obtained by LIBS analysis. This saves the user the trouble of estimating the component to be analyzed in the sample and considering whether to subject the sample to an analysis device suitable for organic substances or an analysis device suitable for inorganic substances before starting the analysis of the sample. Furthermore, it is possible to eliminate the risk of performing an inappropriate analysis, such as performing LIBS analysis first and then performing infrared spectroscopy on a denatured sample. As described above, a system capable of comprehensively analyzing organic substances to inorganic substances can be provided.

[0092] (Item 7) In the combined analysis device described in item 6, the combined analysis device further includes a plurality of mirrors. The positions of the plurality of mirrors can be a first position and a second position. In the first position, a first optical path is formed. In the first optical path, infrared light generated from the infrared light source is incident on a specific position, and the infrared light emitted from the specific position is incident on a detector. In the second position, a second optical path is formed. In the second optical path, laser light generated from the laser light source is incident on a specific position, and an emission line generated at the specific position is incident on a spectrometer.

[0093] According to the combined analysis device described in paragraph 7, after performing infrared spectroscopic analysis, LIBS analysis can be performed at the same position as the infrared spectroscopic analysis by moving the position of the mirror. This saves the user the trouble of resetting the focus. In addition, infrared light analysis and LIBS analysis can be performed at exactly the same position.

[0094] The embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0095] 5,5A sample holder, 10,10A infrared light source, 11 detector, 15,15A first optical path, 20 laser light source, 21 spectrometer, 25 second optical path, 31-40 mirror, 51A through hole, 90 control device, 100 composite analysis device, 101,101A analysis device, 151,152,251,252 optical path, 361,362 position, 1511,1511A,1512,1512A,1521,1521A,1522 infrared light, 2511,2512 laser light, 2521,2522 emission line, S sample, S0,S0A specific position.

Claims

1. An analytical method performed on a sample using a combined analytical instrument capable of performing infrared spectroscopy and LIBS analysis by laser-induced breakdown spectroscopy, The steps include: irradiating the sample with infrared light and performing the infrared spectroscopic analysis; The steps include: irradiating the sample with laser light to perform the LIBS analysis; The process includes the step of identifying the components of the sample based on the first analytical data obtained by the infrared spectroscopic analysis and the second analytical data obtained by the LIBS analysis, The step of performing the infrared spectroscopic analysis is performed before the step of performing the LIBS analysis.

2. The step of performing the aforementioned infrared spectroscopic analysis is: The step includes irradiating a specific location on the sample with infrared light generated from an infrared light source, The step of performing the aforementioned LIBS analysis is: The analytical method according to claim 1, further comprising the step of irradiating the specific position with laser light generated from a laser light source.

3. The aforementioned combined analyzer further comprises multiple mirrors, The step of performing the aforementioned infrared spectroscopic analysis is: The step further includes positioning the plurality of mirrors in a first position, The step of performing the aforementioned LIBS analysis is: The further step includes arranging the plurality of mirrors in a second position different from the first position, At the first position, a first optical path is formed. In the first optical path, infrared light generated from the infrared light source is incident on the specific position, and infrared light emitted from the specific position is incident on the detector. At the second position, a second optical path is formed. The analysis method according to claim 2, wherein in the second optical path, laser light generated from the laser light source is incident on the specific position, and the emission line generated at the specific position is incident on a spectrometer.

4. The step of performing the aforementioned infrared spectroscopic analysis is: The analytical method according to any one of claims 1 to 3, comprising the step of performing infrared spectroscopic analysis of reflected light from the sample, or the step of performing infrared spectroscopic analysis of transmitted light from the sample.

5. The analytical method according to any one of claims 1 to 3, further comprising the step of deciding to perform either the step of performing infrared spectroscopic analysis and the step of performing LIBS analysis, or both, based on information about the components of the sample to be analyzed.

6. The sample holder in which the sample is placed, An infrared light source that generates infrared light to irradiate the aforementioned sample, A detector that detects infrared light emitted from the sample upon irradiation with the aforementioned infrared light, A laser light source that generates laser light to irradiate the sample, A spectrometer for spectrally analyzing the emission lines generated in the sample by irradiation with the laser light, Equipped with a control device, The control device is First analysis data obtained by infrared spectroscopy analysis of infrared light emitted from the sample, and second analysis data obtained by LIBS analysis of the emission lines generated in the sample are obtained. Based on the first and second analysis data, the components of the sample are identified. The control device is a combined analytical device that irradiates the sample with infrared light before irradiating the sample with laser light.

7. The aforementioned combined analyzer further comprises multiple mirrors, The aforementioned multiple mirrors can take on positions of a first position and a second position. At the first position, a first optical path is formed. In the first optical path, infrared light generated from the infrared light source is incident on a specific position, and infrared light emitted from the specific position is incident on the detector. At the second position, a second optical path is formed. The composite analytical apparatus according to claim 6, wherein in the second optical path, laser light generated from the laser light source is incident on the specific position, and the emission line generated at the specific position is incident on the spectrometer.