Quantitative analysis method, quantitative analysis system, and program for quantitative analysis system

Abstract

To provide a quantitative analysis method for improving the accuracy of a quantitative analysis based on a fluorescent X-ray spectrum by accurately identifying light elements included an unknown sample.SOLUTION: A quantitative analysis method includes: a Raman spectrum measurement step of measuring a Raman scattered light spectrum generated from an unknown sample by irradiating light to the unknown sample; a Raman spectrum analysis step of identifying information on light elements equal to or smaller than a prescribed atomic number included in the unknown sample on the basis of the measured Raman spectrum; a fluorescent X-ray spectrum measurement step of irradiating an X-ray to the unknown sample to measure a fluorescent X-ray spectrum that is generated; and a fluorescent X-ray spectrum analysis step of determining a quantity of elements of chemical compounds by an FP (fundamental parameter) method on the basis of the measured fluorescent X-ray spectrum. The fluorescent X-ray spectrum analysis step includes a remaining component setting step of setting a remaining component in the FP method on the basis of information on light elements identified by the Raman spectrum analysis step.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for quantifying compounds or elements contained in an unknown sample based on a measured fluorescent X-ray spectrum. [Background technology]

[0002] X-ray fluorescence analysis is sometimes used as a type of analytical method to non-destructively quantify the components (compounds or elements) contained in a sample. Specifically, in X-ray fluorescence analysis, a sample is irradiated with primary X-rays and the spectrum of fluorescent X-rays generated by the sample is measured. Based on the measured spectrum of fluorescent X-rays, the components contained in the sample are quantified using the calibration curve method or the FP (fundamental parameter) method.

[0003] The FP method is used to quantify each component of an unknown sample for which a standard sample with a known concentration of each component cannot be prepared. In other words, in the FP method, the concentration (content) of each component thought to be contained in the unknown sample is estimated by qualitative analysis using fluorescent X-rays, etc., under the assumption that the sum of these is, for example, 100%, and the theoretical X-ray intensity thought to be generated from the estimated concentration of each component is calculated. Then, the theoretical X-ray intensity is compared with the actually measured fluorescent X-ray intensity, and the estimated concentration is changed and successive calculations are repeated until a specified condition is met, thereby determining the concentration of each component that most reasonably explains the measured fluorescent X-ray spectrum.

[0004] However, fluorescent X-rays generated by light elements such as C, H, and O, whose atomic numbers are smaller than a certain value, are difficult to detect with sufficient intensity, and therefore cannot be qualified in practice by fluorescent X-ray analysis. In other words, when an unknown sample contains light elements, if the FP method is performed on components specified only by the results of qualitative analysis by fluorescent X-ray analysis, the sum of the concentrations of the qualified components is estimated to be 100%, ignoring those light elements. Therefore, the influence of the unqualified light elements will cause errors in the quantified concentrations.

[0005] In order to reduce such errors in quantification, an X-ray fluorescence analyzer equipped with the FP method is provided with a function of designating compounds or elements that are thought to be contained in the unknown sample other than the components qualified by the X-ray fluorescence as the remaining components. For example, in the X-ray fluorescence analyzer described in Patent Document 1, since the unknown sample is a resin, the remaining component is assumed to be CHO, and the concentration of the remaining component is calculated based on the RhKα Compton scattering radiation from the target of the X-ray tube. Then, the sum of the calculated concentration of the remaining component and the concentration of each qualified component is set to 100%, and the FP method is performed on the components other than the remaining component to reduce the quantitative error of each component. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2010-223908 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, if the type of light elements contained in the unknown sample and the ratio of their atomic numbers can be predicted, the residual components can be specified as appropriate as described above to reduce the quantitative error of the FP method, but this is difficult to apply when the light elements contained in the unknown sample cannot be predicted at all. Also, if the residual components are expected to be elements whose concentrations are difficult to quantify using scattered radiation, it is possible to quantify the concentrations of the residual components by gas analysis of the unknown sample using, for example, ICP or high-frequency melting, but in the case of very valuable samples, it is not possible to use a quantitative method that destroys and loses such samples.

[0008] The present invention has been made in consideration of the above-mentioned problems, and has an object to provide a quantitative analysis method that can accurately identify light elements contained in an unknown sample and improve the accuracy of quantitative analysis by the FP method based on the fluorescent X-ray spectrum. [Means for solving the problem]

[0009] That is, the quantitative analysis method according to the present invention comprises a Raman spectrum measurement step of irradiating an unknown sample with light and measuring the spectrum of Raman scattered light generated from the unknown sample, a Raman spectrum analysis step of identifying at least information regarding light elements having a predetermined atomic number or less contained in the unknown sample based on the measured spectrum of Raman scattered light, a fluorescent X-ray spectrum measurement step of irradiating the unknown sample with primary X-rays and measuring the spectrum of fluorescent X-rays generated from the unknown sample, and a fluorescent X-ray spectrum analysis step of quantifying elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured fluorescent X-ray spectrum, wherein the fluorescent X-ray spectrum analysis step comprises a residual component setting step of setting residual components in the FP method based on information regarding the light elements contained in the unknown sample identified in the Raman spectrum analysis step.

[0010] Furthermore, the quantitative analysis system according to the present invention comprises a Raman scattered light measurement mechanism that irradiates an unknown sample with light and measures the spectrum of Raman scattered light generated from the unknown sample; a Raman spectrum analysis unit that identifies at least information regarding light elements contained in the unknown sample having a predetermined atomic number or less based on the measured spectrum of Raman scattered light; an X-ray fluorescence spectrum measurement mechanism that irradiates the unknown sample with primary X-rays and measures the spectrum of fluorescent X-rays generated from the unknown sample; and an X-ray fluorescence spectrum analysis unit that quantifies elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured fluorescent X-ray spectrum, wherein the X-ray fluorescence spectrum analysis unit comprises a residual component setting unit that sets a residual component in the FP method based on information regarding the light elements contained in the unknown sample identified in the Raman spectrum analysis step.

[0011] In this way, information on light elements with a predetermined atomic number or less is obtained based on the Raman scattered light generated in the unknown sample, so that light elements that are difficult to identify by fluorescent X-ray analysis can be accurately identified or quantified. In addition, since the spectrum of Raman scattered light is used, not only the elements contained in the unknown sample but also the manner in which the elements are bonded to other elements can be qualitatively determined. Therefore, the components that are actually contained in the unknown sample and cannot be quantified by fluorescent X-ray analysis are accurately set as the remaining components, so that the quantitative accuracy of each component quantified by the FP method can be improved. In addition, by using the bond information of light elements and carrying out the FP method while further taking into account small differences such as the absorption coefficient of X-rays, it is possible to improve the quantitative accuracy of the components that can be measured by fluorescent X-rays and the quantitative accuracy of the remaining components.

[0012] In addition, since the analysis is based on the Raman scattering light and fluorescent X-rays generated in the unknown sample, it is possible to perform the quantitative analysis of the unknown sample non-destructively. Therefore, even if the unknown sample is rare and in trace amounts, it is possible to perform the component analysis. Furthermore, each analysis method analyzes the surface of the unknown sample, and the portions of the unknown sample analyzed in each analysis can be the same. Therefore, only the light elements present in the portion where the fluorescent X-ray analysis is performed can be set as the remaining components, thereby reducing the error factors in the quantitative analysis.

[0013] In addition, analysis using Raman scattered light allows more types of elements contained in an unknown sample to be identified than analysis using, for example, FTIR, etc. Therefore, the number of types of elements that can be accurately set as the remaining components also increases.

[0014] In order to avoid performing quantification by the FP method for elements that cannot be or are difficult to measure with fluorescent X-rays and to improve the accuracy of quantification by the FP method by performing qualitative or quantitative analysis by Raman spectroscopy, the light elements may be elements with atomic numbers up to 12. For example, in the case where quantitative analysis of Na and Mg is possible because fluorescent X-ray analysis is performed in a vacuum, the light elements may have atomic numbers up to 10 (Ne).

[0015] Specific examples of the information on light elements obtained by Raman spectroscopy to set the remaining components include information on the qualitative results of light elements, and information on the bonding state or chemical state of light elements or compounds containing light elements. With such information, physical constants such as X-ray absorption coefficients required to quantify the light elements set as the remaining components in the FP method can be made accurate, thereby improving the quantitative accuracy of the FP method.

[0016] In order to further improve the quantitative accuracy by performing an FP method taking into account the difference in physical constants due to the bonding state or chemical compound state using the information on the light elements obtained by Raman spectroscopic analysis, the information on the light elements contained in the unknown sample should be information on the light elements or on the bonding state or chemical compound state including the light elements, and the X-ray absorption coefficient of the remaining components should be set according to the bonding state or chemical compound state.

[0017] For example, in order to set the X-ray absorption coefficient of the remaining components by simple input, treat the remaining components as a balance, and quantify each component in an unknown sample by the FP method, the information on the light elements contained in the unknown sample may be the composition of a compound containing the light elements or the element names of the light elements, and the remaining components may be set as molecular formulas containing the light elements or element symbols of the light elements. In such a case, for example, a remaining component setting function attached to an existing X-ray fluorescence analyzer may be used to automatically set various physical constants of the remaining components required to implement the FP method, and accurate quantification may be performed.

[0018] In order to treat the concentration of the remaining components as a fixed value and further improve the quantitative accuracy of each component in the unknown sample by the FP method, the information on the light elements contained in the unknown sample is the concentration of a compound containing a light element or a light element in the unknown sample, and is set so that the sum of the concentration of the component quantified by the FP method and the concentration of the remaining components is 100%.

[0019] To realize the quantitative analysis system according to the present invention using an existing Raman scattering light measurement mechanism or X-ray fluorescence spectrum measurement mechanism, for example by updating the software, it is sufficient to use a program used in a quantitative analysis system equipped with a Raman scattering light measurement mechanism that irradiates an unknown sample with light and measures the spectrum of Raman scattered light generated from the unknown sample, and an X-ray fluorescence spectrum measurement mechanism that irradiates the unknown sample with primary X-rays and measures the spectrum of fluorescent X-rays generated from the unknown sample, the program causing a computer to perform the functions of a Raman spectrum analysis unit that identifies at least information regarding light elements having a predetermined atomic number or less contained in the unknown sample based on the measured spectrum of Raman scattered light, and an X-ray fluorescence spectrum analysis unit that quantifies elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured spectrum of fluorescent X-rays, and the quantitative analysis system program is characterized in that the X-ray fluorescence spectrum analysis unit includes a residual component setting unit that sets residual components in the FP method based on information regarding the light elements contained in the unknown sample identified in the Raman spectrum analysis step.

[0020] The program for the quantitative analysis system may be distributed electronically, or may be recorded on a program recording medium such as a CD, a DVD, or a flash memory. Effect of the Invention

[0021] In this way, the quantitative analysis method according to the present invention obtains information about light elements contained in the unknown sample by analysis based on Raman scattered light, and sets the remaining components in the FP method based on that information, so that the remaining components can be accurately specified, including their composition. As a result, the quantitative accuracy of the FP method can be improved. Furthermore, since the analysis is based on Raman scattered light or fluorescent X-rays, the unknown sample can be analyzed non-destructively, and even rare samples can be analyzed. [Brief description of the drawings]

[0022] [Figure 1] 1 is a schematic diagram showing a quantitative analysis system according to an embodiment of the present invention; [Diagram 2] FIG. 2 is a schematic diagram showing the Raman scattered light measuring device of the embodiment. [Diagram 3] FIG. 2 is a schematic diagram showing the fluorescent X-ray analyzer of the embodiment. [Figure 4] Graph showing the results of Raman spectrum measurement of geochemical reference material JSO-1. [Diagram 5] A graph showing the results of measuring the fluorescent X-ray spectrum of the geochemical reference material JSO-1. [Figure 6] Graph showing the quantitative results of the geochemical reference material JSO-1 using the FP method. [Figure 7] Graph showing the results of Raman spectrum measurement of an LDPE standard sample. [Figure 8] Graph showing the quantitative results of LDPE standard samples by FP method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] A quantitative analysis system 300 according to one embodiment of the present invention will be described with reference to the accompanying drawings.

[0024] The quantitative analysis system 300 of this embodiment analyzes organic matter and the like contained in an unknown sample S by Raman spectroscopy, and non-destructively quantifies each component by X-ray fluorescence analysis using the obtained information on the organic matter. Specifically, the system is configured to set the remaining components that are not quantified by the FP (fundamental parameter) method based on information on elements smaller than a predetermined atomic number identified by Raman spectroscopy. Examples of the unknown sample S include geological samples containing amorphous carbon and amino acids derived from plants, animals, microorganisms, etc., as well as minerals and rocks that are to be quantitatively analyzed by X-ray fluorescence analysis, and rare trace samples.

[0025] As shown in FIG. 1, the quantitative analysis system 300 includes a Raman spectroscopic analysis apparatus 100 that analyzes an unknown sample S based on Raman scattered light generated by the unknown sample S, and a fluorescent X-ray analysis apparatus 200 that analyzes the unknown sample S based on fluorescent X-rays generated by the unknown sample S.

[0026] The Raman spectroscopic analyzer 100 includes a Raman spectroscopic analysis mechanism 10, which is a hardware part, and a Raman spectrum analysis unit 11, which is a software part whose function is realized by a computer COM. The fluorescent X-ray analyzer 200 includes a fluorescent X-ray analysis mechanism 20, which is a hardware part, and a fluorescent X-ray spectrum analysis unit 21, which is a software part whose function is realized by a computer COM. In this embodiment, the functions of the Raman spectrum analysis unit 11 and the fluorescent X-ray spectrum analysis unit 21 are realized by separate computers COM, but these functions may be integrated and realized by one computer COM. The computer COM includes a CPU, a memory, an A / D converter, a D / A converter, various input / output devices, etc., and is configured to execute a program for a quantitative analysis system stored in the memory, and to function as at least the Raman spectrum analysis unit 11 and the fluorescent X-ray spectrum analysis unit 21 by cooperation of the various devices.

[0027] The Raman spectroscopic analysis device 100 of this embodiment is configured as a microscopic laser Raman spectroscopic measurement device. The Raman spectroscopic analysis mechanism 10 includes a laser irradiation system that irradiates laser light onto an unknown sample S placed on a sample stage as shown in Fig. 2, and a spectroscopic detection system that detects Raman scattered light generated in the unknown sample S by dispersing it.

[0028] The laser irradiation system includes a laser oscillator 12, a bandpass filter 13, a neutral density filter 14, a Rayleigh light cut filter 15, a half mirror 16, and an objective lens 17. The laser emitted from the laser oscillator 12 passes through the bandpass filter 13 and the neutral density filter 14, and is then reflected by the Rayleigh light cut filter 15 toward the sample stage 1S. The laser light then passes through the half mirror 16 and the objective lens 17 to be irradiated onto the unknown sample S on the sample stage.

[0029] The spectroscopic detection system includes an objective lens 17, a half mirror 16, a Rayleigh light cutting filter 15, a spectrometer slit 19, a grating 1G, and a CCD 1C. The Raman scattered light generated in the unknown sample S passes through the objective lens 17, the half mirror 16, the Rayleigh light cutting filter 15, and the spectrometer slit 19, and is then dispersed by the grating 1G, and a Raman spectrum indicating the intensity of the Raman scattered light at each wave number is detected by the CCD 1C. In addition, a portion of the reflected light and scattered light originating from the unknown sample S is reflected by the half mirror 16 and imaged by the observation camera 18.

[0030] The Raman spectrum analysis unit 11 performs qualitative or quantitative analysis on the unknown sample S based on the spectrum of the Raman scattered light generated in the unknown sample S obtained based on the output signal of the CCD 1C. For example, the Raman spectrum analysis unit 11 has various information on the characteristic peaks in the Raman spectrum of known elements and compounds as a database, and qualifies and quantifies the elements or compounds contained in the unknown sample S by comparing the peaks appearing in the measured Raman spectrum with the database. In this embodiment, the Raman spectrum analysis unit 11 is configured to qualitatively and quantitatively analyze C, H, O, or organic compounds composed of these contained in the unknown sample S. In addition, the Raman spectrum analysis unit 11 externally displays the measured Raman spectrum, or externally outputs information on the qualitatively and quantified elements or compounds. In this embodiment, the information on the light elements contained in the unknown sample S includes at least the composition of the compound containing the light element or the element name of the light element, and the compound containing the light element or the concentration of the light element in the unknown sample S.

[0031] Next, the fluorescent X-ray analyzer 200 will be described. The fluorescent X-ray analyzer 200 of this embodiment is configured as a tabletop fluorescent X-ray analyzer, and is configured to irradiate an unknown sample S placed on a sample stage 2S with primary X-rays from below, and detect fluorescent X-rays generated from the unknown sample S below the sample stage 2S. That is, the fluorescent X-ray analysis mechanism 20 includes a primary X-ray irradiation system consisting of an X-ray tube 22, a primary X-ray filter 23, and a collimator 24, and an X-ray detector 25.

[0032] The fluorescent X-ray spectrum analysis unit 21 qualifies the components contained in the unknown sample S based on the spectrum of fluorescent X-rays detected by the X-ray detector 25, and quantifies the elements or compounds contained in the unknown sample S by the FP method.

[0033] Specifically, the fluorescent X-ray spectrum analysis unit 21 includes a qualitative analysis unit 21A that qualifies the components contained in the unknown sample S based on the peak wavelength of the fluorescent X-ray spectrum, a remaining component setting unit 21B that sets the remaining components that are not quantified in the FP method, and a quantitative analysis unit 21C that quantifies each component by the FP method, the components that have been qualified by the qualitative analysis unit 21A or specified components, excluding the components that have been set as the remaining components.

[0034] The qualitative analysis section 21A qualifies the elements or compounds contained in the unknown sample S from the energy of each peak of the measured fluorescent X-ray spectrum by referring to a database relating to the fluorescent X-ray energy of each element.

[0035] The remaining component setting unit 21B receives input of information on light elements contained in the unknown sample S analyzed in the Raman spectrum analysis unit 11. The remaining component setting unit 21B displays to the user elements or compounds that cannot be measured by X-ray fluorescence analysis in the input Raman spectrum analysis result as candidates for the remaining component. For example, when the user inputs an input to approve the displayed element or compound as the remaining component, or inputs a compound or element to be set as the remaining component in the form of, for example, a composition formula, a chemical formula, or an element symbol, the remaining component setting unit 21B sets the specified component as the remaining component for the quantitative analysis unit 21C. Here, the input composition formula or chemical formula does not have to be a compound that can actually exist, and may simply formally represent the ratio of the atomic numbers of each element.

[0036] The quantitative analysis unit 21C performs quantification of each component by the FP method with the set remaining components corrected, for example, for the unknown sample S, with the elements identified by the qualitative analysis unit 21A or compounds such as oxides estimated based on the qualitative results as quantification targets. Alternatively, the user looks at the fluorescent X-ray spectrum displayed by the qualitative analysis unit 21A, and sets the elements or oxides of the elements corresponding to each peak as quantification targets, and the quantitative analysis unit 21C performs quantification by the FP method.

[0037] For the FP method, an existing algorithm can be used. That is, for components whose fluorescent X-rays can be measured by the X-ray fluorescence analysis mechanism 20, the theoretical X-ray intensity of each component calculated based on the estimated concentration of each component and the instrument constant is compared with the actually measured X-ray intensity, and each estimated value of the concentration is updated and calculated sequentially until the difference converges. In this way, the concentration of the component set as the target to be quantified is determined.

[0038] Meanwhile, the concentration of the component set as the remaining component is calculated by regarding the difference between the theoretical X-ray intensity and the measured X-ray at each stage of the iterative calculation of the FP method as the absorption of X-rays by the component set as the remaining component. In other words, the concentration of the remaining component is estimated from the difference between the theoretical fluorescent X-ray intensity and the measured fluorescent X-ray intensity and the X-ray absorption coefficient of the remaining component. The iterative calculation in the FP method is repeated until the concentrations of the component to be quantified and the remaining component converge respectively. In this way, the FP method quantifies the concentration of the remaining component, which is a component not to be analyzed and for which it is difficult to detect a peak at the corresponding energy value in the fluorescent X-ray spectrum.

[0039] In this manner, quantitative analysis unit 21C determines the concentration of each component to be quantified by the FP method such that the sum of the concentration of each component and the concentration of the remaining components is 100%.

[0040] In addition, when there are multiple types of elements or compounds to be set as the remaining components, one component may be treated as the remaining component, and the other components may be given fixed values ​​as known concentrations, and then the quantification of the quantification target may be performed by the FP method, or the concentrations of all the remaining components may be set to fixed values ​​as known concentrations. For example, when the concentration of light elements in the unknown sample S can be calculated by Raman spectroscopy, such values ​​may be used as known concentrations.

[0041] Here, the absorption coefficient of the remaining component used can be set more accurately by referring to a database based on information such as the bonding state of each element obtained by Raman spectroscopy, which leads to improved quantitative accuracy by the FP method. For example, even if it is the same carbon, the absorption coefficient differs depending on whether it is graphite or amorphous carbon, so the quantitative accuracy of each component can be improved by setting a more accurate absorption coefficient according to information on the bonding state obtained by Raman spectroscopy. In other words, if only the elements expected to be contained are simply set as the remaining components without performing Raman spectroscopy, a value different from the absorption coefficient of the remaining components in the unknown sample S will be selected, which will in turn reduce the quantitative accuracy of the components to be quantified.

[0042] Next, the results of analysis using the quantitative analysis system 300 of this embodiment will be described.

[0043] First, as an example of the case where the unknown sample S is a geological sample, the geochemical reference material JSO-1 was analyzed. Figure 4 shows the measurement results of the Raman spectrum of the geochemical reference material JSO-1 outputted from the Raman spectrum analysis unit 11. -1 and 1580cm -1 These peaks are characteristic of amorphous carbon with a six-membered ring structure, which indicates that the geochemical reference material JSO-1 contains amorphous carbon. In addition, there is a Raman band (encircled by the dotted ellipse at 3000 cm) corresponding to the CH stretching vibration derived from organic matter. -1 Therefore, it can be confirmed that it is sufficient to set at least carbon C as the residual component in the FP method described later.

[0044] FIG. 5 shows the measurement result of the fluorescent X-ray spectrum of the geochemical reference material JSO-1 outputted by the qualitative analysis unit 21A. It can be seen from each peak that Fe, Si, Al, P, S, K, CA, Ti, VMn, Zn, and Sr are contained in the geochemical reference material JSO-1. Note that the fluorescent X-ray analyzer 200 of this embodiment is configured to perform analysis in the atmosphere, so that the corresponding peaks for Na and Mg cannot be detected. For example, if the fluorescent X-ray analysis is performed in a vacuum, it is possible to detect peaks for Na and Mg and to qualitatively and quantitatively determine them. In the following description, the quantification of each element is performed under the assumption that the peaks of Na and Mg contained in the geochemical reference material JSO-1 are also detected by the fluorescent X-ray analysis.

[0045] Based on the above-mentioned results and assumptions, quantitative analysis was performed by the FP method for the elements suggested by the X-ray fluorescence spectrum and for C, which was set as the remaining component. In other words, the concentration of each component was calculated by regarding the difference between the theoretical X-ray intensity and the measured X-ray intensity as the absorption of C, which is the remaining component. In addition, for Na2O and MgO, which correspond to Na and Mg, which are assumed to be qualitatively determined by X-ray fluorescence analysis in a vacuum, fixed values ​​of 0.66 mass% and 2.11 mass%, which are the certified values ​​of the geochemical reference material JSO-1, were set to improve the quantitative accuracy of C. The relationship between the quantified value and the certified value or reference value of the geochemical reference material JSO-1 is shown in Figure 6. Both major elements with a concentration of 1 mass% or more and trace elements with a concentration of less than 1 mass% were quantified with a correlation coefficient of 0.991 or 0.962. In addition, carbon C, which cannot be quantified by X-ray fluorescence analysis, was quantified with sufficient accuracy.

[0046] Next, the results of analysis of an LDPE standard sample using the quantitative analysis system 300 will be described. Figure 7 shows the results of Raman spectrum measurement of an LDPE standard sample. In Figure 7, a characteristic Raman spectrum pattern due to CH stretching motion is observed at the Raman band 2722 cm -1 , 2850cm -1 , 2881cm -1. Therefore, it can be seen from the results of the Raman spectroscopy that at least CH should be set as the remaining component. Note that Raman bands were also observed in other wave number regions (not shown), and it was confirmed that polyethylene was present overall. For this reason, ethylene, which is a format that can be input into the fluorescent X-ray analyzer 200, was set as the remaining component. In addition, although not shown, peaks corresponding to Cr, Br, Pb, Cd, and Hg were observed in the fluorescent X-ray spectrum. Therefore, each element identified from the fluorescent X-ray spectrum and ethylene, which is the remaining component, were targeted for quantification using the FP method.

[0047] The relationship between the quantified values ​​and the certified or reference values ​​of the LDPE standard sample is shown in Figure 8. For all elements except Cd, the quantification was satisfactory with a correlation coefficient of 0.915. As for Cd, the thickness of the sample did not reach the infinite thickness of Cd, and the strength was insufficient, which is thought to be why the quantified value was smaller than the certified value.

[0048] In this way, the quantitative analysis system 300 of this embodiment can analyze the bonding state of light elements and compounds that cannot be measured by fluorescent X-ray analysis based on Raman spectroscopy, and the detected light elements and their bonding state can be accurately set as the remaining components in the FP method. As a result, the components that are qualitatively identified and quantified from the fluorescent X-ray spectrum can be quantified with high accuracy. In addition, since the chemical composition of the unknown sample S can be clarified non-destructively, it can be suitably used for the analysis of valuable samples, for example.

[0049] Furthermore, since both Raman spectroscopy and X-ray fluorescence analysis are methods for analyzing the surface of a sample, the quantitative accuracy of the FP method can be improved by leaving only the light elements in the area where the X-ray fluorescence analysis is actually performed as the remaining components. For example, if the light elements in a sample are qualitatively analyzed by gas extraction or the like, there is a risk that the quantitative accuracy will decrease because the light elements extracted from the area not subject to the X-ray fluorescence analysis will be left as the remaining components. With the quantitative analysis system 300 of this embodiment, such a problem can be prevented from occurring.

[0050] Other embodiments will now be described.

[0051] The present invention can be applied to various aspects of the FP method, for example, standardless analysis, semi-fundamental parameter method, bulk FP method quantitative analysis, etc.

[0052] When the light element identified by the Raman spectroscopic analysis is set as the remaining component, the method of calculating the concentration is not limited to that described in the above embodiment. For example, when the concentration of the light element is known by the Raman spectroscopic analysis, the value may be set as a fixed value. In addition, when the light element is carbon, the concentration of the remaining component may be calculated based on the Compton scattering radiation, and the calculated concentration may be used as a fixed value.

[0053] In addition, rather than measuring the Raman spectrum and then the X-ray fluorescence spectrum, the Raman spectrum may be measured after the X-ray fluorescence spectrum is measured. In this case, analysis such as quantitative analysis may be started after the Raman spectrum measurement is completed.

[0054] In order to be able to measure Raman and X-ray fluorescence spectra on one sample stage, the quantitative analysis system may be configured as an integrated system. The light elements analyzed by the Raman spectrometer are not limited to elements with atomic numbers of 12 or less. The settings may be made according to the elements that can be quantified by the X-ray fluorescence analyzer.

[0055] When setting the residual component based on the result of Raman spectroscopy, for example, a physical constant corresponding to the bonding state or the compound state of a light element or a compound containing a light element may be set to perform the FP method. That is, setting the residual component is a concept including directly setting a physical constant such as an X-ray absorption coefficient, rather than simply inputting a chemical formula or an element name into an X-ray fluorescence analyzer. That is, if there is a difference in the X-ray absorption coefficient depending on whether carbon C has a diamond bond sp3 or a carbon bond sp2, or whether each bond is mixed as in amorphous carbon, or the composition ratio thereof, such a difference can be reflected to further improve the quantitative accuracy by the FP method.

[0056] The X-ray fluorescence analyzer may be a microscopic X-ray fluorescence analyzer. Since the Raman microscopic spectroscopic analyzer can obtain information about light elements for each coordinate in the sample, the use of the X-ray fluorescence microscope makes it possible to switch between information about light elements for each coordinate in the sample and perform individual quantification by the FP method.

[0057] In addition, various modifications of the embodiments and combinations of parts of each embodiment may be made without departing from the spirit of the present invention. [Explanation of symbols]

[0058] 300 Quantitative Analysis System 100 Raman spectroscopic analyzer 10. Raman Spectroscopic Analysis Mechanism 11 Raman Spectroscopic Analysis Section 200...X-ray fluorescence analyzer 20. X-ray fluorescence analysis mechanism 21 X-ray fluorescence spectrum analysis section 21A...Qualitative Analysis Department 21B...Residual component setting section 21C...Quantitative Analysis Department

Claims

1. a Raman spectrum measuring step of irradiating an unknown sample with light and measuring the spectrum of Raman scattered light generated from the unknown sample; A Raman spectrum analysis step of identifying at least information about light elements having a predetermined atomic number or less contained in the unknown sample based on the spectrum of the measured Raman scattered light; a fluorescent X-ray spectrum measuring step of irradiating the unknown sample with primary X-rays and measuring a spectrum of fluorescent X-rays generated from the unknown sample; and an X-ray fluorescence spectrum analysis step of quantifying elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured X-ray fluorescence spectrum, The X-ray fluorescence spectroscopy analysis step comprises: A quantitative analysis method comprising a residual component setting step of setting a residual component that is regarded as a deviation between theoretical X-ray intensity and actually measured X-ray at each stage of the sequential calculation of the FP method, based on information on light elements contained in the unknown sample identified in the Raman spectrum analysis step.

2. 2. The method of claim 1, wherein the light elements are elements having atomic numbers up to 12.

3. 3. The quantitative analysis method according to claim 1, wherein the information on the light elements includes at least one of information on a qualitative result on the light elements and information on a bonding state or a chemical state of the light elements or compounds containing the light elements.

4. The information on the light element contained in the unknown sample is information on the light element or a bonding state or a compound state containing the light element, 4. The method of quantitative analysis according to claim 1, further comprising setting an X-ray absorption coefficient of said remaining component in accordance with a bonding state or a chemical compound state.

5. The information about the light element contained in the unknown sample is a chemical formula, an element symbol, or an element name of a compound containing the light element, 5. The quantitative analysis method according to claim 1, wherein the remaining components are set by a chemical formula, an element symbol, or an element name of a compound containing a light element.

6. The information about the light element contained in the unknown sample is a compound containing the light element or a concentration of the light element in the unknown sample; 6. The quantitative analysis method according to claim 1, wherein the sum of the concentration of the component quantified by the FP method and the concentration of the remaining components is set to be 100%.

7. A quantitative analysis method as described in any one of claims 1 to 6, wherein the residual component setting step calculates the concentration of the component set as the residual component by considering the deviation between the theoretical X-ray intensity and the measured X-ray at each stage of the sequential calculation of the FP method to be the absorption of X-rays by the component set as the residual component.

8. A quantitative analysis method described in any one of claims 1 to 7, wherein the residual component setting step displays candidates for the residual components in the FP method based on information regarding light elements contained in the unknown sample identified in the Raman spectrum analysis step.

9. The quantitative analysis method according to claim 1, wherein the Raman spectrum measurement step is followed by the X-ray fluorescence spectrum measurement step.

10. a Raman scattered light measurement mechanism for irradiating an unknown sample with light and measuring a spectrum of Raman scattered light generated from the unknown sample; a Raman spectrum analysis unit that identifies at least information regarding light elements having a predetermined atomic number or less contained in the unknown sample based on the spectrum of the measured Raman scattered light; a fluorescent X-ray spectrum measuring mechanism for irradiating the unknown sample with primary X-rays and measuring a spectrum of fluorescent X-rays generated from the unknown sample; and an X-ray fluorescence spectrum analysis unit that quantifies elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured X-ray fluorescence spectrum, The X-ray fluorescence spectrum analysis unit A quantitative analysis system comprising a residual component setting unit that sets a residual component that is regarded as a deviation between a theoretical X-ray intensity and an actually measured X-ray at each stage of the sequential calculation of the FP method, based on information on light elements contained in the unknown sample identified by the Raman spectrum analysis unit.

11. A program for use in a quantitative analysis system including a Raman scattered light measurement mechanism for irradiating an unknown sample with light and measuring a spectrum of Raman scattered light generated from the unknown sample, and an X-ray fluorescence spectrum measurement mechanism for irradiating the unknown sample with primary X-rays and measuring a spectrum of fluorescent X-rays generated from the unknown sample, a Raman spectrum analysis unit that identifies at least information regarding light elements having a predetermined atomic number or less contained in the unknown sample based on the spectrum of the measured Raman scattered light; and an X-ray fluorescence spectrum analysis unit that quantifies elements or compounds contained in the unknown sample by a fundamental parameter (FP) method based on the measured X-ray fluorescence spectrum, The X-ray fluorescence spectrum analysis unit A program for a quantitative analysis system, comprising a residual component setting unit that sets a residual component that is regarded as a deviation between theoretical X-ray intensity and actually measured X-ray at each stage of the sequential calculation of the FP method, based on information on light elements contained in the unknown sample identified by the Raman spectrum analysis unit.

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