X-ray analysis device

Abstract

Provided is an X-ray analysis device that analyzes an element contained in a measurement sample that is transported along a prescribed direction, and includes: an X-ray irradiation section that irradiates an X-ray toward the measurement sample; an X-ray detection section that detects a fluorescent X-ray generated from the measurement sample toward the measurement sample; and a standard sample that is disposed in a region in which an irradiation region of the X-ray irradiated from the X-ray irradiation section and a detectable region in which the fluorescent X-ray can be detected by the X-ray detection section overlap, and that contains an element that is known.

Description

Technical Field

[0001] This invention relates to X-ray analysis apparatus. Background Technology

[0002] Conventionally, as shown in Patent Document 1, a fluorescence X-ray analysis device has been used as an apparatus for quantitative or qualitative analysis of elements in a transported sample. This fluorescence X-ray analysis device irradiates the transported sample with X-rays from an X-ray source and detects the fluorescence X-rays generated from the sample using an X-ray detector, thereby determining the composition ratio and film thickness of the sample. Existing technical documents Patent documents

[0003] Patent Document 1: Japanese Patent Application Publication No. 2022-13497 Summary of the Invention The problem that the invention aims to solve

[0004] However, when calibrating an X-ray detector, in addition to normal measurements, a calibration measurement is required at the measurement location using a standard sample containing known components and their concentrations. In X-ray analysis equipment that analyzes samples transported in the aforementioned manner, the standard sample needs to be placed alongside the production line, and the X-ray analysis equipment is temporarily moved during calibration to measure the standard sample. Therefore, the measurement of the test sample cannot be performed while the standard sample is being measured. This results in periods of missing measurement data. Furthermore, during periods when the production line is running for extended periods, the calibration interval becomes longer, and there is a problem that even if deviations in the measured values ​​occur during these periods, the deviations may not be detected.

[0005] The present invention was completed to solve the above-mentioned problems in one fell swoop. Its main objective is to enable calibration operations to be performed simultaneously with the analysis and measurement of the sample in a fluorescence X-ray analysis device for analyzing and transporting the sample. Methods for solving problems

[0006] That is, the X-ray analysis apparatus of the present invention analyzes the elements contained in a test sample transported along a predetermined direction, characterized in that the X-ray analysis apparatus comprises: an X-ray irradiation unit for irradiating the test sample with X-rays; an X-ray detection unit for detecting fluorescent X-rays generated from the test sample; and a standard sample disposed in an overlapping region of the irradiation area of ​​the X-rays irradiated by the X-ray irradiation unit and the detectable region of the fluorescent X-rays detectable by the X-ray detection unit, the standard sample containing known elements.

[0007] With such a structure, since a standard sample containing a known element is placed in the overlapping region of the irradiation area of ​​the X-ray irradiation unit and the detectable region of the fluorescent X-rays detectable by the X-ray detection unit, the X-ray detection unit can simultaneously detect the fluorescent X-rays generated from the test sample and the fluorescent X-rays generated from the standard sample. Therefore, the calibration operation of the X-ray detection unit can be performed while analyzing the test sample. For example, by pre-storing information related to the energy of the fluorescent X-rays of the elements contained in the standard sample, comparing the energy of the elements contained in the standard sample with the peak position of the elements in the spectrum generated based on the output of the X-ray detection unit, and calculating the deviation, the energy of the X-ray analysis device can be calibrated.

[0008] As a specific embodiment of the X-ray analysis apparatus, the X-ray analysis apparatus may further include: a spectrum generation unit that generates a spectrum of fluorescent X-rays generated from the test sample, i.e., a measured spectrum, based on the output of the X-ray detection unit; an element information storage unit that stores first energy information related to the energy of the fluorescent X-rays inherent to a first element contained in the standard sample; a peak detection unit that analyzes the generated measured spectrum and detects the peak value corresponding to the first element; and a correction unit that performs energy correction based on the first energy information stored in the element information storage unit and information related to the position of the peak value of the first element detected by the peak detection unit. If such a structure is used, the deviation can be determined by comparing the position of the first energy information with the peak value of the first element, and the energy correction of the X-ray analysis device can be performed.

[0009] Furthermore, preferably, in the X-ray analysis apparatus, the standard sample or the test sample contains a second element different from the first element, the element information storage unit stores second energy information related to the energy of the fluorescent X-rays inherent to the second element, the peak detection unit analyzes the measured spectrum and detects the peak corresponding to the second element, and the correction unit performs energy correction based on the first energy information and the second energy information stored in the element information storage unit, as well as information related to the position of the respective peaks of the first element and the second element detected by the peak detection unit. In this way, by using the information of the peak positions of two points in the fluorescence spectrum, the energy correction of the X-ray analysis device can be performed more accurately.

[0010] In order to perform intensity calibration of the X-ray analysis device while analyzing and measuring the sample, it is preferable that the element information storage unit also stores standard intensity information related to the intensity of fluorescent X-rays originating from the first element, which is obtained in advance by irradiating the standard sample with X-rays. The calibration unit performs intensity calibration based on the standard intensity information stored in the element information storage unit and the information related to the peak intensity of the first element detected by the peak detection unit.

[0011] Furthermore, preferably, in the X-ray analysis apparatus, the spectrum generation unit generates an analytical spectrum for analyzing the sample to be measured and a calibration spectrum for calibration by the calibration unit, which are used as the measured spectrum, and the cumulative number of times the spectrum is generated when the calibration spectrum is generated is greater than the cumulative number of times the spectrum is generated when the analytical spectrum is generated. In this way, when performing quantitative analysis of the sample, the analytical spectrum with fewer cumulative counts is used at shorter intervals, while the calibration spectrum with more cumulative counts and a larger SN is used to perform calibration operations with high precision.

[0012] Preferably, the spectrum generation unit accumulates multiple measured spectra with low noise components near the peak corresponding to the first element from multiple recently generated measured spectra to generate the correction spectrum. In this way, by accumulating the spectrum with less noise component (background) near the peak corresponding to the first element, a higher precision correction spectrum can be generated as a correction spectrum for comparison with the first energy information.

[0013] Furthermore, preferably, the X-ray analysis apparatus further includes: a reference spectrum storage unit that stores a reference spectrum in advance for determining the calibration timing of the calibration unit; and a spectrum comparison unit that compares the reference spectrum stored in the reference spectrum with the measured spectrum generated by the spectrum generation unit to determine whether they are similar. When the spectrum comparison unit determines that the measured spectrum is similar to the reference spectrum, the peak detection unit performs analysis of the measured spectrum. In this way, since correction can be performed only when the similarity to a pre-stored reference spectrum is high, the correction operation can be performed at the appropriate timing without receiving instructions from the outside. This method is particularly effective when the test sample is a sample in which different states are repeatedly produced, such as intermittently coated with a cover film on a substrate material.

[0014] As a specific example of the X-ray analysis apparatus, the sample being measured may repeatedly present multiple states with different constituent elements in the repeating region as it is transported, and the reference spectrum is generated based on the output of the X-ray detection unit in one of the multiple states.

[0015] Since the peak position of the first element to be detected gradually changes due to changes in the surrounding environment such as temperature, drastic changes are relatively rare in the analysis. Therefore, preferably, in the X-ray analysis apparatus, the element information storage unit stores a peak position, i.e. a reference peak position, corresponding to the energy of the fluorescent X-rays inherent in the first element, as the first energy information. When the deviation between the peak position of the first element detected by the peak detection unit and the reference peak position stored in the element information storage unit is greater than or equal to a predetermined value, the correction unit performs energy correction. In this way, since energy correction is not performed every time the measured spectrum is analyzed to detect the peak position, but only when the peak position of the first element contained in the standard sample gradually changes and shifts from the reference peak position to the extent that it may affect the measurement accuracy, the correction frequency can be reduced while ensuring the measurement accuracy and the processing speed in the correction unit can be increased.

[0016] Furthermore, preferably, in the X-ray analysis apparatus, the peak detection unit refers to information related to the reference peak position stored in the element information storage unit to detect the peak corresponding to the first element from the measured spectrum. In this way, since the peak detection unit searches for the peak of the first element from the vicinity of the reference peak position where the peak of the first element is highly likely to exist, the time spent on peak detection can be shortened.

[0017] However, in order to reduce noise components by detecting only fluorescent X-rays originating from the test sample in the X-ray detection unit, it is preferable that the overlapping area between the irradiation area of ​​the X-ray irradiation unit and the detectable area of ​​the X-ray detection unit is formed only near the surface of the test sample. However, in an apparatus for analyzing transported test samples as described in this invention, if the test sample is transported, for example, by a conveyor belt or is a thin film transported roll to roll, the test sample will shake during transport. Therefore, if a standard sample is placed in the overlapping area near the surface of the test sample, the shaken test sample may come into contact with the standard sample. Therefore, in the aforementioned X-ray analysis apparatus, considering the potential for sample swaying, it is preferable to establish a repeating region not only near the surface of the sample but also at a sufficient distance from the surface (a safety margin), and to place a standard sample within this repeating region while maintaining this safety margin. This safety margin is a distance that prevents interference (contact) even when the transported sample sways.

[0018] More specifically, as a specific embodiment of the X-ray analysis apparatus, the X-ray analysis apparatus may further include a housing that houses the X-ray irradiation unit and the X-ray detection unit, and an opening is formed on one side wall to allow X-rays generated from the X-ray irradiation unit and fluorescent X-rays generated from the test sample to pass through, wherein the standard sample is disposed in the repeating region set in the housing near the opening. With such a structure, by setting up a repeating area inside the chamber and arranging a standard sample in the repeating area inside the chamber, it is possible to place the standard sample at a safe distance while bringing the X-ray irradiation unit and the X-ray detection unit as close as possible to the surface of the sample to be measured.

[0019] As a specific form of the standard sample, the standard sample may be in the form of filaments, meshes, rings, or films. If the standard sample is used in this way, even if it is placed in the repeating area, most of the X-rays irradiated from the X-ray irradiation unit and directed toward the sample can pass through, as can most of the fluorescent X-rays generated from the sample and directed toward the X-ray detection unit, enabling calibration operations to be performed without hindering the analysis of the sample. Invention Effects

[0020] According to the present invention described above, in a fluorescence X-ray analysis apparatus for analyzing transported test samples, calibration operations can be performed simultaneously with the analysis of the test samples. Attached Figure Description

[0021] Figure 1 This is a diagram showing the overall structure of an X-ray analysis apparatus according to one embodiment of the present invention. Figure 2 This is a functional block diagram of an X-ray analysis apparatus with the same implementation method. Figure 3 This is a top view showing the structure near the opening of the X-ray analysis apparatus of the same embodiment. Figure 4 This is a diagram showing an example of a fluorescence spectrum obtained by an X-ray analysis apparatus according to the same embodiment. Detailed Implementation

[0022] Hereinafter, an X-ray analysis apparatus 100 according to one embodiment of the present invention will be described with reference to the accompanying drawings.

[0023] like Figure 1As shown, the X-ray analysis apparatus 100 of this embodiment is an apparatus that irradiates a test sample W transported along a predetermined transport direction (left-right direction on the paper) with X-rays (also called primary X-rays) and detects the fluorescent X-rays (also called secondary X-rays) generated from the test sample W, thereby performing quantitative or qualitative analysis of the elements contained in the test sample W (so-called fluorescent X-ray analysis apparatus). As described in detail below, the X-ray analysis apparatus 100 of this embodiment is configured to perform calibration of the X-ray detection unit 2 while analyzing the elements contained in the transported test sample W (i.e., while the test sample W is being transported).

[0024] In this embodiment, the test sample W is formed by coating a film material W2 onto one surface of a thin-film substrate material W1, and is transported along the transport direction at approximately a constant speed using, for example, a roll-to-roll transport mechanism (not shown). Furthermore, the film material W2 constituting the test sample W is coated onto the surface of the substrate material W1 at approximately constant intervals along the transport direction. The X-ray analysis apparatus 100 is configured to irradiate the film material W2 of the test sample W with X-rays and detect the generated secondary X-rays.

[0025] Specifically, the X-ray analysis apparatus 100 includes: an X-ray irradiation unit 1 that irradiates the test sample W with primary X-rays; an X-ray detection unit 2 that detects secondary X-rays generated from the test sample W; and an information processing unit 4 that analyzes the test sample W based on the output from the X-ray detection unit 2.

[0026] The X-ray irradiation unit 1 includes an X-ray source and a collimator. The X-ray source includes an X-ray tube, which uses thermionic electrons generated from a filament to excite a target metal to produce primary X-rays. The collimator has a passage window through which the primary X-rays generated by the X-ray source pass, and uses this passage window to reduce the irradiation angle of the primary X-rays.

[0027] In this embodiment, the X-ray irradiation unit 1 irradiates the test sample W with radial primary X-rays that extend at a predetermined radiation angle θ1. The X-ray source in this embodiment is configured such that the central axis A1 of the emitted primary X-rays is perpendicular to the surface of the test sample W.

[0028] The X-ray detection unit 2 includes an X-ray detector 21 and a signal processing unit 22 that processes signals from the X-ray detector 21 and outputs them to the information processing device 4.

[0029] The X-ray detector 21 is, for example, composed of an X-ray detection element such as a Si element (e.g., a silicon drift detector (SDD)). In this X-ray detector 21, the field of view θ2 capable of detecting secondary X-rays is set within a specified range, and secondary X-rays generated from this field of view can be detected. The X-ray detector 21 is configured such that the central axis A2 of its detection field of view is inclined relative to the surface of the sample W being measured.

[0030] The signal processing unit 22 detects the accumulated amount of charge output from the X-ray detector 21 as fluorescent X-rays generated from the test sample W are incident on it, and converts it into an accumulated signal (voltage signal) corresponding to the accumulated amount. Then, the signal processing unit 22 shapes the accumulated signal into a pulse signal with a trapezoidal wave having a wave height value corresponding to the energy of the fluorescent X-rays, detects the wave height value of the pulse signal, and outputs it to the information processing device 4. In this embodiment, the signal processing unit 22 pre-stores a correction coefficient (hereinafter also referred to as a first correction coefficient) for energy correction, and calculates the corrected wave height value by multiplying the first correction coefficient by the detected wave height value. Then, the signal processing unit 22 uses a multi-channel analyzer to count the corrected wave height values ​​by wave height, and outputs wave height classification count data representing the number of counts by wave height to the information processing device 4. Furthermore, the signal processing unit 22 accumulates the number of counts by wave height output from the multi-channel analyzer for a predetermined time, and outputs it as wave height classification count data information to the processing device 4.

[0031] The X-ray irradiation unit 1 and the X-ray detection unit 2 are housed within the enclosure 3. An opening 3a is formed on one side wall 31 of the enclosure 3, through which primary X-rays emitted from the X-ray irradiation unit 1 at an angle θ1 irradiate the test sample W. Furthermore, secondary X-rays generated from the test sample W are detected by the X-ray detector 21 through the opening 3a.

[0032] The irradiation area 1R of primary X-rays irradiated by X-ray irradiation unit 1 and the detectable area 2R of secondary X-rays detectable by X-ray detector 21 are arranged in the chamber 3 in a manner that repeats at least on the surface of the sample W. Figure 1 As shown, the irradiation area 1R of the X-ray irradiation unit 1 and the detectable area 2R of the X detector also overlap near the opening 3a inside the housing 3.

[0033] Information processing device 4 is a computer having a CPU, memory, input / output interfaces, display, and input unit, such as... Figure 2As shown, at least the functions of the spectrum generation unit 41 and the analysis unit 42 are performed. The spectrum generation unit 41 generates a spectrum of fluorescent X-rays based on the output of the X-ray detection unit 2 (i.e., the corrected wave height value), and the analysis unit 42 performs qualitative or quantitative analysis on the elements contained in the sample W based on the spectrum of the fluorescent X-rays. The fluorescence spectrum displays the intensity of the secondary X-rays (counts per second) as a function of energy.

[0034] The spectrum generation unit 41 generates an X-ray spectrum based on the wave height classification and counting data output from the X-ray detection unit 2. In this embodiment, the spectrum generation unit 41 pre-stores correction coefficients (hereinafter also referred to as second correction coefficients) for intensity correction, and outputs a corrected X-ray spectrum (hereinafter also referred to as the measured spectrum) obtained by multiplying the X-ray intensity of the generated X-ray spectrum by the second correction coefficients. In this embodiment, the spectrum generation unit 41 generates the measured spectrum at predetermined time intervals (e.g., every 3 seconds) and outputs it sequentially to the analysis unit 42.

[0035] Furthermore, the X-ray analysis apparatus 100 of this embodiment includes a standard sample 5, which is positioned at a predetermined location (calibration position) in the overlapping region between the irradiation area 1R of the X-ray irradiation unit 1 and the detectable area 2R of the X-ray detection unit 2, which can detect fluorescent X-rays, so that the X-ray detection unit 2 can be calibrated while analyzing the transported test sample W. This standard sample 5, used for calibration of the X-ray detection unit 2, contains one or more elements of known concentration (all elements not contained in the test sample W). In this embodiment, the standard sample 5 contains the element Mo (hereinafter referred to as the first element), which has a known concentration.

[0036] Although the standard sample 5 is placed in the repeating region, it has the characteristic of allowing most (e.g., more than 90%) of the X-rays irradiated from the X-ray irradiation unit 1 and directed toward the measurement sample W to pass through, and also allowing most (e.g., more than 90%) of the fluorescent X-rays generated from the measurement sample W and directed toward the X-ray detection unit 2 to pass through. Figure 3 As shown, the standard sample 5 in this embodiment is specifically a metal wire, which is arranged along the direction of the X-ray source and the X-ray detector 21 when viewed from the side of the test sample W. More specifically, it is arranged in a manner consistent with the straight line connecting the central axis A1 of the X-ray source and the central axis A2 of the detection field of view of the X-ray detector 21.

[0037] Furthermore, the standard sample 5 is positioned such that it will not interfere with the test sample W even if the transported test sample W is shaken. Specifically, the standard sample 5 is positioned at a safe distance relative to the surface of the test sample W, a safe distance that will not be touched even if the transported test sample W is shaken. More specifically, in this embodiment, the X-ray irradiation unit 1 and the X-ray detection unit 2 are positioned and oriented such that their repeating areas are formed within the housing 3, and the standard sample 5 is positioned within the repeating area near the opening 3a of the housing 3.

[0038] Furthermore, the information processing device 4 in this embodiment also functions as an element information storage unit 43, a peak detection unit 44, and a correction unit 46.

[0039] The element information storage unit 43 pre-stores first energy information related to the energy of the fluorescence X-rays inherent to the first element contained in the standard sample 5, and second energy information related to the energy of the fluorescence X-rays inherent to the second element, which is different from the first element. The second element is an element contained in the standard sample 5 or the test sample W. In this embodiment, the element contained in the test sample W is used as the second element.

[0040] In addition, the element information storage unit 43 stores standard intensity information related to the intensity of fluorescent X-rays originating from the first element, which is obtained in advance by irradiating the standard sample 5 set at the calibration position with X-rays from the X-ray irradiation unit 1.

[0041] The peak detection unit 44 analyzes the measured spectrum generated by the spectrum generation unit 41 according to a prescribed algorithm, such as the peak fitting method, and detects the peak values ​​corresponding to the first element and the second element, respectively.

[0042] The correction unit 46 is configured to perform energy correction of the X-ray detection unit 2 based on the first energy information and the second energy information stored in the element information storage unit 43, as well as information related to the position of the peak values ​​of the first element and the second element detected by the peak detection unit 44.

[0043] Specifically, the correction unit 46 calculates the deviation between the fluorescence X-ray energy represented by the peak positions of the detected first element and the peak positions of the second element and the fluorescence X-ray energy represented by the first energy information and the second energy information, respectively, and performs energy correction on the X-ray detection unit 2 to eliminate the deviation. More specifically, it updates the first correction coefficient pre-stored in the signal processing unit 22 of the X-ray detection unit 2 to eliminate the calculated deviation. More specifically, as... Figure 4As shown, in the measured spectrum generated by the spectrum generation unit 41, there are peaks originating from the first element contained in the standard sample 5 and peaks originating from the second element contained in the measured sample W. The correction unit 46 compares the energy represented by the positions of these two peaks with the energy of the fluorescent X-rays represented by the first energy information and the second energy information, respectively, and performs energy correction (specifically, updates the stored first correction coefficient).

[0044] Furthermore, the correction unit 46 in this embodiment is configured to perform intensity correction based on the standard intensity information stored in the element information storage unit 43 and information related to the peak intensity of the first element detected by the peak detection unit 44. Specifically, the correction unit 46 calculates the deviation by comparing the intensity of the fluorescent X-rays originating from the first element stored in the standard intensity information with the detected peak intensity of the first element, and updates the second correction coefficient stored in the spectrum generation unit 41 to eliminate the deviation.

[0045] Furthermore, in the X-ray analysis apparatus 100 of this embodiment, in order to enable the calibration unit 46 to perform calibration operations at appropriate timing, the information processing unit 4 also functions as a reference spectrum storage unit 47 and a spectrum comparison unit 48.

[0046] The reference spectrum storage unit 47 stores a reference spectrum in advance for determining the calibration timing of the calibration unit 46. As described above, in this embodiment, the test sample W alternately presents the surface of the film material W2 and the surface of the substrate material W1 in the repeating region as it is transported, thereby repeatedly exhibiting various states (specifically two states) with different constituent elements. This reference spectrum is a fluorescence spectrum obtained by irradiating the test sample W, which is set up in such a way that it becomes one of the multiple states, with X-rays before the analysis begins. In this embodiment, the spectrum of the fluorescence X-rays generated from the substrate material W1 is used as the reference spectrum, but it is not limited to this.

[0047] The spectral comparison unit 48 compares the reference spectrum stored in the reference spectrum storage unit 47 with the measured spectrum generated by the spectrum generation unit 41 to determine whether they are similar. Specifically, the spectral comparison unit 48 calculates the similarity between the reference spectrum and the measured spectrum based on a predetermined known algorithm, and determines that they are similar if the similarity is above a predetermined value.

[0048] Then, when the spectral comparison unit 48 determines that the measured spectrum is similar to the reference spectrum, the correction unit 46 performs a correction operation. Specifically, when the spectral comparison unit 48 determines that they are similar, the peak detection unit 44 analyzes the measured spectrum and detects the peak values ​​of the first and second elements, and then the correction unit 46 performs the correction operation (energy correction and / or intensity correction).

[0049] Furthermore, in this embodiment, to speed up the peak detection and correction operations performed by the peak detection unit 44, the peak detection unit 44 refers to the first energy information and the second energy information stored in the element information storage unit 43, and detects the peak values ​​corresponding to the first element and the second element from the measured spectrum. Specifically, in this embodiment, the element information storage unit 43 stores the peak positions corresponding to the energies of the fluorescence X-rays inherent to the first element and the second element, namely, the first reference peak position and the second reference peak position, as the first energy information and the second energy information. Moreover, the peak detection unit 44 uses the first reference peak position and the second reference peak position as references to detect the peak values ​​of the first element and the second element from the newly generated measured spectrum.

[0050] Furthermore, in this embodiment, the correction unit 46 is configured to compare the peak position of the first element detected by the peak detection unit 44 from the newly generated measured spectrum with the first reference peak position stored in the element information storage unit 43, and perform energy correction of the X-ray detection unit 2 if the deviation is above a predetermined value.

[0051] According to the X-ray analysis apparatus 100 of this embodiment, since a standard sample 5 containing a known element is arranged in an overlapping region of the irradiation area 1R of X-rays irradiated by the X-ray irradiation unit 1 and the detectable area 2R of fluorescent X-rays that can be detected by the X-ray detection unit 2, the X-ray detection unit 2 can simultaneously detect fluorescent X-rays generated from the test sample W and fluorescent X-rays generated from the standard sample 5, and the calibration operation of the X-ray detection unit 2 can be performed while analyzing the test sample W. For example, by pre-storing information related to the energy of fluorescent X-rays of the elements contained in the standard sample 5, comparing the energy of the elements contained in the standard sample 5 with the peak position of the element in the spectrum generated based on the output of the X-ray detection unit 2, and calculating the deviation, the energy correction of the X-ray detection unit 2 can be performed.

[0052] Furthermore, the present invention is not limited to the embodiments described above. For example, the standard sample 5, i.e., the metal wire, in the above embodiment is arranged along the direction in which the X-ray source and X-ray detector 21 are arranged, but it is not limited to this. In other embodiments, the standard sample 5, i.e., the metal wire, may also be arranged along a direction intersecting the direction in which the X-ray source and X-ray detector 21 are arranged. In this case, multiple metal wires may also be arranged in the direction in which the X-ray source and X-ray detector 21 are arranged.

[0053] Furthermore, the standard sample 5 in other embodiments is not limited to metal wires; for example, it can be a mesh or film structure. When the standard sample 5 is in the form of a film, it can be, for example, a product in which a metal layer is deposited on a resin film such as polyimide, rolled beryllium foil, or graphene film that is easily transmissible to X-rays.

[0054] Furthermore, in the above embodiments, the second element is included in the test sample W, but this is not a limitation. In other embodiments, the second element may also be included in the standard sample 5.

[0055] Furthermore, in the X-ray analysis apparatus 100 of this embodiment, the calibration unit 46 calibrates the X-ray detector 21 based on information from the two peak values ​​of the first element and the second element, but is not limited to this. In other embodiments, the calibration unit 46 may also calibrate the X-ray detector 21 based solely on information from the peak value of the first element, without using information from the peak value of the second element.

[0056] Furthermore, X-ray analysis apparatus 100 in other embodiments may not have the functions of reference spectrum storage unit 47 and spectrum comparison unit 48. As long as an X-ray analysis apparatus 100 in one embodiment can perform energy correction and / or intensity correction, it can perform energy correction and / or intensity correction.

[0057] Furthermore, the number of times (or the accumulation time) of the measured spectra generated by the spectrum generation unit 41 can be the same or different in both the spectra used for quantitative analysis in the analysis unit 42 and the spectra used for various corrections in the correction unit 46. For example, when generating the measured spectra (correction spectra) used for various corrections in the correction unit 46, the number of times the spectra are accumulated (or the accumulation time is longer) is greater than that used for generating the measured spectra (analytical spectra) used for quantitative analysis in the analysis unit 42. In this way, correction operations can be performed with high precision while performing quantitative analysis at shorter intervals. For example, for analytical spectra obtained every 3 seconds by accumulating spectra over 3 seconds, the correction spectra are generated by accumulating the most recent few times.

[0058] Furthermore, when generating the calibration spectrum, the spectrum generation unit 41 preferably accumulates multiple analytical spectra that have low noise components near the peak corresponding to the first element from among the recently generated analytical spectra. The term "noise components near the peak corresponding to the first element" can include, for example, noise components originating from the first element contained in the sample being measured (not a standard sample) and noise components caused by scattered X-rays. In other words, "analytical spectra with low noise components near the peak corresponding to the first element" refers to spectra from which the peak of the first element contained in the calibration sample can be easily detected.

[0059] Furthermore, the spectrum generation unit 41 more preferably accumulates multiple analytical spectra that are recently generated, have few noise components near the peak corresponding to the first element, and have a peak corresponding to the second element, to generate a correction spectrum.

[0060] Furthermore, the spectrum generation unit 41 can also refer to the similarity with the reference spectrum calculated by the spectrum comparison unit 48 to determine whether the generated analytical spectrum is an "analytical spectrum with few noise components near the peak corresponding to the first element". For example, if the similarity with the reference spectrum is above a predetermined value, a flag indicating "accumulated analytical spectrum suitable for generating correction spectra" can be set on the analytical spectrum for which the similarity is calculated.

[0061] Furthermore, in other embodiments, the X-ray analysis apparatus 100 may also include a range sensor for measuring the distance between the test sample W and the test sample W entering the repeating region, and an imaging device for photographing the test sample W entering the repeating region. The spectrum generation unit 41 may also determine, based on information output from the range sensor or the imaging device, whether the generated analytical spectrum is an "analytical spectrum with low noise components near the peak corresponding to the first element". Additionally, the spectrum generation unit 41 may also determine, based on various information output from the transport mechanism (e.g., information related to transport speed, time, etc.), whether the generated analytical spectrum is an "analytical spectrum with low noise components near the peak corresponding to the first element". For example, as in the above embodiment, when the test sample W is formed by intermittently coating a film material W2 onto one surface of a thin film substrate material W1, the analytical spectrum generated based on the fluorescent X-rays produced from the film material W2 can be labeled as "the cumulative analytical spectrum suitable for generating the calibration spectrum" by referring to the information output from the ranging sensor, imaging device, or conveying mechanism.

[0062] Furthermore, in the X-ray analysis apparatus 100 of the above embodiment, the X-ray detection unit 2 stores a first correction coefficient for energy correction, and the X-ray detection unit 2 performs energy correction, but is not limited to this. In other embodiments, the information processing device 4 may also be configured to store the first correction coefficient, and energy correction may be performed in the information processing device 4 (e.g., the spectrum generation unit 41).

[0063] Furthermore, various modifications and combinations of embodiments are permissible as long as they do not deviate from the spirit of this invention. Industrial applicability

[0064] According to the present invention, in a fluorescence X-ray analysis apparatus for analyzing transported test samples, calibration operations can be performed simultaneously with the analysis of the test samples. Explanation of reference numerals in the attached figures:

[0065] 100: X-ray analysis device; 1: X-ray irradiation unit; 1R: irradiation area; 2: X-ray detection unit; 2R: detectable area; 5: standard sample; W: test sample.

Claims

1. An X-ray analysis apparatus for analyzing elements contained in a sample being measured, transported along a predetermined direction, wherein, The X-ray analysis device includes: The X-ray irradiation unit irradiates the test sample with X-rays; The X-ray detection unit faces the test sample and detects fluorescent X-rays generated from the test sample. as well as The standard sample is disposed in an overlapping region of the irradiation area of ​​the X-ray irradiation unit and the detectable region of the fluorescent X-ray that can be detected by the X-ray detection unit, and contains known elements.

2. The X-ray analysis apparatus according to claim 1, wherein, The X-ray analysis device also includes: The spectrum generation unit generates the spectrum of fluorescent X-rays generated from the test sample, i.e., the measured spectrum, based on the output of the X-ray detection unit. The element information storage unit stores first energy information related to the energy of the fluorescent X-rays inherent to the first element contained in the standard sample; The peak detection unit analyzes the generated measured spectrum and detects the peak value corresponding to the first element; as well as The correction unit performs energy correction based on the first energy information stored in the element information storage unit and information related to the position of the peak value of the first element detected by the peak detection unit.

3. The X-ray analysis apparatus according to claim 2, wherein, The standard sample or the test sample contains a second element that is different from the first element. The element information storage unit stores second energy information related to the energy of the fluorescent X-rays inherent in the second element. The peak detection unit analyzes the measured spectrum and detects the peak value corresponding to the second element. The correction unit performs energy correction based on the first energy information and the second energy information stored in the element information storage unit, as well as information related to the position of the peak values ​​of the first element and the second element detected by the peak detection unit.

4. The X-ray analysis apparatus according to claim 2 or 3, wherein, The element information storage unit also stores standard intensity information related to the intensity of fluorescent X-rays originating from the first element, which is obtained in advance by irradiating the standard sample with X-rays. The correction unit performs intensity correction based on the standard intensity information stored in the element information storage unit and information related to the peak intensity of the first element detected by the peak detection unit.

5. The X-ray analysis apparatus according to any one of claims 2 to 4, wherein, The spectral generation unit generates an analytical spectrum for analyzing the sample to be measured and a calibration spectrum for calibration by the calibration unit, which are used as the measured spectrum. The cumulative number of times the calibration spectrum is generated is greater than the cumulative number of times the analytical spectrum is generated.

6. The X-ray analysis apparatus according to claim 5, wherein, The spectrum generation unit accumulates multiple recently generated measured spectra with low noise components near the peak corresponding to the first element to generate the correction spectrum.

7. The X-ray analysis apparatus according to any one of claims 2 to 6, wherein, The X-ray analysis device also includes: The reference spectrum storage unit stores reference spectra in advance for determining the calibration timing of the calibration unit; as well as The spectral comparison unit compares the stored reference spectrum with the measured spectrum generated by the spectral generation unit to determine whether they are similar. When the spectral comparison unit determines that the measured spectrum is similar to the reference spectrum, the peak detection unit performs analysis of the measured spectrum.

8. The X-ray analysis apparatus according to claim 7, wherein, As the test sample is transported, it repeatedly presents multiple states with different constituent elements in the repeating region. The reference spectrum is generated based on the output of the X-ray detection unit in one of the plurality of states.

9. The X-ray analysis apparatus according to any one of claims 2 to 8, wherein, The element information storage unit stores the peak position, i.e., the reference peak position, corresponding to the energy of the inherent fluorescence X-rays of the first element, as the first energy information. If the deviation between the peak position of the first element detected by the peak detection unit and the reference peak position stored in the element information storage unit is greater than or equal to a predetermined value, the correction unit performs energy correction.

10. The X-ray analysis apparatus according to claim 9, wherein, The peak detection unit refers to information related to the reference peak position stored in the element information storage unit to detect the peak corresponding to the first element from the measured spectrum.

11. The X-ray analysis apparatus according to any one of claims 1 to 10, wherein, The standard sample is positioned within a region that maintains a safe distance from the surface of the transported test sample, ensuring that it will not come into contact with that surface.

12. The X-ray analysis apparatus according to any one of claims 1 to 11, wherein, The X-ray analysis apparatus further includes a housing that houses the X-ray irradiation unit and the X-ray detection unit, with an opening formed on one side wall to allow X-rays generated from the X-ray irradiation unit and fluorescent X-rays generated from the sample to be measured to pass through. The standard sample is positioned within the repeating region located near the opening inside the chamber.

13. The X-ray analysis apparatus according to any one of claims 1 to 12, wherein, The standard sample is in the form of filaments, mesh, rings, or film.

14. The X-ray analysis apparatus according to any one of claims 1 to 13, wherein, The elements contained in the standard sample are different from those contained in the test sample.

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