WO2017026200A1 - 蛍光x線分析装置 - Google Patents
蛍光x線分析装置 Download PDFInfo
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- WO2017026200A1 WO2017026200A1 PCT/JP2016/069689 JP2016069689W WO2017026200A1 WO 2017026200 A1 WO2017026200 A1 WO 2017026200A1 JP 2016069689 W JP2016069689 W JP 2016069689W WO 2017026200 A1 WO2017026200 A1 WO 2017026200A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
- G01N2223/0766—X-ray fluorescence with indicator, tags
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- the present invention irradiates a specimen in which a single-layer or multi-layer thin film is formed on a substrate or independently, and irradiates the primary X-ray, and based on the measured intensity of the generated secondary X-ray, the thin film composition and
- the present invention relates to a fluorescent X-ray analyzer for obtaining a quantitative value of thickness.
- secondary X-rays to be measured that is, measurement lines are appropriately selected and set depending on the type of sample to be analyzed.
- thin film samples such as semiconductor wafers and iron-zinc alloy plated steel sheets, thin films Therefore, it is not easy to select the measurement line, and accurate analysis cannot be performed if the selection is inappropriate.
- the measurement line evaluation means changes the first theoretical intensity and the thickness or content rate at the specified thickness and composition for each layer of the thin film by a predetermined amount for each specified measurement line.
- Calculate a second theoretical strength at the thickness and composition calculate a predetermined thickness accuracy or content rate accuracy using the first and second theoretical strengths, based on the thickness accuracy or content rate accuracy, Whether or not analysis can be performed using the designated measurement line is determined, and whether or not the analysis is possible is displayed on the display, so that the operator can easily select the measurement line based on the display.
- both the thickness and composition of the plating layer, which is a thin film, are analyzed, and iron is included as an element common to the substrate and the plating layer, which are different layers. In such a case, it may not be correctly determined whether the analysis using the designated measurement line is possible.
- the present invention has been made in view of the above-described conventional problems.
- fluorescent X-ray analysis of a thin film sample both the composition and thickness of each layer of the thin film are analyzed, and the same element is included in different layers.
- Another object of the present invention is to provide an apparatus that facilitates selection of an appropriate measurement line and enables accurate analysis.
- the first configuration of the present invention is to measure a secondary X-ray generated by irradiating a sample in which a single-layer or multilayer thin film is formed on a substrate or independently and irradiating a primary X-ray.
- Fluorescence X-ray analysis apparatus for obtaining a quantitative value of the composition and / or thickness of the thin film by a fundamental parameter method based on intensity, and a quantitative error with respect to analysis by a measurement line that is a secondary X-ray whose intensity should be measured
- Measurement line evaluation means for estimating whether or not analysis is possible
- display control means for displaying a quantitative error obtained by the measurement line evaluation means and / or analysis possibility on a display.
- the measurement line evaluation unit first calculates the estimated measurement intensity by theoretical intensity calculation and apparatus sensitivity for all of the designated measurement lines based on the composition and / or thickness designated for the thin film.
- the composition of the thin film after the change in the estimated measurement intensity by the fundamental parameter method and The procedure for obtaining the quantitative value of the thickness is repeated by changing the measurement line for changing the estimated measurement intensity.
- estimation of the quantitative error and / or determination of whether analysis is possible is performed.
- the estimated measurement intensity is calculated by theoretical intensity calculation and apparatus sensitivity for all the specified measurement lines based on the composition and / or thickness specified for the thin film. Change only the estimated measurement intensity of the measurement line by a predetermined amount, and obtain the quantitative value of the thin film composition and / or thickness after the change of the estimated measurement intensity by the fundamental parameter method. Based on the obtained quantitative value and the specified composition and / or thickness, the quantitative error is estimated and / or analyzed.
- a primary X-ray is irradiated on a sample in which a single-layer or multilayer thin film is formed on a substrate or independently, and based on the measured intensity of the generated secondary X-ray, the fundamental parameter method is used.
- Fluorescence X-ray analysis apparatus for obtaining a quantitative value of the composition and / or thickness of the thin film, and for the analysis using a measurement line that is a secondary X-ray whose intensity is to be measured, estimation of quantitative error and / or the possibility of analysis Measurement line evaluation means for determining the optimal measurement line combination and the measurement line evaluation means, and the quantitative error and / or analysis availability obtained by the measurement line evaluation means and the display for displaying the optimal measurement line combination on the display Control means.
- the measurement line evaluation means first calculates an estimated measurement intensity by theoretical intensity calculation and apparatus sensitivity for all measurement lines that can measure the intensity based on the composition and / or thickness specified for the thin film.
- a combination of measurement lines for determining a quantitative value of the composition and / or thickness of the thin film is created from all the measurement lines capable of measuring the intensity.
- for each combination of the measurement lines based on a set of estimated measurement intensities in which only the estimated measurement intensity of one measurement line of the set of estimated measurement intensities of the measurement lines included in the combination is changed by a predetermined amount.
- the procedure for obtaining the quantitative value of the composition and / or thickness of the thin film after the change in the estimated measurement intensity by the fundamental parameter method is repeated while changing the measurement line for changing the estimated measurement intensity.
- estimation of the quantitative error and / or determination of whether analysis is possible and selection of an optimal measurement line combination are performed.
- the estimated measurement intensity is calculated by theoretical intensity calculation and apparatus sensitivity for all measurement lines capable of measuring the intensity based on the composition and / or thickness specified for the thin film, Create a combination of measurement lines to obtain a quantitative value of the composition and / or thickness of the thin film, and change the estimated measurement intensity of one measurement line by a predetermined amount for each combination of the measurement lines.
- the procedure for obtaining the quantitative value of the composition and / or thickness of the thin film after the change of the estimated measurement intensity is repeated by changing the measurement line for changing the estimated measurement intensity, and the obtained quantitative value and the specified composition and / or Based on the thickness, estimation of the quantitative error and / or determination of the possibility of analysis and selection of an optimal combination of measurement lines are performed.
- this apparatus irradiates a primary X-ray 2 from an X-ray source 1 such as an X-ray tube onto a sample 3 in which a single-layer or multilayer thin film is formed on a substrate or independently.
- the intensity of the generated secondary X-ray 4 is measured by the detection means 9, and the quantitative value of the composition and / or thickness of the thin film is obtained by the fundamental parameter method (hereinafter also referred to as FP method) based on the measured intensity.
- FP method fundamental parameter method
- Measuring line evaluation means 23 for estimating the quantitative error and / or determining whether or not the analysis is possible for the analysis by the measuring line 4 which is a secondary X-ray whose intensity is to be measured, and the measurement thereof.
- Display control means 22 for displaying the quantitative error obtained by the line evaluation means 23 and / or the possibility of analysis on a display 16 such as a liquid crystal display.
- the sample 3 is a so-called thin film sample, for example, an iron-zinc alloy-plated steel plate, and is placed on the sample table 8.
- the detection means 9 is composed of a spectroscopic element 5 that splits secondary X-rays 4 such as fluorescent X-rays generated from the sample 3 and a detector 7 that measures the intensity of each of the split secondary X-rays 6. .
- the display control means 22 and the measurement line evaluation means 23 are included in the analysis condition creation means 20.
- the determination of the quantitative value of the composition and / or thickness of the thin film by the FP method based on the measured intensity is based on the assumed composition and / or thickness of each thin film (may be a single layer) constituting the sample 3.
- the theoretical intensity of the secondary X-ray 4 generated from the sample 3 by being excited by the primary X-ray 2 is calculated, and the theoretical intensity and the converted measured intensity obtained by converting the measured intensity of the sample 3 into the theoretical intensity scale are
- the assumed composition and / or thickness of each thin film is calculated by successive approximate correction to obtain a quantitative value of the composition and / or thickness.
- the measurement line evaluation means 23 provided in the X-ray fluorescence analyzer of the first embodiment specifically operates as shown in the flowchart of FIG. First, in step S1, the composition (content ratio of each component) Wi1 and / or thickness Ti1 (reference numeral 1 is designated) for the thin film i by an operator using an input means (not shown) provided in the analysis condition creating means 20
- the measured intensity IipM1 (the sign M indicates the measured intensity scale) is calculated based on the theoretical intensity calculation and the instrument sensitivity for all of the specified measurement lines ip. calculate.
- the estimated measurement intensity IipM1 is obtained by dividing the theoretical intensity IipT1 calculated by theoretical calculation for each measurement line ip (the sign T indicates the theoretical intensity scale) by the apparatus sensitivity kip and converting it to the measured intensity scale. Is calculated.
- the device sensitivity kip is obtained in advance by measuring a standard sample such as a pure substance for each measurement line ip, and obtaining it as the ratio of the theoretical intensity to the measurement intensity and storing it in the measurement line evaluation means 23.
- step S2 based on the set of estimated measurement intensity IipM2 in which only the estimated measurement intensity of one measurement line of the set of estimated measurement intensity IipM1 calculated in step S1 is changed by a predetermined amount, the estimated measurement is performed by the FP method.
- the quantitative value Wi2 (ip) and / or the quantitative value Ti2 (ip) of the thin film composition after the intensity change is obtained (the symbol 2 ⁇ indicates that the value has changed from the specified value). More specifically, first, the accuracy Sip for the intensity of each measurement line ip is estimated by the following equation (1).
- Sip (IipM1 / t) 1/2 (1)
- t is the measurement time (seconds), for example, 40 seconds.
- IipM2 IipM1 + ⁇ ⁇ Sip (2)
- the original estimated measurement intensity IipM1 is obtained from the following equation (3).
- IipM2 IipM1 (3)
- a new set of estimated measurement intensities IipM2 is created from the estimated measurement intensities IipM2 by these formulas (2) and (3). Then, based on the set of new estimated measurement intensities IipM2, a quantitative value Wi2 (ip) and / or a quantitative value Ti2 (ip) of the thickness of the thin film after the change of the estimated measurement intensity is obtained by the FP method. Note that an upper limit value (for example, twice) may be provided for the number of repeated calculations in the FP method up to the quantitative value. This operation is performed by changing the estimated measurement intensity of the measurement line ip one by one to IipM1 + ⁇ ⁇ Sip.
- step S2 is repeated until the measurement line ip for changing the estimated measurement intensity IipM1 is changed and the estimated measurement intensity IipM1 is changed for all of the designated measurement lines ip. Since the variation in the X-ray intensity of the measurement line is a phenomenon independent for each measurement line, the rationality is not lost even if only the estimated measurement intensity of each measurement line is changed in this way.
- step S3 the quantitative value Wi2 (ip) and / or the thickness quantitative value Ti2 (ip) of the composition obtained in step S2 and the specified composition Wi1 and / or thickness Ti1 are determined.
- the error ⁇ Wi and / or ⁇ Ti is estimated and / or judged as to whether analysis is possible. More specifically, first, according to the following formulas (4) and / or (5), the quantitative value Wi2 (ip) and / or the thickness of the composition after the change for each measurement line ip in which the estimated measurement intensity is changed. The difference between the quantitative value Ti2 (ip) of the material and the specified composition Wi1 and / or thickness Ti1 is obtained.
- the composition quantitative error ⁇ Wi and / or the thickness of each thin film i in consideration of the designated total measurement line ip Estimate the quantitative error ⁇ Ti.
- n is the number of measurement lines.
- ⁇ Wi ( ⁇ ip ⁇ Wi (ip) 2 / n) 1/2 (6)
- ⁇ Ti ( ⁇ ip ⁇ Ti (ip) 2 / n) 1/2 (7)
- the following measurement formulas (8) and / or (9) indicate whether the analysis can be performed using the designated measurement line. You may make a judgment.
- Rs is a required relative accuracy, for example, uniformly 0.05, but may be set individually for each thin film i. Then, if the formulas (8) and / or (9) are satisfied with respect to the composition and / or thickness of all the thin films, it is determined that the analysis is possible, and if even one is not satisfied, it is determined that the analysis is impossible.
- the determination as to whether analysis is possible may be performed for each measurement line designated by the following equation (10) and / or (11), or may be performed in a loop of step S2.
- the quantitative error ⁇ Wi and / or ⁇ Ti obtained by the measurement line evaluation means 23 and / or the possibility of analysis are displayed on the display 16 by the display control means 22.
- the quantitative error ⁇ WiW and / or Since ⁇ Ti is estimated and / or analysis is possible and the result is displayed on the display 16
- both the composition and thickness of each layer of the thin film are analyzed, and the same element is applied to different layers. Even in such a case, the operator can easily and appropriately select the measurement line based on the displayed result, and can perform an accurate analysis.
- this apparatus irradiates a primary X-ray 2 onto a sample 3 on which a single-layer or multilayer thin film is formed on a substrate or independently, and generates a measurement intensity of a secondary X-ray 4 generated.
- a fluorescent X-ray analysis apparatus for obtaining a quantitative value of the composition and / or thickness of the thin film based on the FP method, and estimating a quantitative error for the analysis by the measurement line 4 which is a secondary X-ray whose intensity is to be measured.
- / or measurement line evaluation means 33 for determining whether analysis is possible and selecting an optimum combination of measurement lines, and the quantitative error obtained by the measurement line evaluation means 33 and / or analysis availability and the optimal measurement line.
- Display control means 32 for displaying the combination on the display 16.
- the apparatus of the second embodiment is different from the apparatus of the first embodiment in the operation of the measurement line evaluation unit 33 and the operation of the display control unit 32, that is, the contents displayed on the display device 16, and will be described.
- the measurement line evaluation means 33 provided in the apparatus of the second embodiment operates as shown in the flowchart of FIG.
- the apparatus of the first embodiment is used for all the measurement lines ip that can measure the intensity based on the composition Wi1 and / or the thickness Ti1 specified for the thin film i in the same manner as the apparatus of the first embodiment.
- the estimated measured intensity IipM1 is calculated by theoretical intensity calculation and apparatus sensitivity.
- the measurement line ip capable of measuring the intensity is retrieved from the table of measurement lines for each element constituting the thin film i stored in the measurement line evaluation means 33 based on the configuration of the device to be used (for example, a spectroscopic element).
- Sample 3 is an iron-zinc alloy-plated steel plate in which a plating film made of iron and zinc is formed on a substrate that is a steel plate, the specified composition Wi1 is the iron content, and zinc is the remainder.
- the substrate is made of iron, six measurement lines ip of Zn -K ⁇ , Zn -K ⁇ , Zn -L ⁇ , Fe -K ⁇ , Fe -K ⁇ , and Fe -L ⁇ are searched.
- step S2A-1 a combination j of measurement lines ip for obtaining a quantitative value of the composition and / or thickness of the thin film is created from all the measurement lines ip searched in step S1A.
- 15 combinations are created since two measurement lines are used to analyze the iron content and thickness of the plating film.
- step S2A-2 for each combination jip of measurement lines ip created in step S2A-1, one of the sets of estimated measurement intensities IipM1 calculated in step S1A for the measurement line ip included in the combination j.
- the quantitative value Wi2 (ip, j) and / or the thickness of the thin film composition after the estimated measurement intensity change by the FP method The procedure for obtaining the quantitative value Ti2 (ip, j) is repeated by changing the measurement line ip for changing the estimated measurement intensity IipM1. That is, the operation of step S2 in the measurement line evaluation unit 23 of the apparatus of the first embodiment is performed for all the combinations j ⁇ of the measurement lines ip created in step S2A-1.
- step S3A the composition quantitative value Wi2 (ip, j) and / or the thickness quantitative value Ti2 (ip, j) obtained in step S2A-2 and the specified composition Wi1 and / or thickness Ti1 are determined. Based on the above, the estimation of the quantitative error ⁇ Wij and / or ⁇ Tij and / or determination of the possibility of analysis and selection of the optimum combination of measurement lines are performed. More specifically, first, according to the following formulas (12) and / or (13), for each measurement line ip in which the estimated measurement intensity is changed for all the combinations j of the measurement lines ip created in step S2A-1. Then, the difference between the quantitative value Wi2 (ip, j) of the composition after change and / or the quantitative value Ti2 (ip, j) of the thickness and the specified composition Wi1 and / or thickness Ti1 is obtained.
- ⁇ Wi (ip, j) Wi2 (ip, j) -Wi1 (12)
- ⁇ Ti (ip, j) Ti2 (ip, j) ⁇ Ti1 (13)
- n is the number of measurement lines.
- ⁇ Wij ( ⁇ ip ⁇ Wi (ip, j) 2 / n) 1/2 (14)
- the composition quantitative relative error ⁇ Wij and / or the thickness quantitative error ⁇ Tij thus estimated, for example, at each combination j of the measurement line ip, the composition quantitative relative error ⁇ Wij / Wi1 and / or the thickness
- the quantitative relative error ⁇ Tij / Ti1 is calculated and the quantitative relative error with the largest numerical value is set as the representative quantitative relative error of the combination j.
- the combination with the smallest representative quantitative relative error is selected as the optimum measurement line. Select as a combination.
- the optimum combination of the measurement lines obtained by the measurement line evaluation means 33 and the quantitative error ⁇ Wij and / or ⁇ Tij in the combination j ⁇ and / or the possibility of analysis in the combination j are displayed control means. 32 is displayed on the display 16.
- the display 16 may display a layer incapable of thickness analysis and / or a component incapable of content analysis and a layer including the component.
- Table 1 shows the estimation results of quantitative errors by the measuring line evaluation means 33, taking as an example the case of analyzing the iron-zinc alloy layer of the iron-zinc alloy-plated steel sheet using the apparatus of the second embodiment.
- the specified Fe content is 10.0% and the specified thickness is 4.3 ⁇ m.
- the amount of change in the estimated measurement intensity in the previous equation (2) is twice the accuracy, and the lower limit of the relative accuracy of the X-ray intensity is 0.05% in consideration of various reproducibility.
- “RMS” in Table 1 is the quantitative error (square root of the root mean square error) estimated by the previous formulas (14) and (15), and “no solution” is consistent with the content and thickness. This means that no quantitative value was obtained.
- the combination of Zn -K ⁇ and Zn -L ⁇ that minimizes the quantitative error RMS estimated for the content and thickness in Table 1 is selected by the measurement line evaluation means 33 as the optimum combination of measurement lines.
- the display control means 32 displays the effect on the display 16.
- the optimum combination of measurement lines is also selected, so both the composition and thickness of each layer of the thin film are analyzed, and even when the same element is contained in different layers, Appropriate measurement lines can be automatically selected for accurate analysis.
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Abstract
Description
3 試料
4 2次X線(測定線)
16 表示器
22,32 表示制御手段
23,33 測定線評価手段
Claims (2)
- 単層もしくは多層の薄膜を基板上にまたは独立して形成した試料に1次X線を照射し、発生する2次X線の測定強度に基づいてファンダメンタルパラメーター法により前記薄膜の組成および/または厚さの定量値を求める蛍光X線分析装置であって、
強度を測定すべき2次X線である測定線による分析について、定量誤差の推定および/または分析の可否の判断を行う測定線評価手段と、
その測定線評価手段によって得られた定量誤差および/または分析の可否を表示器に表示させる表示制御手段とを備え、
前記測定線評価手段が、
前記薄膜について指定された組成および/または厚さに基づいて、指定された測定線のすべてについて理論強度計算および装置感度により推定測定強度を算出し、
その推定測定強度の組のうち1つの測定線の推定測定強度のみを所定量変化させた推定測定強度の組に基づいて、ファンダメンタルパラメーター法により推定測定強度変化後の前記薄膜の組成および/または厚さの定量値を求める手順を、推定測定強度を変化させる測定線を変えて繰返し、
求めた定量値と前記指定された組成および/または厚さとに基づいて、前記定量誤差の推定および/または分析の可否の判断を行う蛍光X線分析装置。 - 単層もしくは多層の薄膜を基板上にまたは独立して形成した試料に1次X線を照射し、発生する2次X線の測定強度に基づいてファンダメンタルパラメーター法により前記薄膜の組成および/または厚さの定量値を求める蛍光X線分析装置であって、
強度を測定すべき2次X線である測定線による分析について、定量誤差の推定および/または分析の可否の判断ならびに最適な測定線の組み合わせの選択を行う測定線評価手段と、
その測定線評価手段によって得られた定量誤差および/または分析の可否ならびに最適な測定線の組み合わせを表示器に表示させる表示制御手段とを備え、
前記測定線評価手段が、
前記薄膜について指定された組成および/または厚さに基づいて、強度を測定できる測定線のすべてについて理論強度計算および装置感度により推定測定強度を算出し、
前記強度を測定できる測定線のすべてから、前記薄膜の組成および/または厚さの定量値を求めるための測定線の組み合わせを作成し、
その測定線の組み合わせごとに、その組み合わせに含まれる測定線の前記推定測定強度の組のうち1つの測定線の推定測定強度のみを所定量変化させた推定測定強度の組に基づいて、ファンダメンタルパラメーター法により推定測定強度変化後の前記薄膜の組成および/または厚さの定量値を求める手順を、推定測定強度を変化させる測定線を変えて繰返し、
求めた定量値と前記指定された組成および/または厚さとに基づいて、前記定量誤差の推定および/または分析の可否の判断ならびに最適な測定線の組み合わせの選択を行う蛍光X線分析装置。
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EP16834897.7A EP3336527B1 (en) | 2015-08-10 | 2016-07-01 | X-ray fluorescence spectrometer |
CN201680003309.3A CN107076687A (zh) | 2015-08-10 | 2016-07-01 | 荧光x射线分析装置 |
JP2017520570A JP6175662B2 (ja) | 2015-08-10 | 2016-07-01 | 蛍光x線分析装置 |
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WO2022091597A1 (ja) | 2020-10-30 | 2022-05-05 | 株式会社リガク | 蛍光x線分析装置 |
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JP6732347B1 (ja) * | 2019-03-29 | 2020-07-29 | 株式会社リガク | 蛍光x線分析装置 |
CN110530912B (zh) * | 2019-09-12 | 2022-01-04 | 岛津企业管理(中国)有限公司 | 一种含镀层贵金属成分的x射线荧光光谱分析方法 |
JP6838754B1 (ja) * | 2019-09-26 | 2021-03-03 | 株式会社リガク | 蛍光x線分析装置 |
JP7178725B2 (ja) * | 2020-11-30 | 2022-11-28 | 株式会社リガク | 蛍光x線分析装置 |
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WO2022091598A1 (ja) | 2020-10-30 | 2022-05-05 | 株式会社リガク | 蛍光x線分析装置 |
WO2022091597A1 (ja) | 2020-10-30 | 2022-05-05 | 株式会社リガク | 蛍光x線分析装置 |
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CN112378938A (zh) | 2021-02-19 |
JPWO2017026200A1 (ja) | 2017-08-31 |
EP3336527A4 (en) | 2019-04-17 |
EP3336527A1 (en) | 2018-06-20 |
US10012605B2 (en) | 2018-07-03 |
EP3336527B1 (en) | 2020-04-22 |
CN107076687A (zh) | 2017-08-18 |
US20170322165A1 (en) | 2017-11-09 |
JP6175662B2 (ja) | 2017-08-09 |
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