Fluorescence X-ray analysis device

Abstract

The measurement line evaluation mechanism (23) calculates the estimated measurement intensity for all the specified measurement lines by theoretical calculation based on the composition and / or thickness specified for the film, changes the estimated measurement intensity of only one measurement line by a specified amount, and for each changed measurement line, calculates the quantitative value of the composition and / or thickness of the film after the change in the estimated measurement intensity by the basic parameter method, and judges whether the quantitative error can be estimated and / or analyzed based on the quantitative value and the specified composition and / or thickness.

Description

[0001] The present invention is a divisional application of the invention patent application No. 201680003309.3 filed on July 1, 2016, with the invention name “Fluorescence X-ray Analyzer”.

[0002] Related Applications

[0003] The present invention claims the benefit of priority from Japanese Patent Application No. 2015-157958, filed on August 10, 2015, the entirety of which is incorporated herein by reference as a part of the present application. Technical Field

[0004] The present invention relates to a fluorescent X-ray analysis device, in which a sample is irradiated with primary X-rays. The sample is formed by forming a single layer or multiple layers of thin film on a substrate or formed separately. Based on the measured intensity of the generated secondary X-rays, the quantitative value of the composition and / or thickness of the above-mentioned thin film is obtained by the fundamental parameter method. Background Art

[0005] In fluorescent X-ray analysis, when appropriately selecting and setting the secondary X-ray to be measured, that is, the measurement line, according to the type of sample to be analyzed, in the case of so-called thin film samples such as semiconductor wafers and steel plates plated with iron-zinc alloys, it is not easy to select the measurement line because both the composition and thickness of the thin film are to be analyzed, or the same element is contained in different layers or substrates. If the selection is inappropriate, correct analysis cannot be performed.

[0006] Therefore, as a prior art, there is a fluorescent X-ray analyzer as described below (see Patent Document 1). In the fluorescent X-ray analyzer, a measurement line evaluation mechanism calculates, for each of the specified measurement lines, a first theoretical intensity of the thickness and composition specified for each layer of the thin film and a second theoretical intensity of the thickness and composition after the thickness or content is changed by a specified amount, and calculates a specified thickness accuracy or content accuracy using the first theoretical intensity and the second theoretical intensity. Based on the thickness accuracy or content accuracy, the feasibility of the analysis based on the specified measurement line is determined, and the feasibility of the analysis is displayed on a display, so that the operator can easily determine the measurement line based on it.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: JP-A-2001-356103 Summary of the invention

[0010] Problems to be solved by the invention

[0011] However, when analyzing both the thickness and composition of the coating layer as a thin film, such as when the sample is a steel plate coated with an iron-zinc alloy, and when the substrate and the coating layer as different layers contain a common element of iron, it is impossible to correctly judge whether the analysis of the designated measurement line is possible. The reason is that in the conventional apparatus, for each designated measurement line, a first theoretical intensity of the thickness and composition designated for the coating layer, a second theoretical intensity of only changing the thickness by a predetermined amount, and a second theoretical intensity of only changing the content by a predetermined amount are calculated, and the predetermined thickness accuracy and content accuracy are calculated using these theoretical intensities. When judging whether the analysis of the designated measurement line is possible based on the thickness accuracy and content accuracy, in fact, the change in the corresponding quantitative value of the thickness and the composition does not correspond to the change in the intensity of the individual measurement line, and the intensity of each measurement line greatly depends on both the thickness and the composition of the coating layer.

[0012] The present invention has been proposed in view of the above-mentioned existing problems, and an object of the present invention is to provide a fluorescent X-ray analysis device, wherein, in the fluorescent X-ray analysis of a thin film sample, even when analyzing both the composition and thickness of each layer of the thin film and the same element is contained in different layers, it is still possible to easily select an appropriate measurement line and perform correct analysis.

[0013] Technical solutions to solve problems

[0014] In order to achieve the above-mentioned purpose, the first scheme of the present invention relates to a fluorescent X-ray analysis device, in which a sample is irradiated with primary X-rays, and the sample is formed by forming a single layer or multiple layers of thin film on a substrate or formed separately. According to the measured intensity of the generated secondary X-rays, the quantitative value of the composition and / or thickness of the above-mentioned thin film is obtained by the fundamental parameter method. The fluorescent X-ray analysis device includes: a measurement line evaluation mechanism, which estimates the quantitative error and / or determines the feasibility of the analysis of the measurement line of the secondary X-ray whose intensity is to be measured; and a display control mechanism, which displays the quantitative error and / or the feasibility of the analysis obtained by the measurement line evaluation mechanism on a display.

[0015] The measurement line evaluation mechanism first estimates the measurement intensity for all the established measurement lines by theoretical intensity calculation and device sensitivity calculation based on the composition and / or thickness specified for the film. Next, the step of repeatedly obtaining the quantitative value of the composition and / or thickness of the film after the estimated measurement intensity is changed by the fundamental parameter method in a manner that changes the estimated measurement intensity of the measurement line of the estimated measurement intensity according to the estimated measurement intensity group in which the estimated measurement intensity of only one measurement line in the group of estimated measurement intensity is changed by a specified amount. Then, the determination of the feasibility of the estimation and / or analysis of the quantitative error is performed based on the obtained quantitative value and the specified composition and / or thickness.

[0016] In the fluorescent X-ray analysis device of the first scheme, based on the composition and / or thickness specified for the thin film, the measurement intensity is estimated for all the specified measurement lines by theoretical intensity calculation and device sensitivity calculation, and the estimated measurement intensity of only one measurement line is changed by a specified amount. In such a way as to change the measurement line for which the estimated measurement intensity is estimated, the steps of obtaining the quantitative value of the composition and / or thickness of the above-mentioned thin film after the change in the estimated measurement intensity by the fundamental parameter method are repeated, and based on the above-mentioned quantitative value that has been obtained and the above-mentioned specified composition and / or thickness, the feasibility of the estimation and / or analysis of the above-mentioned quantitative error is judged.

[0017] That is, since the intensity of each measurement line depends largely on the composition and thickness of the film, the quantitative error can be estimated and / or the feasibility of the analysis can be determined. Therefore, even when both the composition and thickness of each layer of the film are analyzed and the same element is contained in different layers, it is easy to select the appropriate measurement line and correct analysis can be performed.

[0018] A second scheme of the present invention relates to a fluorescent X-ray analysis device, in which a sample is irradiated with primary X-rays, and the sample is formed by forming a single layer or multiple layers of thin film on a substrate or formed separately, and a quantitative value of the composition and / or thickness of the above-mentioned thin film is obtained by a fundamental parameter method based on the measured intensity of the generated secondary X-rays. The fluorescent X-ray analysis device includes: a measurement line evaluation mechanism, which estimates the quantitative error and / or determines the feasibility of analysis and selects the best combination of measurement lines for the analysis of the measurement line of the secondary X-ray whose intensity is to be measured; and a display control mechanism, which displays the quantitative error and / or the feasibility of analysis and the best combination of measurement lines obtained by the measurement line evaluation mechanism on a display.

[0019] In addition, the measurement line evaluation mechanism first calculates the estimated measurement intensity for all the established measurement lines by theoretical intensity calculation and device sensitivity based on the composition and / or thickness specified for the above-mentioned film, and then, based on all the measurement lines that can measure the above-mentioned intensity, a combination of measurement lines for obtaining the quantitative value of the composition and / or thickness of the above-mentioned film is prepared. Then, for each combination of the measurement lines, the estimated measurement intensity of only one measurement line in the group of the estimated measurement intensity of the measurement lines included in the combination is changed by a specified amount, and the step of obtaining the quantitative value of the composition and / or thickness of the above-mentioned film after the estimated measurement intensity is changed by the fundamental parameter method is repeated. Thereafter, based on the obtained quantitative value and the above-mentioned specified composition and / or thickness, the possibility of the estimation and / or analysis of the above-mentioned quantitative error and the selection of the best combination of measurement lines are performed.

[0020] In the fluorescent X-ray analysis device of the second scheme, all measurement lines whose intensities can be measured are used according to the composition and / or thickness specified for the thin film. The measurement intensity is estimated by theoretical intensity calculation and device sensitivity calculation, and a combination of measurement lines for obtaining the quantitative value of the composition and / or thickness of the above-mentioned thin film is prepared. For each combination of the measurement lines, the estimated measurement intensity of only one measurement line is changed by a specified amount. In such a manner as to change the measurement line whose estimated measurement intensity is changed, the step of obtaining the quantitative value of the composition and / or thickness of the above-mentioned thin film after the estimated measurement intensity is changed by the fundamental parameter method is repeated. Based on the above-mentioned quantitative value that has been obtained and the above-mentioned specified composition and / or thickness, the feasibility of the estimation and / or analysis of the above-mentioned quantitative error and the selection of the best combination of measurement lines are performed.

[0021] That is, since the intensity of each measurement line depends largely on the composition and thickness of the film, not only is the quantitative error estimated and / or the feasibility of the analysis determined, but also the optimal combination of measurement lines is selected. Therefore, even when analyzing both the composition and thickness of each layer of the film and the same element is contained in different layers, the appropriate measurement line is automatically selected, allowing correct analysis.

[0022] Any combination of at least two structures disclosed in the claims and / or the specification and / or the drawings is included in the present invention. In particular, any combination of two or more of the claims in the claims is also included in the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are used for simple illustration and description and should not be used to limit the scope of the present invention. The scope of the present invention is determined by the appended claims. In the drawings, the same component number in multiple drawings represents the same or corresponding part.

[0024] Figure 1 Schematic diagram showing a fluorescent X-ray analysis device according to the first and second embodiments of the present invention;

[0025] Figure 2 This is a flowchart showing the operation of the fluorescent X-ray analysis device according to the first embodiment;

[0026] Figure 3 This is a flowchart showing the operation of the fluorescent X-ray analyzer according to the second embodiment. DETAILED DESCRIPTION

[0027] Next, the device according to the first embodiment of the present invention will be described with reference to the accompanying drawings. Figure 1 As shown, the device is a fluorescent X-ray analysis device as follows, in which a sample 3 is irradiated with a primary X-ray 2 from an X-ray source 1 such as an X-ray tube, and the sample 3 is formed by forming a single-layer or multi-layer thin film on a substrate or is formed separately, and the intensity of the generated secondary X-ray 4 is measured by a detection mechanism 9, and based on the measured intensity, a quantitative value of the composition and / or thickness of the above-mentioned thin film is obtained by a basic parameter method (hereinafter also referred to as the "FP method"). The fluorescent X-ray analysis device includes: a measurement line evaluation mechanism 23, which estimates the quantitative error and / or determines the feasibility of the analysis caused by the measurement line 4 as the secondary X-ray whose intensity is to be measured; and a display control mechanism 22, which displays the quantitative error and / or the feasibility of the analysis obtained by the measurement line evaluation mechanism 23 on a display 16 such as a liquid crystal display.

[0028] Here, the sample 3 is a so-called thin film sample, such as a steel plate coated with an iron-zinc alloy, which is placed on a sample stand 8. The detection mechanism 9 is composed of a spectroscopic element 5 and a detector 7. The spectroscopic element 5 spectroscopically separates the secondary X-rays 4 such as fluorescent X-rays generated by the sample 3, and the detector 7 measures the intensity of each spectroscopic secondary X-ray 6. In addition, instead of using the spectroscopic element 5, a detector with a high detection energy resolution may be used as the detection mechanism. In addition, the display control mechanism 22 and the measurement line evaluation mechanism 23 are included in the analysis condition preparation mechanism 20.

[0029] The point that the quantitative value of the composition and / or thickness of the thin film is obtained by the FP method based on the measured intensity means that: based on the assumed composition and / or thickness of each thin film constituting the sample 3 (including the case of a single layer), the theoretical intensity of the secondary X-ray 4 generated by the sample 3 excited by the primary X-ray 2 is calculated, and the assumed composition and / or thickness of each thin film is calculated by successively making approximate corrections in a manner consistent with the theoretical intensity and the converted measured intensity obtained by converting the measured intensity for the sample 3 into a theoretical intensity level, thereby obtaining the quantitative value of the composition and / or thickness.

[0030] Specifically, the measurement line evaluation mechanism 23 of the fluorescent X-ray analysis apparatus according to the first embodiment is Figure 2 The operation is performed as shown in the flowchart. First, in step S1, the operator uses an input mechanism (not shown in the figure) provided in the analysis condition preparation mechanism 20 to calculate the estimated measurement intensity IipM1 (symbol M represents the measurement intensity level) for all the measurement lines ip specified in the same manner, based on the composition (content ratio of each component) Wil and / or thickness Til (label 1 represents the specified numerical value) specified for the film i, through theoretical intensity calculation and device sensitivity. The estimated measurement intensity IipM1 is calculated in the following manner: the theoretical intensity IipT1 (symbol T represents the theoretical intensity level) calculated by theoretical calculation for each measurement line ip is divided by the device sensitivity kip, and converted into the measurement intensity level for calculation. In addition, for the device sensitivity kip, a standard sample of a pure substance or the like is measured in advance for each measurement line ip, and the ratio of the theoretical intensity relative to the measurement intensity is obtained, and it is stored in the measurement line evaluation mechanism 23 in advance.

[0031] Next, in step S2, based on the group of estimated measurement intensity IipM2 in which the estimated measurement intensity of only one measurement line in the group of estimated measurement intensity IipM1 calculated in step S1 is changed by a specified amount, the quantitative value Wi2(ip) of the composition of the film after the estimated measurement intensity change and / or the quantitative value Ti2(ip) of the thickness are obtained by the FP method (the reference numeral 2 indicates a value changed relative to a specified value). More specifically, first, the precision Sip of the intensity for each measurement line ip is estimated by the following formula (1):

[0032] Sip=(IipM1 / t) 1 / 2 …(1)

[0033] Here, t represents the measurement time (seconds), for example, 40 seconds. Next, only the estimated measurement intensity IipM1 of one measurement line ip in the group of estimated measurement intensities IipM1 calculated in step S1 is added with a predetermined multiple (α times, for example, twice) of the precision Sip by the following formula (2), and the estimated measurement intensity IipM2 is set:

[0034] IipM2=IipM1+α×Sip…(2)

[0035] For other measurement lines ip, the estimated measurement intensity IipM1 is formed as it is by the following formula (3):

[0036] IipM2=IipM1…(3)

[0037] Based on the estimated measurement intensity IipM2 of these formulas (2) and (3), a new group of estimated measurement intensity IipM2 is prepared. Next, based on the new group of estimated measurement intensity IipM2, the quantitative value Wi2(ip) of the composition of the film after the estimated measurement intensity is changed and / or the quantitative value Ti2(ip) of the thickness is obtained by the FP method. In addition, an upper limit value (for example, twice) can be set for the number of repeated calculations of the FP method when the quantitative value is reached. This action is performed in a manner that the estimated measurement intensity of the measurement line ip is changed to IipM1+α×Sip one by one. That is, before changing the measurement line ip for which the estimated measurement intensity IipM1 is changed, the processing of step S2 is repeated until the estimated measurement intensity IipM1 is changed for all the specified measurement lines ip. Since the error of the X-ray intensity of the measurement line is a phenomenon independent of each measurement line, even in the case of changing the estimated measurement intensity of only one measurement line, it still does not lose rationality.

[0038] Next, in step S3, the quantitative value Wi2(ip) of the composition and / or the quantitative value Ti2(ip) of the thickness obtained in step S2 and the above-specified composition Wi1 and / or thickness Til are used to determine whether the quantitative error ΔWi and / or ΔTi can be estimated and / or analyzed. More specifically, first, for each measurement line ip for which the estimated measurement intensity is changed, the difference between the quantitative value Wi2(ip) of the composition after the change and the specified composition Wi1 and / or thickness Til is determined by the following formula (4) and / or (5):

[0039] ΔWi(ip)=Wi2(ip)-Wi1…(4)

[0040] ΔTi(ip)=Ti2(ip)-Ti1…(5)

[0041] Next, as the square root of the average of the squares of the errors expressed by the following equations (6) and / or (7), the quantitative error ΔWi of the composition and / or the quantitative error ΔTi of the thickness taking into account all the specified measurement lines ip are estimated for each film i. Here, n represents the number of measurement lines:

[0042] ΔWi=(∑ipΔWi(ip)2 / n) 1 / 2 …(6)

[0043] ΔTi=(∑ipΔTi(ip) 2 / n) 1 / 2 …(7)

[0044] Instead of estimating the quantitative errors ΔWi and / or ΔTi, or in addition to estimating the quantitative errors ΔWi and / or ΔTi, the feasibility of the analysis of the designated measurement line may be determined by the following equations (8) and / or (9):

[0045] ΔWi / Wi1<Rs…(8)

[0046] ΔTi / Ti1<Rs…(9)

[0047] Here, Rs represents the required relative accuracy, for example, it is always 0.05, and it can be set for each film i. Then, if the composition and / or thickness of all films satisfy equations (8) and / or (9), it is determined that the analysis can be performed. If even one equation is not satisfied, it is determined that the analysis cannot be performed. In addition, the determination of whether the analysis is possible can be performed for each specified measurement line or in the loop of step S2 by the following equations (10) and / or (11):

[0048] ΔWi(ip) / Wi1<Rs…(10)

[0049] ΔTi(ip) / Ti1<Rs…(11)

[0050] In this way, the quantitative errors ΔWi and / or ΔTi obtained by the measurement line evaluation means 23 and / or the feasibility of the analysis are displayed on the display 16 by the display control means 22. As described above, in the fluorescent X-ray analysis apparatus of the first embodiment, since the quantitative errors ΔWi and / or ΔTi are estimated and / or the feasibility of the analysis is determined based on the fact that the intensity of each measurement line ip depends largely on both the composition and thickness of the thin film, and the results are displayed on the display 16, even when both the composition and thickness of each layer of the thin film are analyzed and the same element is contained in different layers, the operator can easily and appropriately select the measurement line based on the displayed results, and can perform correct analysis.

[0051] Next, a fluorescent X-ray analyzer according to a second embodiment of the present invention will be described. Figure 1As shown, the device is a fluorescent X-ray analysis device as follows, in which a sample 3 is irradiated with a primary X-ray 2, and the sample is formed by forming a single layer or multiple layers of a thin film on a substrate or formed separately, and the quantitative value of the composition and / or thickness of the above-mentioned thin film is obtained by the FP method based on the measured intensity of the generated secondary X-ray 4. The device includes: a measurement line evaluation mechanism 33, which estimates the quantitative error and / or determines the feasibility of the analysis and selects the best combination of measurement lines for the analysis of the measurement line 4 of the secondary X-ray whose intensity is to be measured; and a display control mechanism 32, which displays the quantitative error and / or the feasibility of the analysis and the best combination of measurement lines obtained by the measurement line evaluation mechanism 33 on the display 16.

[0052] In the device of the second embodiment, since 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 16 are different from those of the device of the first embodiment, these are described below.

[0053] Specifically, the measurement line evaluation mechanism 33 of the device of the second embodiment is Figure 3 The operation is performed as shown in the flow of . First, in step S1A, based on the composition Wil and / or thickness Til specified for the thin film i in the same manner as in the first embodiment, the measured intensity IipM1 is estimated by theoretical intensity calculation and device sensitivity calculation for all the measurement lines ip whose intensity can be measured, as in the device of the first embodiment. According to the structure of the device used (such as a spectroscopic element), the table of measurement lines of each element constituting the thin film i stored in the measurement line evaluation unit 33 is used to retrieve the measurement line ip whose intensity can be measured. For example, if the sample 3 is an iron-zinc alloy-plated steel plate in which a plating film formed of iron and zinc is formed on a substrate as a steel plate, when the specified composition Wil is the content of iron, zinc is the remaining component, and the substrate is iron, the six measurement lines ip of Zn-Kα, Zn-Kβ, Zn-Lα, Fe-Kα, Fe-Kβ, and Fe-Lα are retrieved.

[0054] Next, in step S2A-1, a combination j of measurement lines ip for obtaining quantitative values ​​of the composition and / or thickness of the thin film is prepared based on all the measurement lines ip retrieved in step S1A. In the above example, since two measurement lines are used to analyze the iron content and thickness of the plated film, 15 combinations are prepared.

[0055] Then, in step S2A-2, for each combination j of the measurement lines ip produced in step S2A-1, the measurement line ip for which the estimated measurement intensity IipM1 is changed is changed according to the group of estimated measurement intensity IipM2 in which the estimated measurement intensity of only one measurement line in the group of estimated measurement intensity IipM1 calculated in step S1A for the measurement lines ip included in the combination j, and the step of obtaining the quantitative value Wi2(ip, j) of the composition and / or the quantitative value Ti2(ip, j) of the thickness of the film after the estimated measurement intensity is changed by the FP method is repeated. That is, the operation of step S2 of the measurement line evaluation mechanism 23 of the apparatus of the first embodiment is performed for all the combinations j of the measurement lines ip produced in step S2A-1.

[0056] Then, in step S3A, the quantitative errors ΔWij and / or ΔTij are estimated, and / or the feasibility of the analysis is judged, and the best combination of measurement lines is selected, based on the quantitative value Wi2(ip, j) of the composition and / or the quantitative value Ti2(ip, j) of the thickness obtained in step S2A-2 and the above-mentioned specified composition Wi1 and / or thickness Ti1. More specifically, first, for all the combinations j of the measurement lines ip obtained in step S2A-1, each of the measurement lines ip for estimating the measurement intensity is changed, and the difference between the quantitative value Wi2(ip, j) of the composition and / or the quantitative value Ti2(ip, j) of the thickness after the change and the specified composition Wi and / or thickness Ti1 is obtained:

[0057] ΔWi(ip,j)=Wi2(ip,j)-Wi1…(12)

[0058] ΔTi(ip,j)=Ti2(ip,j)-Ti1…(13)

[0059] Next, the quantitative error ΔWij of the composition and / or the quantitative error ΔTij of the thickness are estimated for each film i in all the combinations j of the measurement lines ip prepared in step S2A-1 by using the following formula (14) and / or (15). In addition, as mentioned above, n represents the number of measurement lines:

[0060] ΔWij=(ΣipΔWi(ip,j) 2 / n) 1 / 2 …(14)

[0061] ΔTij=(∑ipΔTi(ip,j) 2 / n) 1 / 2 …(15)

[0062] In addition, based on the quantitative error ΔWij of the composition and / or the quantitative error ΔTij of the thickness calculated in this way, for example, for each combination j of the measurement line ip, the quantitative relative error ΔWij / Wi1 of the composition and / or the quantitative relative error ΔTij / Ti1 of the thickness is calculated, and the quantitative relative error with the largest value is taken as the representative quantitative relative error of the combination j. Among all the combinations, the combination with the smallest representative quantitative relative error is selected as the optimal combination of measurement lines.

[0063] Furthermore, for the selected optimal combination of measurement lines, it is also possible to determine whether analysis is feasible using the above-mentioned equations (8) and / or (9).

[0064] In this case as well, if the composition and / or thickness of all the thin films satisfy the formula (8) and / or (9), it is determined that the analysis is possible, and if none of the formulas are satisfied, it is determined that the analysis is not possible. In addition, the determination of whether the analysis is possible is performed for each combination j of the measurement lines ip in step S2A-2 by using the above-mentioned formula (10) and / or (11), and the processing of the combination is terminated at the moment when it is determined that the analysis is not possible, and the processing of the next combination is transferred.

[0065] Thus, the best combination of measurement lines obtained by the measurement line evaluation means 33, the quantitative errors ΔWij and / or ΔTij in the combination j, and / or the feasibility of the analysis in the combination j are displayed on the display 16 by the display control means 32. In the case where analysis is not possible, the layer with an unanalyzable thickness and / or the component with an unanalyzable content and the layer containing the component can also be displayed on the display 16.

[0066] Taking the case of analyzing the iron-zinc alloy layer of an iron-zinc alloy-plated steel plate using the device of the second embodiment as an example, Table 1 shows the results of the calculation of the quantitative error based on the measurement line evaluation mechanism 33. In this example, the specified Fe content is 10.0%, and the specified thickness is 4.3μm. In addition, as mentioned above, there are 6 measurement lines that can measure the intensity, and a combination of 15 measurement lines is made. The change in the estimated measured intensity in the above formula (2) is set to twice the accuracy, and considering various reproducibility, the lower limit of the relative accuracy of the X-ray is set to 0.05%. The "RMS" in Table 1 is the quantitative error (the square root of the average of the squares of the errors) calculated by the above formulas (14) and (15), and "no solution" means that no integrated quantitative value is obtained based on the content and thickness.

[0067] [Table 1]

[0068]

[0069]

[0070] The combination of Zn-Kβ and Zn-Lα, which minimizes the quantitative error RMS respectively estimated for the content and thickness in Table 1, is selected as the optimal measurement line combination by the measurement line evaluation unit 33 and displayed on the display 16 by the display control unit 32.

[0071] As described above, in the fluorescent X-ray analysis apparatus of the second embodiment, since the intensity of each measurement line greatly depends on both the composition and thickness of the thin film, not only the quantitative error is estimated and / or the feasibility of the analysis is determined, but also the optimal combination of measurement lines is selected. Therefore, even when both the composition and thickness of each layer of the thin film are analyzed and the same element is contained in different layers, the selection of the appropriate measurement line is still automatic, and correct analysis can be performed.

[0072] As described above, preferred embodiments have been described with reference to the accompanying drawings, but, if a person skilled in the art reads this specification, various changes and modifications will be easily thought of within the obvious scope. Thus, such changes and modifications are interpreted as modes within the scope of the present invention determined according to the claims.

[0073] Description of the label:

[0074] Reference numeral 2 indicates an X-ray;

[0075] Reference numeral 3 indicates a specimen;

[0076] Reference numeral 4 represents secondary X-ray (measurement line);

[0077] Reference numeral 16 denotes a display;

[0078] Reference numerals 22 and 32 denote display control mechanisms;

[0079] Reference numerals 23 and 33 denote measurement line evaluation mechanisms.

Claims

1. A fluorescent X-ray analysis device, in which a sample is irradiated with primary X-rays, and quantitative values ​​of the composition and thickness of the following thin films are obtained by a fundamental parameter method based on the measured intensity of the generated secondary X-rays, wherein the sample is formed by forming a multi-layer thin film without a substrate, by forming a single-layer thin film on a substrate, or by forming a multi-layer thin film on a substrate, The fluorescent X-ray analysis device comprises: a measurement line evaluation unit that estimates a quantitative error and / or determines whether the analysis is feasible or not, with respect to the analysis of the measurement line of the secondary X-ray whose intensity is to be measured; display control means for displaying the quantitative error obtained by the measurement line evaluation means and / or the feasibility of the analysis on a display, The measurement line evaluation means estimates the measurement intensity for all the specified measurement lines by theoretical intensity calculation and device sensitivity calculation based on the composition and thickness specified for the film. The method comprises the following steps: repeating the step of obtaining the quantitative value of the composition and thickness of the film after the estimated measurement intensity is changed by a fundamental parameter method in a manner that changes the measurement line of the estimated measurement intensity according to the estimated measurement intensity group in which the estimated measurement intensity of only one measurement line in the group of estimated measurement intensity is changed by a predetermined amount; Based on the obtained quantitative value and the above-specified composition and thickness, the feasibility of the above-mentioned estimation of the quantitative error and / or analysis is determined.

2. The fluorescent X-ray analysis device according to claim 1, wherein: The measurement line evaluation mechanism further selects an optimal combination of measurement lines; The display control means further displays the best combination of measurement lines on the display. The measurement line evaluation means estimates the measured strength for all the measurement lines whose strength can be measured by theoretical strength calculation and device sensitivity calculation based on the composition and thickness specified for the film. A combination of measurement lines for obtaining quantitative values ​​of the composition and thickness of the film is prepared based on all measurement lines capable of measuring the strength. for each combination of the measurement lines, the step of repeatedly performing the step of obtaining the quantitative values ​​of the composition and thickness of the film after the estimated measurement intensity is changed by the fundamental parameter method in such a manner that the measurement line of the estimated measurement intensity is changed by a predetermined amount based on the estimated measurement intensity of only one measurement line in the group of the estimated measurement intensity of the measurement lines included in the combination, Based on the obtained quantitative value and the specified composition and thickness, the feasibility of the estimation and / or analysis of the quantitative error and the selection of the optimal combination of measurement lines are determined.

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