JP3108660B2 - X-ray analysis method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an X-ray analysis method and apparatus for determining the content of each component in a sample to be analyzed based on the measured intensity of X-ray fluorescence from the sample to be analyzed. The present invention relates to an X-ray analysis method and apparatus capable of correction.

[0002]

2. Description of the Related Art Conventionally, there is a so-called calibration curve method as one of X-ray analysis methods for obtaining the content of each component in a sample to be analyzed based on the measured intensity of fluorescent X-rays from the sample to be analyzed. In this calibration curve method, primary X-rays are radiated to a plurality of standard samples having different compositions, and the intensity of fluorescent X-rays generated from each component in the standard samples is measured. Is previously determined as a calibration curve for each component.
Then, the sample to be analyzed is irradiated with primary X-rays, and the intensity of fluorescent X-rays generated from each component in the sample to be analyzed is measured.
The calibration curve is applied to each measurement intensity to determine the content of each component in the sample to be analyzed.

Here, for example, there is a case where the Ni-Kβ1 line overlaps with the fluorescent X-ray Cu-Kα line to be measured at a part of the wavelength as an interference line. Then, in order to remove the influence of the interference line, a calibration curve shown in the following equation (1) corrected using the linear expression γ _ij W _j relating to the content W _j of each component j that generates the interference line is used. , The content W _i of each component i in the sample to be analyzed is determined.

[0004] _{W i = (a i I i} 2 + b i I i + c i) (1 + Σα ij W j) -Σγ ij W j ... (1)

Here, I _i is the intensity measured as each fluorescent X-ray, a _i , b _i , and c _i are calibration curve constants, Σα _ij W _j is a so-called matrix correction term for coexisting elements, and α _ij is a matrix The correction coefficient, γ _ij, is an overlap correction coefficient. a
_i , b _i , c _i , α _ij , γ _ij are obtained from measurements on a plurality of different standard samples whose compositions are known. The reason why the overlap correction term is set to γ _ij W _j is that the influence of the interference of the interference component j on the fluorescent X-ray to be measured is determined by the interference component j.
On the assumption that it is proportional to the content ratio W _j of.

[0006]

However, this premise is not always correct, and the overlap correction cannot be made sufficiently accurately. In addition, the measured intensity I of the interference line is included in the overlap correction term.
with _j, there is a method of the gamma _ij I _j, configuration and equipment, the degree of overlap to the fluorescent X-ray to be measured of the disturbing lines, and if not assayed interference line, if can not be measured, Overlap correction cannot be performed.

The present invention has been made in view of the above-mentioned conventional problems, and an X-ray analysis method for determining the content of each component in a sample to be analyzed based on the measured intensity of X-ray fluorescence from the sample to be analyzed. It is an object of the present invention to provide an X-ray analysis method and apparatus capable of performing more accurate overlap correction.

[0008]

[0009]

[0010]

[MEANS FOR SOLVING THE PROBLEMS] To achieve the above object
According to the method of claim 1, the X-ray analysis method is for determining at least one of the thickness and the content of each component in the sample to be analyzed based on the measured intensity of the fluorescent X-rays from the sample to be analyzed. A fluorescent X-ray having a wavelength band that at least partially overlaps a wavelength band of the fluorescent X-ray to be used as the interference line, and the interference line calculated by assuming at least one of the thickness and the content of each component in the sample to be analyzed. The measured intensity is corrected using the theoretical intensity of

According to the method of the first aspect , since the measured intensity is corrected using the theoretical intensity of the interference line, more accurate overlap correction can be performed even when the interference line cannot be measured.

[0012] In a second aspect of the method, the analysis based on the measured intensity of the fluorescent X-rays from the target sample, determine at least one of the content of the thickness of the or each component in the analysis sample X
In the X-ray analysis method, the fluorescent X-ray having a wavelength band at least partially overlapping the wavelength band of the fluorescent X-ray to be measured.
The theoretical intensity of the interference line calculated assuming at least one of the thickness and the content of each component in the sample to be analyzed or the theory of the fluorescent X-ray having the same series as the interference line and having a similar wavelength. The intensity is used to correct the measured intensity.

According to the method of the second aspect, the measured intensity is corrected using the theoretical intensity of the disturbing line or the theoretical intensity of the fluorescent X-ray having the same system and a wavelength close to the disturbing line, so that the disturbing line cannot be measured. In some cases, for example, even when the theoretical strength of the disturbing line cannot be calculated, more accurate overlap correction can be performed.

[0014]

[0015]

According to a third aspect of the present invention, first, a sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, and the intensity of fluorescent X-rays generated from the sample are measured. Detection means. Further, a primary X-ray is irradiated from the X-ray source to the sample to be analyzed, and the intensity of the fluorescent X-ray generated from each component in the sample to be analyzed is measured by the detecting means, and the measured intensity is stored. And calculating means for obtaining at least one of the thickness and the content of each component in the sample to be analyzed based on the measured intensity stored in the measuring means. Here, the calculating means sets the fluorescent X-ray having a wavelength band at least partially overlapping with the wavelength band of the fluorescent X-ray to be measured as the obstruction line, and calculates the thickness or the content of each component in the sample to be analyzed. The measured intensity is corrected using a theoretical intensity of the disturbing line calculated on the assumption of at least one. According to the device of the third aspect , the same operation and effect as those of the method of the first aspect are obtained.

According to a fourth aspect of the present invention, first, a sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, and the intensity of fluorescent X-rays generated from the sample are measured. Detection means. Further, a primary X-ray is irradiated from the X-ray source to the sample to be analyzed, and the intensity of the fluorescent X-ray generated from each component in the sample to be analyzed is measured by the detecting means, and the measured intensity is stored. And calculating means for obtaining at least one of the thickness and the content of each component in the sample to be analyzed based on the measured intensity stored in the measuring means. Here, the calculating means sets the fluorescent X-ray having a wavelength band at least partially overlapping with the wavelength band of the fluorescent X-ray to be measured as an obstruction line, and calculates the thickness or the content of each component in the sample to be analyzed. The measured intensity is corrected using the theoretical intensity of the disturbing line calculated on the assumption of at least one of the disturbing lines or the theoretical intensity of fluorescent X-rays having a wavelength close to the same series as the disturbing line. According to the device of the fourth aspect , the same operation and effect as those of the method of the second aspect are obtained.

[0018]

DETAILED DESCRIPTION OF THE INVENTION First, the first, second embodiment of the present invention
A basic method partially common to the method of the embodiment will be described. First, an apparatus used in this method will be described with reference to FIG. The apparatus first includes a sample stage 8 on which the samples 3 and 13 are fixed, an X-ray source 1 for irradiating the samples 3 and 13 with primary X-rays 2, and a fluorescent X-ray 6 generated from the samples 3 and 13. Detecting means 10 for measuring the intensity. The detection means 10 includes a spectroscope 5 for separating the secondary X-rays 4 generated from the samples 3 and 13 and a detector 7 for measuring the intensity of each fluorescent X-ray 6 separated by the spectrometer 5. Further, this apparatus is provided with a control means 15 including the following calibration curve storage means 11, measurement means 12, and calibration curve application means 14.

The calibration curve storage means 11 stores the intensity of the fluorescent X-ray 6 generated from each component in the standard sample 3 when the primary X-ray 2 is irradiated for a plurality of standard samples 3 having different compositions. The correlation between the intensity and the content of each component in the standard sample 3, which is obtained in advance, is stored as a calibration curve for each component. The measurement means 12 irradiates the sample 13 to be analyzed with primary X-rays 2 from the X-ray source 1, and emits the fluorescent X-rays generated from each component in the sample 13.
The intensity of the line 6 is measured by the detecting means 10 and the measured intensity is stored. The calibration curve application unit 14 applies the calibration curve stored in the calibration curve storage unit 11 to the measurement intensity stored in the measurement unit 12 to determine the content of each component in the sample 13 to be analyzed. Here, the calibration curve stored in the calibration curve storage means 11 is a fluorescence X-ray having a wavelength band that at least partially overlaps the wavelength band of the fluorescent X-ray to be measured, and the interference lines are defined as the interference lines. This is corrected using a quadratic expression relating to the content of each component generated.

Using this device, in this basic method:
The content of each component in the analysis target sample 13 is determined as follows. The case where the analysis target sample 13 is a Ni—Cr—Fe alloy and the content of copper is determined will be described with reference to the drawings. The Cu-Kα line is used for the analysis of copper, and the Ni-Kβ1 line overlaps with the Cu-Kα line as an interference line. The inventors examined in detail the correlation between ΔCu, which expresses the influence of the Ni-Kβ1 line on the Cu-Kα line in terms of the copper content, and the nickel content, and obtained the results shown in FIG. Obtained. According to the prior art, the influence ΔCu of the interference of the interference line Ni-Kβ1 with the fluorescent X-ray Cu-Kα line to be measured due to the interference component nickel ( _j ) is proportional to the nickel content (W _j ). Is not necessarily correct, and is not satisfied particularly when the nickel content is high. Therefore, with the conventional technique in which the overlap correction term is γ _ij W _j based on this premise, the overlap correction cannot be performed sufficiently accurately.

Here, the inventors have found that the correlation shown in FIG. 3 is expressed by the following equation (2).

ΔCu = 3.42 × 10 ⁻⁵ W _Ni ² −1.18 W _Ni +0.0529 (2)

[0023] Therefore, by correcting the calibration curve using a quadratic equation regarding content W _j of interfering components j, it is more accurate overlap correction. Therefore, in this basic method, FIG.
As shown in FIG.
Is fixed to a sample stage 8, primary X-rays 2 are radiated from an X-ray source 1, and secondary X-rays 4 generated from a standard sample 3 are spectrally separated by a spectroscope 5. The intensity of the fluorescent X-rays 6 from each component is measured by the detector 7, and the correlation between the measured intensity I _i and the content W _i of each component i in the standard sample 3 is defined as a calibration curve for each component i. It is obtained in advance and stored in the calibration curve storage means 11, and the following equation (3) is used as the calibration curve.

[0024] _{W i = (a i I i} 2 + b i I i + c i) (1 + Σα ij W j) -Σ (γ 1ij W j 2 + γ 2ij W j + γ 3ij) ... (3)

Here, the meanings of the symbols are the same as in the equation (1).
γ _1ij , γ _2ij , γ _3ij are overlap correction coefficients,
It is obtained by regression calculation from the measurement of the standard sample 3 together with a _i , b _i , c _i , and α _ij . That is, this basic
In this method, the fluorescent X-ray 6 having a wavelength band at least partially overlapping the wavelength band of the fluorescent X-ray 6 to be measured is regarded as an obstruction line, and the content W _j of each component j that generates the obstructive line is determined. The calibration curve is corrected using the quadratic equation.
Next, the measuring means 12 assigns 1 to the sample 13 to be analyzed.
The next X-ray 2 is irradiated to measure and store the intensity of the fluorescent X-ray 6 generated from each component i in the sample 13 to be analyzed. Then, the a calibration curve application means 14 applies a calibration curve (3) to each measured intensity I _i, determine the content of W _i of each component i in the analysis sample 13.

In accordance with the present basic method, with reference to the more practical, because to correct the calibration curve using a quadratic equation regarding content W _j of interfering components j, it is more accurate overlap correction.

Next, the method according to the first embodiment of the present invention will be described. First, an apparatus used in this method will be described with reference to FIG. This apparatus is different from the apparatus used in the basic method in that the control means 17 does not include the calibration curve storage means 11 and the calibration curve application means 14 and the calculation means 1
6 whose calculation means 16 determines the fluorescence X to be measured.
A fluorescent X-ray having a wavelength band that at least partially overlaps with the wavelength band of the line is defined as a disturbing line, and is the same as the theoretical intensity of the disturbing line calculated assuming the content of each component in the sample to be analyzed or the disturbing line. The difference is that the measurement intensity is corrected using the theoretical intensity of fluorescent X-rays having similar wavelengths in the series, and the other points are the same. In the apparatus used in the method of the first embodiment, the calculation means 16 has a difference in the method of correcting the measured intensity, but the calibration curve storage means 11 and the calibration curve application means 1 in the apparatus used in the basic method.
4 can be said to be equivalent.

Using this apparatus, in the method of the first embodiment, the content of each component in the sample 13 to be analyzed is obtained as follows. Again, the sample 13 to be analyzed is Ni-C
In the case of obtaining the copper content in an r-Fe alloy,
This will be described in comparison with the related art. First, as a conventional calibration curve method, the measured intensity I _j of the interference line is used for the overlap correction term, and γ
a _ij I _j, there is a method using a calibration curve shown in the following equation (4).

[0029] _{W i = (a i I i} 2 + b i I i + c i) (1 + Σα ij W j) -Σγ ij I j ... (4)

The calibration curve shown in equation (4) is expressed as Ni, Cr, F
For all elements such as e, the measured intensities I _i and I _j are substituted into the right side of the equation (4), and the final analysis value W _i is obtained by successive repetitive calculations. Here, as described above, the Cu-Kα line is used for the analysis of copper, and the Ni-Kβ1 line overlaps with the Cu-Kα line as an interference line. However, since Ni-Kα radiation is usually used for nickel analysis, the intensity I _j of the Ni-Kβ1 radiation is not measured, and the calibration curve of the equation (4) cannot be used. It is conceivable to substitute the measured intensity of the Ni -Keiarufa line as the measured intensity I _j of the disturbing lines, Ni -Kα
The X-ray intensity ratio between the X-ray and the Ni-Kβ1 line is not constant. In particular, when the sample contains an element such as cobalt having an absorption edge between the wavelengths of both lines, this intensity ratio greatly changes.
Therefore, it is substituted by the measured intensity I _j of the disturbing lines in the measured intensity of Ni -Keiarufa line can not accurately overlap correction.

Therefore, in the method of the first embodiment, in the calibration curve method, the fluorescent X-ray to be measured, for example, Cu-Kα
Fluorescent X-rays having a wavelength band at least partially overlapping with the wavelength band of the X-rays, for example, Ni-Kβ1 rays, are regarded as disturbing lines, and the theoretical intensity ^{T of the} disturbing lines is determined by the composition (content of each component) for each of the above-described successive repetition calculations. I _j is calculated, and the measured intensity I _i of the fluorescent X-rays 6 generated from the samples 3 and 13 is corrected using the calculated theoretical intensity ^T I _j of the interference line. That is, the calculation means 16 uses the calibration curves shown in the following equations (5) and (6).

W _i = (a _i ^c I _i ² + b _i ^c I _i + c _i ) (1 + Σα _ij W _j ) (5)

^C I _i = I _i −Σγ _ij ^T I _j (6)

Here, ^c I _i is the theoretical intensity ^T I of the disturbance line.
with _j, a correction intensity overlap was corrected measured intensity I _i. From the measurement and the theoretical intensity calculation for the standard sample 3, I _i and ^T _Ij are obtained, and a _i , b _i , c _i , and c _i are obtained by multiple regression calculation of the expression (6) substituted into the expression (5).
α _ij and γ _ij are obtained. The calculation of the theoretical strength based on the composition is performed by a so-called fundamental parameter method (the details will be described later). Next, calculation means 1
6 applies the calibration curves (5) and (6) to the measured intensity I _i of the analysis target sample 13 measured and stored by the measuring means 12 and the calculated theoretically calculated intensity ^T I _j , and The content W _i of each component i in the sample 13 is determined. Measurements for samples 3 and 13 were made using FIG.
This is performed in the same manner as described in the basic method.

According to the method of the first embodiment, the measured intensity I _i is corrected using the theoretical intensity ^T I _j of the disturbing line. Therefore, when the disturbing line is not measured as in the case of the above-mentioned Ni-Kβ 1 line, Even when the interference line completely overlaps the fluorescent X-ray to be measured and cannot be measured, more accurate overlap correction can be performed.

Note that the theoretical intensity ^{T of the} interference line is included in the overlap correction term.
Using I _j, and γ _ij ^T I _j, there is a method of using a calibration curve shown in the following equation (7).

[0037] _{W i = (a i I i} 2 + b i I i + c i) (1 + Σα ij W j) -Σγ ij T I j ... (7)

Next, a method according to a second embodiment of the present invention will be described. The apparatus used in the method of the second embodiment differs from the apparatus used in the method of the first embodiment shown in FIG. 2 only in the content of the calculation in the calculating means 16 as described below. Is omitted. Second
The method according to the embodiment belongs to a fundamental parameter method (hereinafter, referred to as an FP method), not to a basic method , a calibration curve method using a calibration curve as in the method of the first embodiment. The FP method means that the primary X-ray 2
And intensity ^S I _i obtained by converting the measured intensities I _i of the fluorescent X-ray 6 theoretical strength scale for each content element generated by irradiating each were calculated assuming a content of W _i from the elements of the analysis sample 13 using X-ray fluorescence of elements contained and theoretical strength ^T I _i,
The content W of the assumed element is set so that the two intensities match.
_This is a fluorescent X-ray analysis method in which _i is successively and approximately corrected to calculate an element content W _i in the sample 13 to be analyzed.

Further, analysis sample 13, so-called thin film sample, that is, when a thin film formed by vapor deposition or the like on the substrate, similarly to determine the content of W _i, X-ray fluorescence of the elements contained 6 in terms of the theoretical intensity scale the measured intensity I _i of
Intensities ^S I _i and the theoretical intensity of the fluorescent X-ray of the containing elements were calculated assuming a thickness T in the analysis sample 13 ^T I
_i , the assumed thickness T is successively and approximately corrected and calculated so that the two intensities coincide with each other.
Can be calculated. Further, in the case where both the thickness T and the content W _i of the element are unknown in the sample 13 to be analyzed, which is a thin film sample, the theoretical intensity ^T I of the fluorescent X-ray of each content element calculated on the assumption of both the thickness T and the content W _i and _i, the measured intensity I _i of the fluorescent X-ray 6 of the elements contained in terms of the theoretical intensity scale
Strength by using the ^S I _i, so that both strength match, the assumed thickness T and the element content ratio W _i by successive approximation modified calculate the thickness T of the analysis sample 13 and The content W _{i of the} element can be calculated. In the case of a so-called bulk sample which is not a thin film, the thickness is infinite in X-ray, and only the element content W _i is required.

In the method of the second embodiment, in the FP method, fluorescent X-rays having a wavelength band at least partially overlapping the wavelength band of the fluorescent X-rays to be measured are regarded as interference lines, and the theory of the interference lines The measured intensity I _i is corrected using the intensity ^T I _j . That is, instead of the measurement intensity I _i , the overlap correction intensity ^c I _i of the equation (6) shown in the method of the first embodiment is used. In the method of the second embodiment, the overlap correction coefficient γ _ij and the like are obtained as follows. First, the following equation (8) is assumed.

^T I _i = a _i ^c I _i ² + b _i ^c I _i + c _i (8)

Then, the measurement of the standard sample 3 and
From the theoretical strength calculation, I_i,^TI_i, ^TI_jAnd the expression
By the multiple regression calculation of the equation obtained by substituting (6) into the equation (8),
a_i, B_i, C_i, Γ_ijIs required.

The whole procedure of the method according to the second embodiment will be described below, taking as an example a case where both the thickness T and the content W _i of the element are obtained in the sample 13 to be analyzed, which is a thin film sample. First, the measuring unit 12 assigns 1
The next X-ray 2 is irradiated to measure and store the intensity I _i of the fluorescent X-ray 6 generated from each component i in the sample 13 to be analyzed.
Next, the initial thickness T ⁽⁰⁾ and the content W _i ^{(0) of} each component, which are assumed in advance, are read by the calculating unit 16, and the calculating unit 16 calculates the thickness T and the component Content W _i
Until it converges to a predetermined range.

To explain the n-th calculation, first,
The thickness T ⁽ⁿ⁾ assumed for the n-th time and the content W _i ^{(n) of} each component
Is substituted into a well-known theoretical intensity calculation formula to calculate an n-th theoretical X-ray fluorescence intensity ^T I _i ⁽ⁿ⁾ of each contained element. Here, a fluorescent X-ray having a wavelength band at least partially overlapping with the fluorescent X-ray to be measured is regarded as a disturbing line, and the theoretical intensity ^T I _j ^{(n) of the nth} disturbing line is similarly calculated. next,
The measured intensity I _i is corrected using the theoretical intensity ^T I _j ⁽ⁿ⁾ of this disturbing line. Specifically, the measured intensity I _i and the theoretical intensity ^T I _j ⁽ⁿ⁾ of the interference line are substituted into the equation (6), and the n-th overlap correction intensity ^c I _i ⁽ⁿ⁾ is obtained. Then, the n-th overlap correction intensity ^c I _i ⁽ⁿ⁾ is converted into a theoretical intensity scale.
Intensities ^cS I _i ⁽ⁿ⁾ (in terms of the left-hand side of ^cS I _i of formula (8)
And the theoretical intensity ^T I _i ⁽ⁿ⁾ is compared with n +
First thickness T ^{(n + 1)} and content W _i ^{(n + 1)} of each component are obtained. Specifically, ΔT and ΔW _i are obtained from the following equations (9) and (10), respectively, and the following equations (11) and (1) are respectively obtained.
Substitute in 2).

^CS I _i ⁽ⁿ⁾ = ^T I _i ⁽ⁿ⁾ + ΔT × (d ^T I _i ⁽ⁿ⁾ / dT) (9)

^CS I _i ⁽ⁿ⁾ = ^T I _i ⁽ⁿ⁾ + ΔW _i × (d ^T I _i ⁽ⁿ⁾ / dW _i ) (10)

T ^{(n + 1)} = T ⁽ⁿ⁾ + ΔT (11)

[0048] ^{_{W i (n + 1) =}} W i (n) + Δ W i ... (12)

Note that (d ^T I _i ⁽ⁿ⁾ / dT) in equation (9)
Is the theoretical intensity ^T I _i when the thickness is changed by dT.
^The amount of change of ⁽ⁿ⁾ is ^expressed by (d ^T I _i ⁽ⁿ⁾ / dW _{i in} equation (10).
T) is the amount of change in the theoretical intensity ^T I _i ⁽ⁿ⁾ when the content W _i of each component is changed by dW _i .

When the following expressions (13) and (14) are satisfied, the thickness T ^{(n + 1)} and the content W _i ^{(n + 1) of} each component are obtained.
Are converged, and if they are not satisfied,
The calculation after the calculation of the theoretical intensity ^T I _i ^{(n + 1)} is repeated. Note that α _T and α _W in Expressions (13) and (14) are predetermined convergence determination values.

| T ^{(n + 1)} / T ⁽ⁿ⁾ −1.0 | <α _T (13)

| W _i ^{(n + 1)} / W _i ⁽ⁿ⁾ −1.0 | <α _W (14)

When a plurality of sets of thickness and the content of each component are to be obtained, for example, when the object to be analyzed is a multilayer film, the above equation becomes a plurality of sets of simultaneous equations.

According to the method of the second embodiment, the measured intensity I _i is corrected using the theoretical intensity ^T I _j of the disturbing line. Therefore, even when the disturbing line cannot be measured, the overlap correction can be performed more accurately. Can be.

In the methods of the first and second embodiments, for example, the fluorescent X-ray to be measured is a P-Kα ray, and a constant for calculating the theoretical intensity for the interference line Mo-Ll is prepared. May not be. In such a case, the calculating unit 16, using the theoretical strength ^T I _j of the fluorescent X-ray for example Mo -Eruarufa lines adjacent in wavelength interference lines Mo -Ll line the same sequence, correct the measured intensity I _i I do. In this case, the measurement intensity is corrected using the theoretical intensity of the interference line or the theoretical intensity of the fluorescent X-ray having the same wavelength as that of the interference line, so that the interference line cannot be measured. If the theoretical strength of the line cannot be calculated,
More accurate overlap correction can be performed.

[0056]

[0057]

As described in detail above , according to the first or third aspect of the present invention, since the measured intensity is corrected using the theoretical intensity of the disturbing line, the disturbing line cannot be measured. In such cases, more accurate overlap correction can be performed.

[0058] According to the invention of claim 2 or 4,
The measurement intensity is corrected using the theoretical intensity of the disturbing line or the theoretical intensity of fluorescent X-rays that are in the same series as the disturbing line and have a similar wavelength. Can not be calculated, more accurate overlap correction can be performed.

[Brief description of the drawings]

FIG. 1 is partially the same as the method of the first and second embodiments of the present invention.
It is a front view which shows the apparatus used for the basic method of passing .

FIG. 2 is a front view showing an apparatus used for the X-ray analysis method according to the first or second embodiment of the present invention.

FIG. 3 is a diagram showing the correlation between ΔCu, which represents the influence of the interference of the interference line Ni-Kβ1 on the measurement line Cu-Kα by the copper content, and the nickel content.

[Explanation of symbols]

1: X-ray source, 2: primary X-ray, 3: standard sample, 6: fluorescent X
Line 8, sample stage, 10 detection means, 11 calibration curve storage means, 12 measurement means, 13 sample to be analyzed, 14 calibration curve application means, 16 calculation means.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G01N 23/22-23/227

Claims (4)

(57) [Claims] 1. A sample to be analyzed is irradiated with primary X-rays, the intensity of fluorescent X-rays generated from each component in the sample to be analyzed is measured, and the thickness of the sample to be analyzed is determined based on the measured intensities. Alternatively, in the X-ray analysis method for determining at least one of the content rates of the respective components, a fluorescent X-ray having a wavelength band at least partially overlapping with the wavelength band of the fluorescent X-ray to be measured is regarded as an interference line, An X-ray analysis method, wherein the measured intensity is corrected using a theoretical intensity of the disturbing line calculated assuming at least one of a thickness and a content of each component. 2. A sample to be analyzed is irradiated with primary X-rays, the intensity of fluorescent X-rays generated from each component in the sample to be analyzed is measured, and the thickness of the sample to be analyzed is determined based on the measured intensities. Alternatively, in the X-ray analysis method for determining at least one of the content rates of the respective components, a fluorescent X-ray having a wavelength band at least partially overlapping with the wavelength band of the fluorescent X-ray to be measured is regarded as an interference line, The measured intensity is corrected using the theoretical intensity of the disturbing line calculated assuming at least one of the thickness and the content of each component or the theoretical intensity of the fluorescent X-ray having a wavelength close to the same series as the disturbing line. X-ray analysis method. 3. A sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, detection means for measuring the intensity of fluorescent X-rays generated from the sample, Irradiating primary X-rays from an X-ray source,
A measuring means for causing the detecting means to measure the intensity of the fluorescent X-rays generated from each component in the sample to be analyzed, and storing the measured intensities, based on the measured intensity stored in the measuring means, Calculating means for determining at least one of the thickness and the content of each component, wherein the calculating means obstructs the fluorescent X-rays having a wavelength band at least partially overlapping the wavelength band of the fluorescent X-rays to be measured. An X-ray analyzer that corrects the measured intensity using a theoretical intensity of the disturbing line calculated assuming at least one of a thickness and a content of each component in a sample to be analyzed. 4. A sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, detection means for measuring the intensity of fluorescent X-rays generated from the sample, Irradiating primary X-rays from an X-ray source,
A measuring means for causing the detecting means to measure the intensity of the fluorescent X-rays generated from each component in the sample to be analyzed, and storing the measured intensities, based on the measured intensity stored in the measuring means, Calculating means for determining at least one of the thickness and the content of each component, wherein the calculating means obstructs the fluorescent X-rays having a wavelength band at least partially overlapping the wavelength band of the fluorescent X-rays to be measured. The theoretical intensity of the disturbing line calculated assuming at least one of the thickness and the content of each component in the sample to be analyzed or the theoretical intensity of the fluorescent X-ray having a wavelength close to the same series as the disturbing line is used. An X-ray analyzer for correcting the measured intensity by using the X-ray analyzer.