JP2002181740A - Method and apparatus for semi quantitative analysis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus for semi quantitative analysis whereby the semi quantitative analysis can be easily and correctly carried out even for a sample including elements to be analyzed with the use of an L line or an M line. SOLUTION: In the case of the sample S detected on the basis of the measured result of a measuring means 22 to include a fixed amount or more of elements to be analyzed with the use of the L line or M line, a second re- measurement is carried out on the basis of second sensitivity data related to an apparatus sensitivity when high-resolution slits 5B and 7B are used, and a semi quantitative value is automatically obtained. Therefore, even for the sample S including elements to be analyzed with the use of the L line or M line, the semi quantitative analysis can be executed easily and correctly.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semi-quantitative analysis method and a semi-quantitative analysis method for obtaining a semi-quantitative value which is an approximate calculated value of a sample. Here, the semi-quantitative value refers to an approximate value of the content of each component in the sample, the thickness of the sample, or the attached amount of each component.

[0002]

2. Description of the Related Art Conventionally, there has been known a fluorescent X-ray analyzer which irradiates a sample with X-rays, measures the intensity of fluorescent X-rays generated from each component in the sample, and quantitatively analyzes the sample. This apparatus includes, for example, an X-ray tube that irradiates a sample with X-rays, a solar (resolution) slit that converts fluorescent X-rays generated from the sample into parallel light, a spectral crystal that splits fluorescent X-rays, and a spectral X-ray that has been split. A detector for detecting the intensity of the light.

Here, in order to improve the accuracy of the quantitative analysis, a so-called semi-quantitative method is used to obtain an approximate value of the content of each component (element) in the sample before performing the quantitative analysis. Analysis may be performed. The semi-quantitative analysis method includes, for example, a fundamental parameter method (hereinafter, referred to as an FP method). In the FP method, the element content is obtained from the appropriately set initial value of the element content by successive approximation convergence calculation using theoretical intensity based on the result of the qualitative analysis.

[0004]

However, in the conventional semi-quantitative analysis method, when the sample is a mesh metal or a material of a magneto-optical disk, the fluorescent X-rays generated from each component in the sample by a standard resolution slit. Because the strength was measured,
A plurality of elements to be analyzed using L-rays or M-rays in a sample,
For example, when a rare earth element ( ₅₇ La to ₇₁ Lu) or barium is mixed and contained in a certain amount, many L-series X-ray spectra are generated. Sometimes it was not detected correctly.
In this case, since the operator judged whether or not to perform re-measurement with the high-resolution slit based on the analysis result, the judgment was complicated, and there were individual differences in the judgment, so that accurate semi-quantitative analysis was difficult. .

[0005] The present invention solves the above-mentioned problems, and provides a semi-quantitative analysis that can easily and accurately perform a semi-quantitative analysis even on a sample containing an element to be analyzed using an L-ray or an M-ray. It is intended to provide a method and apparatus.

[0006]

According to one aspect of the present invention, a semi-quantitative value, which is an approximate calculated value of a sample, is obtained. The intensity data of the fluorescent X-rays generated from each of the components is measured, and the sensitivity data on the device sensitivity indicating the relationship between the measured X-ray intensity and the theoretical X-ray intensity for each element. The first sensitivity data relating to the sensitivity and the second sensitivity data relating to the apparatus sensitivity when a high-resolution slit is used are stored, and based on the measurement result of the sample, an L line or an M line is set in the sample. If it is determined that a certain amount of the element to be analyzed is not contained, the first
Of the measured X-ray intensity using the sensitivity data of the above, the first remeasurement for obtaining a semi-quantitative value is performed, and it is determined that the sample contains a certain amount of the element to be analyzed using the L-ray or the M-ray. In this case, the second X-ray intensity is converted using the second sensitivity data to perform a second re-measurement for obtaining a semi-quantitative value.

[0007] According to the above arrangement, in the case of a sample determined to contain a certain amount or more of an element to be analyzed using the L line or the M line based on the measurement result of the sample, the apparatus using the high resolution slit is used. Since the second re-measurement is performed based on the second sensitivity data relating to the sensitivity and a semi-quantitative value is automatically obtained, even a sample containing an element to be analyzed using an L-ray or an M-ray can be easily and accurately measured. A simple semi-quantitative analysis can be performed. Here, sensitivity data (hereinafter referred to as “library”
Or "sensitivity library") is the device sensitivity to fluorescent X-rays generated from each element,
This refers to data on the device sensitivities of a large number of elements from which the device sensitivities of elements having atomic numbers close to each other can be estimated. In the semi-quantitative analysis, an element to be analyzed using an L line refers to ₂₂ Ti to ₉₂ U, and particularly, a rare earth element ( ₅₇ La to ₇₁ Lu) or ₅₆ Ba
Say. The elements to be analyzed using the M line are ₅₇ La to ₉₂ U
Say.

Another configuration of the present invention is to obtain a semi-quantitative value, which is an approximate calculated value of a sample, and irradiates the sample with X-rays to obtain the intensity of fluorescent X-rays generated from each component in the sample. Is measured, and the sensitivity data on the device sensitivity showing the relationship between the measured X-ray intensity and the theoretical X-ray intensity for each element, the first sensitivity data on the device sensitivity when a standard resolution slit is used, and the high resolution slit Is stored, and based on the measurement result of the sample, the measured X-ray intensity is converted using the first sensitivity data, and the semi-quantitative value is calculated. The first re-measurement to be performed is performed, and based on the result of the first re-measurement, when it is determined that the sample contains a certain amount of the element to be analyzed using the L line or the M line, Convert measured X-ray intensity using second sensitivity data Performs a second re-measured to obtain the semi-quantitative value.

[0009] According to the above arrangement, a predetermined amount of the element to be analyzed using the L line or the M line in the sample based on the semi-quantitative value based on the first re-measurement result instead of the measurement result of the sample. Since it is determined whether or not it is included, a more accurate semi-quantitative analysis can be performed in the second re-measurement.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic configuration diagram of a semi-quantitative analyzer according to the first embodiment of the present invention. The present apparatus performs a semi-quantitative analysis for obtaining a semi-quantitative value, which is an estimated value of the sample S, based on the measured intensity of the fluorescent X-rays from the sample S. For example, the FP method is used.

The apparatus comprises a sample stage 9 on which a sample S is fixed,
An X-ray source 2 for irradiating the sample S with primary X-rays B1, and a field of view for restricting the field of view so that only a fluorescent X-ray (secondary X-ray) B2 from a specific measurement site of the sample S is taken into a detector 8 described later. A limiting aperture 4, a primary solar slit 5 for collimating the fluorescent X-ray B2 whose field of view is limited, and a spectroscope that diffracts only the fluorescent X-ray B2 having a wavelength satisfying the Bragg equation at the same diffraction angle θ as the incident angle θ. 6, a secondary solar slit 7 for collimating the diffracted fluorescent X-ray B3, and a detector 8 for detecting the intensity of the fluorescent X-ray B3. The spectroscope 6 and the detector 8 constitute a detecting unit 10.

The primary solar slit 5 has a standard resolution slit 5A and a high resolution slit 5B having two different opening angles α, and the secondary solar slit 7 similarly has a standard resolution slit 7A and a high resolution slit 5A. Slit 7
B. The opening angle α has a relationship of α = 2 s / L with the slit length L and the foil interval s. The high-resolution slits 5B and 7B have a smaller opening angle α and a higher resolution than the standard-resolution slits 5A and 7A. The primary solar slit 5 and the secondary solar slit 7 are provided with slit advance / retreat mechanisms 11 and 12 for moving the respective slits on / off the optical path. The slit advancing / retracting mechanisms 11 and 12 are, for example, rack and pinion type mechanisms, and are controlled by a measuring unit 22, a first re-measurement executing unit 24, and a second re-measurement executing unit 25 in the control unit 20, which will be described later. You.

Further, the present apparatus is provided with a control means 20 including the following storage means 21, measurement means 22, first determination means 23, first remeasurement execution means 24, and second remeasurement execution means 25. ing. The storage means 21 is a library for device sensitivity indicating a relationship between measured X-ray intensity and theoretical X-ray intensity for each element prepared in advance, and is a first library for device sensitivity when the standard resolution slits 5A and 7A are used. And a second sensitivity library relating to the device sensitivity when the high-resolution slits 5B and 7B are used. Hereinafter, the operation of the present apparatus will be described based on the flowchart of FIG.

First, the measuring means 22 irradiates the sample S with primary X-rays B1 from the X-ray source 2 and causes the detecting means 10 to measure the intensity of the fluorescent X-rays B3 generated from each component in the sample S. . At this time, the measuring means 22 is provided with the slit advance / retreat mechanism 1
1 and 12 to control the standard resolution slit 5 on the optical path.
A and 7A are arranged. Based on the measured intensity data of the fluorescent X-ray B3, for example, qualitative analysis is performed by analysis data processing means (not shown) (step S1), and peak detection and identification analysis of the element to be measured are performed by the identification means (step S2). ), The types and contents of the elements contained in the sample S are roughly determined.

Next, the first judging means 23 judges whether the sample S contains, for example, a rare earth element or barium in a predetermined amount or more based on the measurement result of the measuring means 22 (step S1). S3). If it is determined that the sample S does not contain a predetermined amount of rare earth element or barium, the first re-measurement execution unit 24 determines that the sample S contains a predetermined amount or more. Is automatically activated.

If it is determined that the sample S does not contain a predetermined amount of rare earth element or barium, the first re-measurement execution means 24 performs measurement using the first sensitivity library stored in the storage means 21. The first re-measurement for calculating the semi-quantitative value by converting the X-ray intensity is performed (step S4). At this time,
The first re-measurement execution means 24 includes the slit advance / retreat mechanism 11,
12 to control the standard resolution slits 5A, 7A on the optical path.
A is placed. If it is determined that the sample S contains a predetermined amount or more of the rare earth element or barium, the second re-measurement execution unit 25 uses the second sensitivity library stored in the storage unit 21 to perform measurement X-rays. The intensity is converted, and a second re-measurement for obtaining a semi-quantitative value is performed (step S5).
At this time, the second remeasurement executing means 25 controls the slit advance / retreat mechanisms 11 and 12 to arrange the high-resolution slits 5B and 7B on the optical path.

The first and second remeasurement execution means 24, 25
Is to be measured again by the FP method. In the FP method, first, based on the result of the qualitative analysis, the first step is to convert the measured X-ray intensity of the unknown sample into a scale of the theoretical X-ray intensity. At this time, the data is obtained by measuring an appropriate sensitivity calibration (standard) sample.
The first or second sensitivity library relating to the device sensitivity, which indicates the relationship between the measured X-ray intensity and the theoretical X-ray intensity for each element, is used for the conversion. This sensitivity library was created by selecting and measuring representative elements.
Other elements are estimated by interpolation and extrapolation. In some cases, the measured intensity corrected using the overlap correction coefficient is converted to remove the influence of the interference line.

In the second step, the measured X-ray intensity of the sensitivity calibration sample and the measured X-ray intensity of the unknown sample are compared to set a provisional content, and the first theoretical X-ray intensity is calculated there.
The calculated intensity is compared with the converted measured X-ray intensity obtained in the first step to reset the content, and the second theoretical X-ray intensity is calculated. The third step is to set convergence conditions. When the change rate of the difference between the n-th time and the (n-1) -th time becomes smaller than a specified value (convergence) by repeating the second step several times, the set content is the final semi-quantitative value.

Thus, in the case of the sample S which is determined based on the result of the measurement by the measuring means 22 to contain no rare earth element or barium, a standard resolution slit 5A,
The first re-measurement is performed based on the first sensitivity library relating to the device sensitivity when using the sample 7A, and in the case of the sample S determined to contain a certain amount or more, the high-resolution slits 5B and 7B
Since the second re-measurement is performed based on the second sensitivity library relating to the device sensitivity when using, the semi-quantitative value that is the approximate value of the content of each component in the sample S is automatically obtained. Alternatively, even for the sample S containing barium, an accurate semi-quantitative analysis can be easily performed.

Next, a second embodiment will be described.
FIG. 3 shows a schematic configuration diagram of a semi-quantitative analyzer according to the second embodiment of the present invention, and FIG. 4 is a flowchart showing the operation thereof.

In the control means 20 of FIG. 3, the second embodiment includes a second judgment means 26 instead of the first judgment means 23 of the first embodiment. In the flowchart of FIG. 4, in the second embodiment, the first determination unit 23 in the first embodiment determines whether the sample S contains a predetermined amount or more of the rare earth element or barium based on the measurement result by the measurement unit 22. Unlike the determination of whether or not to perform the determination (step S3 in FIG. 2), after the first re-measurement execution means 24 performs the first re-measurement using the first sensitivity library (step T3), The determination means 26 determines whether or not the sample S contains a predetermined amount or more of the rare earth element or barium based on the semi-quantitative value based on the first re-measurement result (step T4). Next, when it is determined that the sample S contains a predetermined amount or more of the rare earth element or barium, the second re-measurement executing means 25 performs the second re-measurement using the second sensitivity library. (Step T5). Other configurations are the same as those of the first embodiment.

According to the present apparatus, the semi-quantitative value of the first re-measurement result by the first re-measurement execution means 24 of the second embodiment is larger than the measurement result by the measurement means 22 of the first embodiment. Because it is more accurate, a more accurate semi-quantitative analysis can be performed in the second remeasurement.

In each of the above embodiments, when the sample S contains a predetermined amount or more of the rare earth element or barium and the sample S is determined to be mainly composed of the rare earth element or barium, A second re-measurement may be performed.

In each of the above embodiments, when the sample S is a thin film formed on a substrate, the approximate value of the attached amount of the thin film on the substrate and the approximate value of the film thickness are obtained instead of the approximate value of the content. Is also good.

[0025]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto. Semi-quantitative analysis was performed using the semi-quantitative device of FIG. 1 based on the flowchart of FIG. The sample was SY-3 (Ca
Using nada Center for Mineral and Energy Technology), a sample was prepared by a glass bead method in which a mixture of a sample and a flux was heated and melted and cooled to obtain a glassy sample. The ratio of sample to flux (eg, Li ₂ B ₄ O ₇ ) is 1: 2
And FIG. 5 shows an example of the result of the semi-quantitative analysis of the present invention and the conventional method, in which L-line use components are extracted. FIG. 6 shows an example of the qualitative chart at the time of the measurement of FIG.

From FIG. 6, it was confirmed that the qualitative chart of the present invention was detected with higher resolution than the conventional method, so that a more accurate semi-quantitative analysis value was obtained.

[0027]

As described above, according to one aspect of the present invention, when a sample is determined to contain a certain amount or more of an element to be analyzed using an L line or an M line based on the measurement result of the sample, Since the second re-measurement is performed based on the second sensitivity data relating to the device sensitivity when using the high-resolution slit and the semi-quantitative value is automatically obtained, the analysis includes the element to be analyzed using the L line or the M line. Even for samples, accurate semi-quantitative analysis can be easily performed.

According to another configuration of the present invention, an element to be analyzed using an L line or an M line in a sample based on a semi-quantitative value based on a first re-measurement result instead of the measurement result of the sample. Is determined to be contained in a certain amount or more, so that a more accurate semi-quantitative analysis can be performed in the second re-measurement.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing a semi-quantitative analyzer according to a first embodiment of the present invention.

FIG. 2 is a flowchart showing the operation of the above device.

FIG. 3 is a schematic configuration diagram showing a semi-quantitative analyzer according to a second embodiment of the present invention.

FIG. 4 is a flowchart showing the operation of the above device.

FIG. 5 is a diagram showing an example of a semi-quantitative analysis result.

FIG. 6 is a diagram showing an example of a qualitative chart at the time of measurement in FIG. 5;

[Explanation of symbols]

2: X-ray source, 5: primary solar slit, 7: secondary solar slit, 5A, 7A: standard resolution slit, 5B, 7
B: high-resolution slit, 10: detecting means, 21: storing means, 22: measuring means, 23: first determining means, 24: first remeasurement executing means, 25: second remeasurement executing means, 2
6: second determination means, S: sample.

Claims (4)

[Claims] 1. A semi-quantitative analysis method for obtaining a semi-quantitative value which is an approximate calculated value of a sample, comprising irradiating the sample with X-rays and measuring the intensity of fluorescent X-rays generated from each component in the sample. The sensitivity data relating to the device sensitivity, which indicates the relationship between the measured X-ray intensity and the theoretical X-ray intensity for each element, wherein the first sensitivity data relating to the device sensitivity when a standard resolution slit is used and the high resolution slit are used. The second sensitivity data relating to the device sensitivity at the time is stored, and based on the measurement result of the sample, the L line or the M
When it is determined that the element to be analyzed using the X-ray is not contained in a certain amount, the measurement X is performed using the first sensitivity data.
A first re-measurement for converting the line intensity to obtain a semi-quantitative value is performed, and when it is determined that the sample contains a certain amount or more of the element to be analyzed using the L line or the M line, A semi-quantitative analysis method in which a measured X-ray intensity is converted using the second sensitivity data to perform a second re-measurement to obtain a semi-quantitative value. 2. A semi-quantitative analysis method for obtaining a semi-quantitative value which is an approximate calculated value of a sample, wherein the sample is irradiated with X-rays and the intensity of fluorescent X-rays generated from each component in the sample is measured. The sensitivity data relating to the device sensitivity, which indicates the relationship between the measured X-ray intensity and the theoretical X-ray intensity for each element, wherein the first sensitivity data relating to the device sensitivity when a standard resolution slit is used and the high resolution slit are used. And second sensitivity data relating to the sensitivity of the apparatus at that time, and based on the measurement result of the sample, convert the measured X-ray intensity using the first sensitivity data to obtain a semi-quantitative value.
If it is determined based on the first re-measurement result that the sample contains a certain amount or more of the element to be analyzed using the L-ray or the M-ray, the second re-measurement is performed. A semi-quantitative analysis method in which the measured X-ray intensity is converted using the sensitivity data of (1) to perform a second re-measurement to obtain a semi-quantitative value. 3. A semi-quantitative analyzer for obtaining a semi-quantitative value which is an approximate calculated amount of a sample, comprising: an X-ray source for irradiating the sample with X-rays; and a detector for measuring the intensity of fluorescent X-rays generated from the sample. Means for irradiating the sample with X-rays from the X-ray source, and measuring the intensity of the fluorescent X-rays generated from each component in the sample by the detection means; and measuring the X-ray intensity and theoretical X-ray intensity for each element. The sensitivity data relating to the device sensitivity indicating the relationship between the line intensities, the first sensitivity data relating to the device sensitivity when a standard resolution slit is used, and the second sensitivity data relating to the device sensitivity when a high resolution slit is used. A first determination unit that determines whether or not a sample contains a predetermined amount or more of an element to be analyzed using an L line or an M line based on a measurement result of the measurement unit. L-line or M in the sample If it is determined that the element to be analyzed using the X-ray is not contained in a certain amount, the first X-ray intensity is converted using the first sensitivity data to perform a first re-measurement for obtaining a semi-quantitative value. A first re-measurement executing means to be performed, and when it is determined that an element to be analyzed using an L line or an M line is contained in a sample in a predetermined amount or more, the second sensitivity data is used. A second remeasurement executing means for performing a second remeasurement for converting the measured X-ray intensity to obtain a semiquantitative value. 4. A semi-quantitative analyzer for obtaining a semi-quantitative value which is an approximate calculated value of a sample, comprising: an X-ray source for irradiating the sample with X-rays; and a detector for measuring the intensity of fluorescent X-rays generated from the sample. Means for irradiating the sample with X-rays from the X-ray source, and measuring the intensity of the fluorescent X-rays generated from each component in the sample by the detection means; and measuring the X-ray intensity and theoretical X-ray intensity for each element. The sensitivity data relating to the device sensitivity indicating the relationship between the line intensities, the first sensitivity data relating to the device sensitivity when a standard resolution slit is used, and the second sensitivity data relating to the device sensitivity when a high resolution slit is used. A first re-measurement for converting a measured X-ray intensity using the first sensitivity data to obtain a semi-quantitative value based on a measurement result of the measuring means. Re-measurement execution means; A second determining means for determining whether or not a sample contains a predetermined amount or more of an element to be analyzed by using an L line or an M line based on the re-measurement result; If it is determined that the element to be analyzed is contained in a certain amount or more by using the second sensitivity data, the measured X-ray intensity is converted using the second sensitivity data to perform a second re-measurement for obtaining a semi-quantitative value. And a second remeasurement execution means for performing the measurement.