X-ray spectrometer and chemical state analysis method using the same

Patent metadata

Field	Value
Publication number	US-11137360-B2
Application number	US-201816651115-A
Country	US
Kind code	B2
Filing date	Jul 25, 2018
Priority date	Sep 27, 2017
Publication date	Oct 5, 2021
Grant date	Oct 5, 2021

Abstract

An X-ray spectrometer includes: an excitation source that irradiates a predetermined irradiation region on a surface of a sample with an excitation ray generating a characteristic X-ray; a flat plate analyzing crystal facing the irradiation region; a slit provided between the irradiation region and the analyzing crystal, the slit being parallel to a predetermined crystal plane of the analyzing crystal; a linear sensor including linear detection elements having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit; and an energy calibration unit that measures two characteristic X-rays in which energy is known by irradiating a surface of a standard sample generating the two characteristic X-rays with the excitation ray from the excitation source, and calibrates the energy of the characteristic X-ray detected by each detection element of the X-ray linear sensor based on the measured energies of the two characteristic X-rays.

First claim

The invention claimed is:

1. An X-ray spectrometer comprising:
a) a sample holder;
b) an excitation source configured to irradiate a predetermined irradiation region on a surface of a sample held by the sample holder with an excitation ray for generating a characteristic X-ray;
c) an analyzing crystal provided to face the irradiation region;
d) a slit provided between the irradiation region and the analyzing crystal, the slit being parallel to the irradiation region and a predetermined crystal plane of the analyzing crystal;
e) an X-ray linear sensor provided such that a plurality of linear detection elements each having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit; and
(f) an energy calibration unit configured to calibrate energy of the characteristic X-ray detected by each of the plurality of detection elements of the X-ray linear sensor at least based on known energies of Kα 1 ray and Kβ 1,3 ray emitted from one kind of element and measured by irradiating the irradiation region on a surface of a standard sample held by the sample holder with the excitation ray from the excitation source.

2. The X-ray spectrometer according to claim 1 , wherein the analyzing crystal is made of a flat plate.

3. The X-ray spectrometer according to claim 1 , wherein the one kind of element is an element contained in a sample of a measurement target.

4. The X-ray spectrometer according to claim 1 , wherein the energy calibration unit determines peak energy of intensity of Kα 1 ray by fitting an intensity curve in which Kα 1 ray and Kα 2 ray detected by the X-ray linear sensor overlap with a Lorentz function of Kα 1 ray and a Lorentz function of Kα 2 ray.

5. The X-ray spectrometer according to claim 4 , wherein the X-ray spectrometer has energy resolution in which intensity at a valley formed between a peak of Kα 1 ray and a peak of Kα 2 ray becomes less than or equal to ½ of the intensity at the peak of Kα 1 ray.

6. The X-ray spectrometer according to claim 1 , wherein the energy calibration unit determines peak energy of intensity of Kα 1,3 ray by fitting an intensity curve in which Kβ 1,3 ray and Kβ′ ray detected by the X-ray linear sensor overlap with a Lorentz function of Kβ 1,3 ray and a Lorentz function of Kβ′ ray.

7. The X-ray spectrometer according to claim 1 , further comprising a standard curve creation unit configured to create a standard curve indicating a relationship between peak energy and a valence based on peak energy of the characteristic X-rays emitted from a plurality of standard samples containing predetermined known elements and known different valences.

8. The X-ray spectrometer according to claim 1 , wherein
the energy calibration unit
obtains, by a least square method, an optical path length between a reference detection element which is one of the plurality of detection elements and the slit and an inclination angle of the analyzing crystal, the inclination angle being defined by a diffraction angle of the characteristic X-ray that is Bragg-reflected by the analyzing crystal through the slit and is incident on a reference detection element, based on known energies of at least three characteristic X-rays measured by irradiating the irradiation region on a surface of the standard sample held by the sample holder with the excitation ray from the excitation source, and
obtains the energy of the characteristic X-ray detected by each of the plurality of detection elements based on the optical path length, the inclination angle, and a distance between each of the plurality of detection elements of the X-ray linear sensor and the reference detection element.

9. The X-ray spectrometer according to claim 1 , wherein the sample holder includes:
a measurement sample holder configured to hold a sample of a measurement target in a region including the irradiation region; and
a standard sample holder configured to hold the standard sample at a position except for the measurement sample holder and a position irradiated with the excitation ray and within a range having a width in a direction perpendicular to the slit.

10. An X-ray spectrometer comprising:
a sample holder;
an excitation source configured to irradiate a predetermined irradiation region on a surface of a sample held by the sample holder with an excitation ray for generating a characteristic X-ray;
an analyzing crystal provided to face the irradiation region;
a slit provided between the irradiation region and the analyzing crystal, the slit being parallel to the irradiation region and a predetermined crystal plane of the analyzing crystal;
an X-ray linear sensor provided such that a plurality of linear detection elements each having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit; and
an energy calibration unit configured to calibrate energy of the characteristic X-ray detected by each of the plurality of detection elements of the X-ray linear sensor at least based on known energies of Kα 1 rays emitted from two kinds of elements and measured by irradiating the irradiation region on a surface of a standard sample held by the sample holder with the excitation ray from the excitation source, wherein the two kinds of elements are an element contained in a sample of a measurement target and an element having an atomic number larger than the element contained in the sample of the measurement target by one, or an element having an atomic number larger than the element contained in the sample of the measurement target by one and another element having an atomic number larger than the element contained in the sample of the measurement target by two.

11. The X-ray spectrometer according to claim 10 , wherein
the elements contained in the sample of the measurement target are two or more kinds of elements having consecutive atomic numbers, and
the two characteristic X-rays generated from the standard sample are Kα 1 ray of an element having an atomic number larger than the element having the largest atomic number in the two or more kinds of elements having consecutive atomic numbers by one and Kα 1 ray of one of the two or more kinds of elements having consecutive atomic numbers.

12. The X-ray spectrometer according to claim 10 , wherein the energy calibration unit determines peak energy of intensity of Kα 1 ray by fitting an intensity curve in which Kα 1 ray and Kα 2 ray detected by the X-ray linear sensor overlap with a Lorentz function of Kα 1 ray and a Lorentz function of Kα 2 ray.

13. The X-ray spectrometer according to claim 12 , wherein the X-ray spectrometer has energy resolution in which intensity at a valley formed between a peak of Kα 1 ray and a peak of Kα 2 ray becomes less than or equal to ½ of the intensity at the peak of Kα 1 ray.

14. A method for analyzing a chemical state of an element in a sample of a measurement target using an X-ray spectrometer comprising:
a sample holder;
an excitation source configured to irradiate a predetermined irradiation region on a surface of a sample held by the sample holder with an excitation ray for generating a characteristic X-ray;
an analyzing crystal provided to face the irradiation region;
a slit provided between the irradiation region and the analyzing crystal, the slit being parallel to the irradiation region and a predetermined crystal plane of the analyzing crystal;
an X-ray linear sensor provided such that a plurality of linear detection elements each having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit; and
an energy calibration unit

Assignees

• Shimadzu Corp

Inventors

• Sato Kenji
• Yoneda Tetsuya
• Adachi Susumu
• Tokuda Satoshi

Classifications

• G01N2223/3037

  standards (constitution) · CPC title

• G01N2223/5015

  linear array · CPC title

• G01N2223/32

  adjustments of elements during operation · CPC title

• G01N23/223

  by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence · CPC title

• G01N23/2076 Primary

  for spectrometry, i.e. using an analysing crystal, e.g. for measuring X-ray fluorescence spectrum of a sample with wavelength-dispersion, i.e. WDXFS · CPC title