JP2008032703A - X-ray fluorescence analyzer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an X-ray fluorescence analyzer, enabling an operator to always perform analysis of high sensitivity and accuracy in a short time, even if the operator is not skilled in optical adjustment, by automatically adjusting the position and angle of primary X-rays emitted from an X-ray source so as to maximize the intensity of fluorescent X-rays emitted from a sample. <P>SOLUTION: In the X-ray fluorescence analyzer 1, adjusting means 19, 22, and 23 controlled by a control means 20 adjust the position and angle of an X-ray tube 11 and a spectroscopic element 13. Offset storage means 21, 24, and 25 store as offsets the differences between the adjusted position and angle and the corresponding position and angle in the device mechanism. The stored offsets are given to an analytical condition setting means. The irradiation position and irradiation angle of the sample 16, irradiated with primary X-rays from the X-ray tube 11, are automatically adjusted so that the intensity of the fluorescent X-rays 17 emitted from the sample 16 becomes maximum. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fluorescent X-ray analyzer that automatically adjusts the irradiation position and irradiation angle of primary X-rays from an X-ray source so that the intensity of fluorescent X-rays generated from a sample is maximized.

  Conventionally, in order to set the rotation mechanism of the spectral crystal, the X-ray detector, the sample stage, etc. to the optimum measurement position, the offsets of these mechanisms are stored, and the stored X-rays are used to drive these mechanisms. There is an analyzer. As one of them, in order to select and use an appropriate spectral crystal according to the purpose of analysis from among multiple crystals, it is equipped with a crystal exchange mechanism that alternately installs multiple spectral crystals at the center position of the X-ray spectrometer. A means for rotating the spectral crystal positioned at the center around the center of the X-ray spectrometer and a mechanism for rotating the X-ray detector around the center of the X-ray spectrometer are provided independently of each other, and rotation of the spectral crystal is performed. A means for detecting the angle and the rotational position of the X-ray detector is provided, and the position of the spectroscopic crystal and the X-ray detector at which the detection output of the characteristic X-ray of the known element is maximized, and the mechanism of the spectroscopic crystal and the X-ray detector. There is a fluorescent X-ray analyzer that stores a difference from the X-ray wavelength corresponding position as an offset amount and drives a spectral crystal (see Patent Document 1).

In order to facilitate fine alignment of the irradiation positions of the plurality of excitation X-rays on the sample surface, the sample stage includes the irradiation position on the sample surface of the primary X-ray irradiated by each excitation X-ray and the sample stage. The position deviation from the origin is obtained using a fluorescent screen, and the obtained deviation is stored as an offset amount for each excitation X-ray source, and the irradiation position and the origin of the sample stage coincide with each other using this offset amount. As described above, there is a fluorescent X-ray analyzer that corrects the position of the sample stage (see Patent Document 2).
JP-A 63-167250 JP 2003-149182 A

  In such a conventional X-ray fluorescence analyzer, offsets such as a rotation mechanism of a spectral crystal, an X-ray detector, and a sample stage are stored at the time of factory adjustment, and the stored offsets are used to drive these mechanisms to position them. It is set, the offset amount is obtained as necessary at the time of measurement, the position is not set using the obtained offset amount, and the position of the X-ray source and the position and angle of the spectroscopic element are controlled by the sample. The primary X-ray irradiation position and angle from the X-ray source are automatically and appropriately adjusted so that the intensity of the generated X-ray fluorescence is maximized, and the fluorescent X-ray analyzer is constantly maintained with high sensitivity and high accuracy. is not. In the X-ray fluorescence analyzer, the primary X-ray from the X-ray source is caused by distortions and deviations in the device mechanism, such as changes in the room temperature due to the season of the device installation room, changes in the device over time, and displacements during X-ray tube replacement. If the irradiation position or irradiation angle on the sample deviates from the optimum state, the sensitivity decreases and the analysis accuracy also decreases.

  In particular, in a total reflection fluorescent X-ray analysis apparatus, X-rays obtained by monochromatizing primary X-rays from an X-ray source with a spectroscopic element are irradiated and analyzed at, for example, 0.05 ° to 0.25 °. If the irradiation position and irradiation angle on the sample are shifted even a little, the sensitivity and analysis accuracy are greatly reduced. Therefore, even if the sample height is the same as in the case of a glass substrate on which a wafer or sample solution has been drip-dried, the sample stage is adjusted by a motor drive each time the measurement sample is replaced, so that the irradiation position and irradiation angle are optimized. It is matched. Also, in the unlikely event that the irradiation position or irradiation angle on the sample is shifted and the sensitivity is greatly reduced, a person skilled in optical adjustment manually adjusts.

  Conventionally, in a fluorescent X-ray analyzer that has a plurality of X-ray sources and selects and uses an X-ray source according to the purpose of analysis, in particular, a total reflection X-ray fluorescence analyzer, each time the X-ray source is replaced, it is transferred to the sample. Since the measurement person was performing an analysis while confirming whether the irradiation position and the irradiation angle were not shifted, extra time was required until the analysis started.

  In view of the above-described conventional problems, the present invention has a single or plural X-ray sources, and a distance difference between the X-ray source position adjusted by the X-ray source adjusting means and the corresponding position on the mechanism of the X-ray source. Is the spectral offset adjusted by the spectroscopic element angle adjusting means, with the distance difference between the spectroscopic element position adjusted by the spectroscopic element position adjusting means and the corresponding position on the mechanism of the spectroscopic element as the spectroscopic element offset distance. The angle difference between the element angle and the corresponding angle on the mechanism of the spectroscopic element is stored as the spectroscopic element offset angle, and the offset amount is controlled so that the intensity of the fluorescent X-ray generated from the sample is maximized. Even if you are not an expert in optical adjustment, the position and angle of primary X-rays are automatically adjusted, for example, once a week and once a month. sensitivity, And to provide a fluorescent X-ray analyzer accuracy analysis can be performed.

  In order to achieve the above object, an X-ray fluorescence analyzer according to a first configuration of the present invention splits a single X-ray source and X-rays generated from the X-ray source into an X-ray having a predetermined wavelength. A fluorescent X-ray analyzer comprising: a spectroscopic element that irradiates a sample on a sample substrate; a detector that measures the intensity of fluorescent X-rays generated from the sample; and an analysis condition setting means that sets analysis conditions X-ray source position adjusting means for adjusting the position of the X-ray source, spectral element position adjusting means for adjusting the position of the spectral element, spectral element angle adjusting means for adjusting the rotation angle of the spectral element, And a control means for controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means based on the intensity of fluorescent X-rays generated from the sample measured by the detector.

  In addition, the distance between the X-ray source position adjusted by the X-ray source position adjusting means and the corresponding position on the mechanism of the X-ray source is stored as an X-ray source offset distance with respect to the X-ray source position origin, The distance between the X-ray source offset distance storage means for giving the stored X-ray source offset distance to the analysis condition setting means, and the spectral element position adjusted by the spectral element position adjusting means and the corresponding position on the mechanism of the spectral element Is stored as a spectroscopic element offset distance with respect to the spectroscopic element position origin, and the spectroscopic element offset distance storage means for applying the stored spectroscopic element offset distance to the analysis condition setting means, and the spectroscopic element adjusted by the spectroscopic element angle adjustment means The angle difference between the angle and the corresponding angle on the spectroscopic element mechanism is stored as a spectroscopic element offset angle with respect to the reference plane, and the stored spectroscopic element is stored. A spectroscopic element offset angle storage means for giving a child offset angle to the analysis condition setting means, and the sample of primary X-rays from the X-ray source so that the intensity of fluorescent X-rays generated from the sample is maximized Automatically adjust the irradiation position and angle.

  In the first configuration of the present invention, the single X-ray source is an X-ray tube made of, for example, tungsten, copper, chromium, molybdenum, platinum, rhodium, or palladium. The spectroscopic element is, for example, a crystal such as LiF, germanium, or graphite, or a cumulative multilayer film. The detector may be a semiconductor detector used in an energy dispersive X-ray fluorescence analyzer or a proportional counter used in a wavelength dispersive X-ray fluorescence analyzer.

  The X-ray source position adjusting means is a position adjusting means for linearly moving the X-ray source with respect to the X-ray source position origin. For example, a pulse motor or a ball screw mechanism is driven and controlled by the control means. The origin of the X-ray source position is on a plane including the X-ray irradiation surface of the sample substrate (hereinafter referred to as a reference plane), and the X-ray source moves linearly perpendicularly to the reference plane by a pulse motor of the X-ray source position adjusting means. It is the origin. The spectroscopic element position adjusting unit is a position adjusting unit that linearly moves the spectroscopic element with respect to the spectroscopic element position origin. For example, a pulse motor or a ball screw mechanism is driven and controlled by the control unit.

  The spectroscopic element position origin is a moving origin that is on the reference plane and linearly moves the spectroscopic element perpendicularly to the reference plane by the pulse motor of the spectroscopic element position adjusting means. The spectroscopic element angle adjusting means is a rotating means that rotationally moves the spectroscopic element with the spectroscopic element rotation center as a center and a reference plane of 0 °. For example, a gear and a pulse motor are driven and controlled by the control means. The X-ray source and the spectroscopic element move and rotate so that the viewing angle of the primary X-ray from the X-ray source to the spectroscopic element, that is, the diffraction angle of the diffracted X-ray diffracted by the spectroscopic element satisfies the Bragg condition.

  The X-ray source offset distance storage means uses the distance difference between the X-ray source position adjusted by the X-ray source position adjustment means and the corresponding position on the mechanism of the X-ray source as the X-ray source offset distance with respect to the X-ray source position origin. The stored X-ray source offset distance is given to the analysis condition setting means. The spectroscopic element offset distance storage means stores the distance difference between the spectroscopic element position adjusted by the spectroscopic element position adjusting means and the corresponding position on the spectroscopic element mechanism as a spectroscopic element offset distance with respect to the spectroscopic element position origin, and stores the stored spectral value. The element offset distance is given to the analysis condition setting means. The spectroscopic element offset angle storage means stores the angle difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjustment means and the corresponding angle on the spectroscopic element mechanism as the spectroscopic element offset angle with respect to the reference plane, and stores the spectroscopic element offset stored therein. An angle is given to the analysis condition setting means. The spectroscopic element angle is an angle formed by the reflection surface of the spectroscopic element and the reference plane.

  The corresponding position and angle on the mechanism of the X-ray source and the spectroscopic element correspond to the mechanism theoretically obtained in the apparatus design corresponding to the position and angle of the X-ray source and spectroscopic element adjusted by each adjusting means. The position and angle of the X-ray source and the spectroscopic element. The X-ray source offset distance storage means, the spectroscopic element offset distance storage means, and the spectroscopic element offset angle storage means include, for example, a pulse motor driving step for driving the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means. Memorize the number. The control means for controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means based on the intensity of fluorescent X-rays generated from the sample measured by the detector is, for example, a computer.

  The spectroscopic element may be a plurality of spectroscopic elements. In the case of a plurality of spectroscopic elements, the spectroscopic element has a spectroscopic element position adjusting unit and a spectroscopic element angle adjusting unit that can adjust the position and angle of each spectroscopic element. It is desirable. The fluorescent X-ray analyzer may be an energy dispersive fluorescent X-ray analyzer or a wavelength dispersive fluorescent X-ray analyzer.

According to the first configuration of the present invention, the intensity of fluorescent X-rays generated from the sample is maximized even when distortion or deviation occurs in the apparatus mechanism due to temperature changes in the apparatus installation chamber or changes in the apparatus over time. Thus, by controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means, the X-ray source offset distance with respect to the X-ray source position origin, the spectroscopic element offset distance with respect to the spectroscopic element position origin, and the reference plane Is automatically obtained, stored in the X-ray source offset distance storage means, the spectral element offset angle storage means, and the spectral element offset angle storage means, and applied to the analysis condition setting means. The irradiation position and irradiation angle of the primary X-ray from the X-ray source to the specimen can be automatically set based on the given offset amount, and high sensitivity is always achieved in a short time even without skilled optical adjustment. Highly accurate analysis can be performed.

  The fluorescent X-ray analyzer according to the second configuration of the present invention further includes an X-ray irradiation angle to the sample substrate and an intensity of the fluorescent X-ray generated from the sample substrate to the fluorescent X-ray analyzer according to the first configuration. A critical angle calculation means for calculating a critical angle of the X-ray irradiation angle by calculation, and an X-ray irradiation angle for correcting the X-ray irradiation angle on the sample based on the critical angle calculated by the critical angle calculation means Correction means.

  In the second configuration of the present invention, the critical angle calculating means drives the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means while sequentially changing the X-ray irradiation angle to the sample substrate. The intensity of fluorescent X-rays generated from the sample substrate corresponding to the X-ray irradiation angle is measured with a detector, and the X-ray irradiation angle is calculated by calculating the X-ray irradiation angle at which the gradient of the fluorescent X-ray intensity with respect to the X-ray irradiation angle is maximized. The critical angle of the irradiation angle is calculated. The X-ray irradiation angle correction means uses the difference between the critical angle calculated by the critical angle calculation means and the theoretical critical angle calculated based on the refractive index of the sample substrate and the irradiation X-ray energy as the irradiation angle offset angle of the X-ray irradiation angle. The X-ray irradiation angle is corrected. For example, a glass substrate or a silicon substrate is used as the sample substrate, and the critical angle calculating means measures the intensity of fluorescent X-ray Si-Kα rays generated from the sample substrate to calculate the critical angle.

  According to the second configuration of the present invention, in addition to the first configuration of the present invention, the critical angle calculation means and the X-ray irradiation angle correction means are provided. The irradiation position and the irradiation angle of the primary X-rays from the source to the sample can be automatically adjusted as appropriate, and analysis with higher sensitivity and higher accuracy can be performed.

  The X-ray fluorescence analyzer according to the third configuration of the present invention is selected by a plurality of X-ray sources, a selection unit that selects one X-ray source from the plurality of X-ray sources, and the selection unit. A spectroscopic element that divides X-rays generated from an X-ray source and irradiates a sample on a sample substrate with X-rays having a predetermined wavelength, a detector that measures the intensity of fluorescent X-rays generated from the sample, and an analysis An X-ray fluorescence analysis apparatus comprising an analysis condition setting means for setting conditions, an X-ray source position adjusting means for adjusting the position of the selected X-ray source, and a spectroscopic element for adjusting the position of the spectroscopic element Position adjusting means, spectral element angle adjusting means for adjusting the rotation angle of the spectroscopic element, the X-ray source position adjusting means, the spectroscopic element based on the intensity of fluorescent X-rays generated from the sample measured by the detector Position adjusting means and the spectroscopic element angle adjusting means And a Gosuru control means.

  In addition, the distance between the X-ray source position adjusted by the X-ray source position adjusting means and the corresponding position on the mechanism of the X-ray source is stored as an X-ray source offset distance with respect to the X-ray source position origin, X-ray source offset distance storage means for applying the stored X-ray source offset distance to the analysis condition setting means; the position of the spectroscopic element with respect to the X-ray source adjusted by the spectroscopic element position adjusting means; and the mechanism of the spectroscopic element The distance from the corresponding position above is stored as a spectral element offset distance with respect to the spectral element position origin, and the spectral element offset distance storage means for giving the stored spectral element offset distance to the analysis condition setting means, and the spectral element angle adjustment The angle difference between the spectroscopic element angle with respect to the X-ray source adjusted by the means and the corresponding angle on the mechanism of the spectroscopic element is defined as A spectroscopic element offset angle storage means for storing the set spectroscopic element offset angle and applying the stored spectroscopic element offset angle to the analysis condition setting means, so that the X-ray fluorescence generated from the sample has a maximum intensity. The irradiation position and irradiation angle of the primary X-ray from the radiation source to the sample are automatically adjusted.

  In the third configuration of the present invention, in order to select and use a plurality of X-ray sources, for example, a copper X-ray tube and a molybdenum X-ray tube according to the purpose of analysis, an X-ray tube selection means is provided. The selection means holds a plurality of X-ray tubes with an X-ray tube holding unit, and when an X-ray tube to be used is selected, drives and controls a mechanism unit such as a pulse motor, and sets the selected X-ray tube as a measurement position. To do. The plurality of X-ray tubes and selecting means may be means for selecting from among the above-mentioned X-ray tubes, including chromium X-ray tubes and tungsten X-ray tubes.

 According to the third configuration of the present invention, the same effects as the fluorescent X-ray analyzer of the first configuration can be obtained, and an X-ray source selected from a plurality of X-ray sources according to the analysis purpose is used. Even when the X-ray source is replaced, the intensity of fluorescent X-rays generated from the sample is maximized without the operator confirming that the irradiation position or irradiation angle on the sample is not shifted. The irradiation position and irradiation angle of the primary X-rays from the selected X-ray source to the sample can be automatically adjusted appropriately, and high sensitivity and high accuracy analysis can always be performed in a short time.

  The X-ray fluorescence analyzer according to the fourth configuration of the present invention further includes an X-ray irradiation angle to the sample substrate and the intensity of the X-ray fluorescence generated from the sample substrate to the X-ray fluorescence analyzer according to the third configuration. A critical angle calculation means for calculating a critical angle of the X-ray irradiation angle by calculation, and an X-ray irradiation angle for correcting the X-ray irradiation angle on the sample based on the critical angle calculated by the critical angle calculation means Correction means.

  In the fourth configuration of the present invention, the critical angle calculating means drives the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means, and sequentially changes the X-ray irradiation angle to the sample substrate. The intensity of fluorescent X-rays generated from the sample substrate corresponding to the X-ray irradiation angle is measured with a detector, and the X-ray irradiation angle is calculated by calculating the X-ray irradiation angle at which the gradient of the fluorescent X-ray intensity with respect to the X-ray irradiation angle is maximized. Calculate the critical angle of the angle. The X-ray irradiation angle correction means uses the difference between the critical angle calculated by the critical angle calculation means and the theoretical critical angle calculated based on the refractive index of the sample substrate and the irradiation X-ray energy as an irradiation angle offset angle of the X-ray irradiation angle. Correct the irradiation angle.

  According to the fourth configuration of the present invention, since the critical angle calculation means and the X-ray irradiation angle correction means are provided in addition to the third configuration of the present invention, the X-ray is more precisely added to the effects of the third configuration. The irradiation position and the irradiation angle of the primary X-rays from the source to the sample can be automatically adjusted as appropriate, and analysis with higher sensitivity and higher accuracy can be performed.

  Hereinafter, the total reflection X-ray fluorescence spectrometer which is the first embodiment of the present invention will be described. As shown in FIG. 1, the total reflection X-ray fluorescence spectrometer 1 converts primary X-rays 12 from a copper X-ray tube 11, which is a single X-ray source, into a spectroscopic element 13 made of, for example, a cumulative multilayer film. The sample X on the glass substrate 15 as the sample substrate is irradiated with the characteristic X-ray 14 monochromatized into Cu-Kα rays, and the fluorescent X-ray 17 generated from the sample 16 is, for example, a semiconductor detector (SSD or SDD). Detection is performed by the detector 18. The sample 16 is, for example, a solution sample containing chromium as a sample for optical axis automatic adjustment which is instilled onto the sample substrate 15 by 50 μl, for example, with a micropipette and dried.

  The X-ray source position adjusting means 19 is connected to the copper X-ray tube 11 by an electric signal from a control means 20 constituted by a computer, for example, by a pulse motor, a pulse motor drive circuit, a ball screw mechanism (or a rack and pinion mechanism). This is a position adjusting means for linear movement from the radiation source position origin. The X-ray source offset distance storage means 21 determines the distance difference between the X-ray source position adjusted by the X-ray source position adjusting means 19 and the corresponding position on the mechanism of the X-ray source with respect to the X-ray source position origin. The stored X-ray source offset distance is stored in the analysis condition setting means 26 as an offset distance.

  The spectroscopic element position adjusting unit 22 is a position adjusting unit that linearly moves the spectroscopic element 13 from the spectroscopic element position origin by using, for example, a pulse motor, a pulse motor drive circuit, a ball screw mechanism, or the like, based on an electrical signal from the control unit 20. The spectroscopic element offset distance storage unit 24 stores a distance difference between the spectroscopic element position adjusted by the spectroscopic element position adjusting unit 22 and the corresponding position on the spectroscopic element mechanism as a spectroscopic element offset distance with respect to the spectroscopic element position origin. The obtained spectral element offset distance is given to the analysis condition setting means 26.

  The spectroscopic element 13 rotates about a rotation axis 138 that is on the reflection surface of the spectroscopic element and intersects the incident X-ray axis to the spectroscopic element at a right angle. The spectroscopic element angle adjusting means 23 is a rotation adjusting means for rotating the spectroscopic element 13 from the reference plane by an electric signal from the control means 20, for example, by a pulse motor, a pulse motor drive circuit, a gear mechanism or the like. The spectroscopic element offset angle storage unit 25 stores an angular difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjustment unit 23 and the corresponding angle on the mechanism of the spectroscopic element as a spectroscopic element offset angle with respect to the reference plane, and stores the stored spectroscopic element. The element offset angle is given to the analysis condition setting means 26. The X-ray tube position storage unit 21, the spectroscopic element offset distance storage unit 24, and the spectroscopic element offset angle storage unit 25 are configured by a computer, for example.

  The control means 20 is constituted by a computer, for example, and based on the fluorescent X-ray intensity measured by the detector 18, the control position of the copper X-ray tube 11 and the spectroscopic element 13 are added to the pulse motor drive circuit of each adjustment means 19, 22, 23. A control pulse signal corresponding to the control position and the control angle is sent to control the control position of the copper X-ray tube 11 and the control position and control angle of the spectroscopic element 13.

  The analysis condition setting unit 26 sets the X-ray irradiation position and the irradiation angle for the sample based on the X-ray source offset distance, the spectroscopic element offset distance, and the spectroscopic element offset angle given from the storage units 21, 24, and 25. Thus, the primary X-rays 14 obtained by monochromatizing the primary X-rays 12 from the copper X-ray tube 11 into Cu-Kα rays by the spectroscopic element 13 so that the intensity of the fluorescent X-rays 17 generated from the sample 16 is maximized. Automatically adjust the irradiation position and angle of the sample.

  Next, the geometric positional relationship of each part in the total reflection X-ray fluorescence analyzer 1 will be described.

  As shown in FIG. 2, the reference plane 160 is a plane including the X-ray irradiation surface of the sample substrate 15. The X-ray irradiation position 162 on the sample of the primary X-ray 14 obtained by monochromatizing the primary X-ray 12 from the copper X-ray tube 11 into Cu-Kα rays by the spectroscopic element 13 is such that the copper X-ray tube 11 is perpendicular to the reference plane 160. The first intersection 112 of the X-ray tube movement linear axis 111 moving to the reference plane 160 and the reference plane 160, and the second intersection 132 of the spectroscopic element movement linear axis 131 where the spectroscopic element 13 moves perpendicular to the reference plane 160 and the reference plane 160. It is comprised so that it may be on the straight line 161 which connects. The first intersection 112 is the X-ray source position origin 112, and the second intersection 132 is the spectroscopic element position origin 132.

  The distance between the irradiation position 162 of the sample 16 and the spectroscopic element position origin 132 is L1, a perpendicular foot (hereinafter referred to as the third intersection) 134 and the X-ray generation point that is lowered from the X-ray generation point 113 to the spectroscopic element movement linear axis 131. 113 is L2, the distance between the incident point 133 (spectral element position) and the spectroscopic element position origin 132 is S, the distance between the spectroscopic element position origin 132 and the third intersection 134 is T, and the primary X-ray 14 is the sample. The angle between the straight line 161 and the primary X-ray 14, which is the irradiation angle with which the irradiation surface is irradiated, is φ, and the angle between the reflection surface 136 of the spectroscopic element 13 and the reference plane 160 is the rotation angle Ω of the spectroscopic element 13. A viewing angle of the primary X-ray 12 from the copper X-ray tube 11 to the spectroscopic element 13, that is, a diffraction angle of the diffracted X-ray 14 that is monochromatized by the spectroscopic element is defined as θ.

  The distance T between the spectroscopic element position origin 132 and the third intersection 134 is the same distance as the distance between the X-ray generation point (copper X-ray tube position) 113 of the copper X-ray tube 11 and the X-ray source position origin 112. This is the distance between the copper X-ray tube position 113 adjusted by the X-ray source position adjusting means 19 and the X-ray source position origin 112.

  In FIG. 2, the relationship of Formula 1-3 is materialized.

      T = L2 tan (2θ−φ) −L1 tan φ (1)

      S = L1tanφ (2)

      Ω = θ−φ (3)

  The operations of the copper X-ray tube 11 and the spectroscopic element 13 for changing the irradiation angle φ of the primary X-ray 14 to the sample 16 will be described using Equations 1 to 3. The diffraction angle θ is a constant angle determined by the d value of the spectroscopic element 13 and the wavelength of the Cu-Kα ray 14 that is a diffraction X-ray, and the distance between L1 and L2 is a fixed distance of the total reflection X-ray fluorescence spectrometer 1. That is, in the three formulas 1 to 3, there are four unknowns, T, S, φ, and Ω. Therefore, if the desired φ is a known number, T, S, and Ω are uniquely determined. Therefore, the copper X-ray tube 11 and the spectroscopic element 13 are linearly moved by the position adjusting means 19 and 22 to appropriately change T and S, and the spectroscopic element angle adjusting means 23 is appropriately changed to the spectroscopic element rotation angle Ω. By doing so, the irradiation angle φ can be changed to a desired angle without changing the irradiation position.

  The copper X-ray tube position 113, the spectroscopic element position 133, and the spectroscopic element angle represented by T, S, and Ω in Equations 1 to 3 are the position and angle on the apparatus mechanism that are theoretically obtained by the apparatus design. However, in an actual apparatus, there are also manufacturing errors, and distortions and deviations in the apparatus mechanism such as changes in room temperature due to the season of the apparatus installation room and changes over time of the apparatus also occur. They are the difference between the position and angle adjusted by each adjusting means 19, 22, and 23 and the corresponding position and angle on the mechanism. This difference is an offset distance and an offset angle with respect to each of the origin positions 112 and 132 and the reference plane 160.

Therefore, in an actual apparatus, Equations 1 to 3 become Equations 4 to 6 having offsets t ₀ , s ₀ , and ω ₀ .

T = L2 tan (2θ−φ) −L1 tan φ + t ₀ (4)

S = L1 tan φ + s ₀ (5)

Ω = θ−φ + ω ₀ (6)

  Next, with reference to the flowchart of FIG. 3, the steps in which the adjustment means 19, 22, and 23 store the offsets in the operation of the total reflection X-ray fluorescence spectrometer 1 will be described. The measurer operates the arrangement of the sample in step S1 and the selection of the automatic adjustment in step S2, and the total reflection X-ray fluorescence spectrometer 1 automatically operates from step S3. In step S1, for example, 50 μl of a solution sample containing chromium is collected with a micropipette, drip-dried onto a glass substrate 15 as a sample substrate, and the total reflection fluorescent X-ray analyzer 1 is used as a sample for optical axis automatic adjustment. Place on the sample stage (not shown). In step S2, automatic adjustment of the irradiation position and irradiation angle of the primary X-ray sample from the copper X-ray tube 11 is selected.

  In step S3, the adjustment means 19, 22, 23, for example, the irradiation position of the primary X-ray sample near the center position where the sample 16 is initially set, and the irradiation angle is initially set to 0.15 °. Set to In step S4, the primary X-ray 12 from the copper X-ray tube 11 is incident on the spectroscopic element 13 set at the diffraction angle and position for monochromatization to Cu-Kα rays, and the monochromatized Cu- Irradiation of Kα rays is started. In step S5, the measurement of the Cr-Kα ray 17 which is a fluorescent X-ray generated by the excitation of chromium contained in the sample by the irradiated Cu-Kα ray is started by the SSD 18 as a detector.

  In step S6, the X-ray tube position adjusting means 19 and the spectroscopic element position adjusting means 22 are controlled by the control means 20, whereby the copper X-ray tube 11 and the spectroscopic element 13 are simultaneously set at the same distance and centered at the set position. And move to a position where the intensity of the Cr-Kα line 17 measured by the SSD 18 becomes maximum. The irradiation position of the Cu—Kα ray on the sample 16 is adjusted by the linear parallel movement of the copper X-ray tube 11 and the spectroscopic element 13.

  In step S7, the X-ray tube position adjusting means 19 moves the copper X-ray tube 11 forward and backward along the X-ray tube moving linear axis 111 around the position adjusted in step S6, and the Cr-Kα ray measured by the SSD 18 is obtained. The copper X-ray tube 11 is adjusted to the position where the strength of 17 is maximized.

  In step S8, the irradiation angle set to 0.15 ° in step S3 is adjusted. As described above, the copper X-ray tube 11 and the spectroscopic element 13 are linearly moved by the position adjusting means 19 and 22 to change T and S according to the relations of Expressions 1 to 3, and the spectroscopic element angle adjusting means 23 performs spectroscopic analysis. By changing the element rotation angle Ω, the desired irradiation angle φ can be set without changing the irradiation position. Therefore, T, S, and Ω are changed by the position adjusting means 19 and 22 and the spectroscopic element angle adjusting means 23 so that the irradiation angle φ changes in steps of 0.005 ° around the set 0.15 °. The irradiation angle φ is adjusted so that the intensity of the Cr—Kα line 17 is maximized. The irradiation angle φ may be changed in 0.01 ° steps.

In step S9, it is determined whether or not steps S6 to S8 have been performed twice. If YES, the process proceeds to step S10. If NO, the process returns to step S6. In step S10, X-ray tube offset distance storing the distance between the corresponding location on the copper X-ray tube position 113 a mechanism that is adjusted until YES determination in step S9 as X-ray tube offset distance t ₀ with respect to the X-ray source position origin Store in means 21. Until the determination in step S9 is YES, the distance between the adjusted spectroscopic element position 133 and the corresponding position on the mechanism is stored in the spectroscopic element position storage unit 24 as the spectroscopic element offset distance s _{0 with} respect to the spectroscopic element position origin. Further, until the YES determination in step S9, the angle difference between the adjusted spectroscopic element angle Ω and the corresponding angle on the spectroscopic element mechanism is stored in the spectroscopic element angle storage means 25 as the spectroscopic element offset angle ω _{0 with} respect to the reference plane. . In the present embodiment, steps S6 to S8 are performed twice, but may be one or three rounds as long as the number of times is appropriate.

Next, the automatic adjustment of the X-ray irradiation position and the irradiation angle to the sample during the unknown sample measurement in the operation of the total reflection X-ray fluorescence analyzer 1 will be described with reference to the flowchart of FIG. In step S11, the glass substrate 15 obtained by drip-drying the unknown solution sample is placed on the sample stage. In step S12, the analysis condition setting means 26 selects an analysis condition for analysis. In step S13, each storage means 21, 24, 25 gives each offset amount t ₀ , s ₀ , ω ₀ stored in step S10 to the analysis condition setting means 26. In step S14, on the basis of each offset amount given to the analysis condition setting means 26, the mechanical parts such as the pulse motor drive circuit, pulse motor, and ball screw of each adjustment means 19, 22, 23 are controlled, and the copper X-ray tube 11 is controlled. And the position and rotation angle of the spectroscopic element 13 are set, and the X-ray irradiation position and the irradiation angle at which the intensity of the fluorescent X-rays 17 generated from the sample 16 reaches the maximum until the YES determination in step S9 is automatically set. Is done.

  Other analysis conditions are also set by the analysis condition setting means 26 in step S12. In step S15, the sample 16 arranged in step S11 is measured. When the measurement of the sample 16 is finished, the operation of the total reflection fluorescent X-ray analyzer 1 is also finished, and the X-ray irradiation and the fluorescent X-ray measurement on the sample 16 in steps S4 and S5 are also finished. When the unknown sample measurement is not performed following steps S1 to S10, the operation of the total reflection fluorescent X-ray analyzer 1 is ended, and the X-ray irradiation and fluorescent X-ray measurement to the sample 16 in steps S4 and S5 are also ended. .

  According to the apparatus of the first embodiment, the intensity of fluorescent X-rays generated from a sample is maximized even if distortion or deviation on the apparatus mechanism occurs due to temperature changes in the apparatus installation chamber or changes over time of the apparatus. As described above, the offset amount for correcting the deviation in the mechanism of the apparatus is automatically obtained, and based on the offset amount, the irradiation position and the irradiation angle of the primary X-ray from the X-ray source to the sample are automatically set. Even if there is no expert in optical adjustment, automatic optical axis adjustment may be performed as appropriate. For example, once a week, once a month, a highly sensitive and accurate analysis is always performed in a short time. Can do.

  Although a glass substrate is used as a sample substrate for drip-drying a solution sample, a silicon substrate may be used, and the amount of drip applied to the sample is not limited to 50 μl, but may be about 10 to 100 μl. The sample is not limited to a solution sample, and the substrate itself may be a sample, and the surface layer portion of the substrate may be analyzed. The setting of the irradiation angle is not limited to 0.15 °, and may be appropriately selected depending on the energy of the characteristic X-ray to be irradiated. In the case of Mo-Kα rays, 0.10 ° is preferable. Although the mechanism parts of the adjusting means 19, 22, and 23 are used for the mechanism parts such as the pulse motor drive circuit, the pulse motor, and the ball screw of the analysis condition setting means 26, they may be independent of each other.

  The X-ray fluorescence analyzer of the second embodiment will be described below. As shown in FIG. 5, the X-ray fluorescence analyzer 5 of the second embodiment is similar to the X-ray fluorescence analyzer of the first embodiment, and further, the X-ray irradiation angle to the sample substrate 15 and the fluorescence X generated from the sample substrate 15. The critical angle calculation means 51 for calculating the critical angle of the X-ray irradiation angle by calculating the intensity of the line 17, and the X-ray irradiation angle to the sample 16 based on the critical angle calculated by the critical angle calculation means 51 X-ray irradiation angle correction means 52 for correcting the above.

  The critical angle calculation means 51 measures the intensity of the fluorescent X-rays 17 generated from the sample substrate 15 at each X-ray irradiation angle by the detector 18, and the gradient of the fluorescent X-ray intensity change with respect to the X-ray irradiation angle is maximized. The critical angle of the X-ray irradiation angle is calculated by calculating the X-ray irradiation angle. More specifically, the X-ray source position adjusting means 19, the spectroscopic element position adjusting means 22 and the spectroscopic element angle adjusting means 23 are driven, and the X-ray irradiation angle to the sample substrate 15 which is a glass substrate is changed from 0 °, for example. The intensity of the fluorescent X-ray Si-Kα rays 17 generated from the sample substrate 15 which is a glass substrate corresponding to each X-ray irradiation angle is measured by the detector 18 while being changed in steps of 0.005 °, and the X-ray irradiation angle is measured. The critical angle of the X-ray irradiation angle is calculated by calculating the X-ray irradiation angle at which the gradient of the intensity change of the Si—Kα ray with respect to the maximum is calculated.

  The X-ray irradiation angle correction unit 52 calculates the difference between the critical angle calculated by the critical angle calculation unit 51 and the theoretical critical angle calculated based on the refractive index of the sample substrate 15 and the energy of the irradiation X-ray 14 as a reference plane 160 ( The X-ray irradiation angle φ (see FIG. 2) is corrected as the irradiation angle offset angle with respect to (see FIG. 2).

  The operation of the total reflection X-ray fluorescence analyzer 5 of the second embodiment will be described. First, the total reflection fluorescent X-ray analyzer 5 operates in the order of steps in the flowchart shown in FIG. Since steps S1 to S8 and S9 to S10 are the same steps as steps S1 to S8 and S9 to S10 of the first embodiment, steps SA1 and SA2 between steps S8 and S9 will be described.

  In step SA1, the critical angle calculation means 51 is used to change the X-ray irradiation angle of the sample substrate 15 while changing the X-ray irradiation angle to the sample substrate 15 which is a glass substrate as in step S8 of the first embodiment. Calculate the critical angle. The X-ray source position adjusting means 19, the spectroscopic element position adjusting means 22 and the spectroscopic element angle adjusting means 23 are driven, and the X-ray irradiation angle to the sample substrate 15 is sequentially changed from 0 ° in, for example, 0.005 ° steps. The intensity of the fluorescent X-ray Si-Kα ray 17 generated from the sample substrate 15 which is a glass substrate corresponding to each X-ray irradiation angle is measured by the detector 18, and the gradient of the intensity change of the Si-Kα ray with respect to the X-ray irradiation angle. The critical angle of the X-ray irradiation angle is calculated by calculating the X-ray irradiation angle at which becomes the maximum. When the X-ray irradiation angle is changed, the intensity of the Si—Kα line 17 generated from the sample substrate 15 changes and becomes a curve as shown in FIG. 7, so that the gradient of the intensity change of the Si—Kα line is maximized. The critical angle calculation means 51 calculates the X-ray irradiation angle. The calculated X-ray irradiation angle is 0.22 °, for example, and this X-ray irradiation angle is a critical angle.

  In Step SA2, the X-ray irradiation angle correction means 52 corrects the X-ray irradiation angle φ on the sample 16 based on the critical angle calculated in Step SA1. The X-ray irradiation angle correction means 52 has a theoretical critical angle calculated from the refractive index of a glass substrate that is a sample substrate used in the present embodiment and the energy of Cu-Kα rays that are characteristic X-rays irradiated to the sample substrate, for example. The difference between the stored theoretical critical angle and the critical angle calculated by the critical angle calculating means 51 is stored as an irradiation angle offset angle with respect to the reference plane 160 (see FIG. 2), and this stored irradiation is stored. Based on the angle offset angle, the X-ray irradiation angle is reset to 0.15 ° which is the X-ray irradiation angle set during the automatic adjustment, and the X-ray irradiation angle is corrected. The X-ray irradiation angle correction means 52 also stores theoretical critical angles calculated from other characteristic X-rays such as a silicon substrate, Cr-Kα ray, and Mo-Kα ray. When used, the X-ray irradiation angle is similarly corrected.

  In the operation of the total reflection X-ray fluorescence spectrometer 5 of the second embodiment, the automatic adjustment of the X-ray irradiation position and the irradiation angle to the sample at the time of unknown sample measurement is the same as steps S11 to S14 of the first embodiment. .

  According to the total reflection X-ray fluorescence analyzer 5 of the second embodiment, a critical angle calculation unit 51 and an X-ray irradiation angle correction unit 52 are provided in addition to the total reflection X-ray fluorescence analyzer 1 of the first embodiment. Therefore, in addition to the effects of the first embodiment, the X-ray irradiation angle is corrected and reset by the X-ray irradiation angle correction means 52 using the critical angle calculated by the critical angle calculation means 51, so that the copper X is more precisely set. The irradiation position and the irradiation angle of the irradiation X-rays 14 from the ray tube 11 to the sample 16 can be automatically adjusted, and analysis with higher sensitivity and higher accuracy can be performed.

  Next, a total reflection X-ray fluorescence analyzer that is a third embodiment will be described. As shown in FIG. 8, the total reflection X-ray fluorescence analyzer 8 includes a copper X-ray tube 11 and a molybdenum X-ray tube 81 in addition to the total reflection X-ray fluorescence analyzer 1 of the first embodiment. And a selection means 82 for selecting one of the copper X-ray tube 11 and the molybdenum X-ray tube 81.

  The copper X-ray tube 11 and the molybdenum X-ray tube 81 which are a plurality of X-ray tubes are attached to a mounting plate which is an X-ray tube replacement part of the selection means 82. When the copper X-ray tube 11 is selected by the operator's selection and the selection means 82 is activated, the pulse motor drive circuit, pulse motor, ball screw, etc. are driven and controlled, the X-ray tube mounting plate moves, and the selected copper X-ray is moved. Tube 11 is set to the measurement position. It is preferable to use the same driving unit as the driving unit of the X-ray tube position adjusting unit, such as a pulse motor driving circuit, a pulse motor, and a ball screw.

  The operation of the total reflection X-ray fluorescence analyzer 8 of the third embodiment will be described. The total reflection X-ray fluorescence analyzer 8 operates in the order of steps in the flowchart shown in FIG. Since steps S1 and S3 to S10 are the same steps as steps S1 and S3 to S10 of the first embodiment, steps SB1 and SB2 between steps S1 and S3 will be described.

  In step SB1, when the copper X-ray tube 11 to be used is selected by the selection means 82, the control unit of the selection means 82 drives the mounting plate, which is an X-ray tube replacement part, by a pulse motor drive circuit, a pulse motor, a ball screw, or the like. The X-ray tube mounting plate is moved, the selected copper X-ray tube 11 is set to the measurement position, and the control unit of the selection unit drives the spectroscopic element position adjusting unit 22 and the spectroscopic element angle adjusting unit 23 to drive the pulse motor. The driving mechanism controls the circuit, pulse motor, ball screw, and the like, sets the spectroscopic element 13 to the measurement angle of the Cr-Kα ray, and automatically proceeds to the next step SB2. In step SB2, automatic adjustment of the irradiation position and irradiation angle of the primary X-ray sample from the copper X-ray tube 11 is automatically selected.

  When the molybdenum X-ray tube 81 is replaced, if the molybdenum X-ray tube 81 is selected in step SB1 of the flowchart shown in FIG. 9, the measurement position and measurement of the molybdenum X-ray tube 81 are the same as the copper X-ray tube 11 described above. The angle is set and the process automatically proceeds to step SB2. In step SB2, automatic adjustment of the irradiation position and irradiation angle of the primary X-ray 14 from the molybdenum X-ray tube 81 to the sample 16 is automatically selected.

  In the above, when step SB1 is completed, the process automatically proceeds to step SB2, and the automatic adjustment of the X-ray irradiation position and the irradiation angle is automatically selected in step SB2. However, step SB2 may be manually operated by the operator. . By performing step SB2 manually, sample measurement can be started in step S15 immediately after step SB1 is completed.

  In the operation of the total reflection X-ray fluorescence spectrometer 8 of the third embodiment, the automatic adjustment of the X-ray irradiation position and the irradiation angle to the sample at the time of unknown sample measurement is the same as steps S11 to S14 of the first embodiment. .

  According to the total reflection X-ray fluorescence analyzer 8 of the third embodiment, the same effect as that of the X-ray fluorescence analyzer of the first embodiment can be obtained, and among a plurality of X-ray sources depending on the analysis purpose. Even when the X-ray tube selected from the above is used, every time the X-ray source is replaced, the fluorescence X generated from the sample without the operator confirming whether the X-ray irradiation position or irradiation angle on the sample is shifted. The X-ray irradiation position and irradiation angle to the primary X-ray sample from the selected X-ray source are automatically set so that the intensity of the line is maximized. It can be carried out.

  The total reflection X-ray fluorescence analyzer 8 of the third embodiment includes a selection means 82 for selecting one of the copper X-ray tube 11 and the molybdenum X-ray tube 81. For example, In addition to these X-ray tubes, a tungsten X-ray tube or a chrome X-ray tube may be further provided, and an X-ray tube to be used may be selected from them.

  Next, a total reflection X-ray fluorescence spectrometer that is a fourth embodiment will be described. As shown in FIG. 10, in addition to the total reflection X-ray fluorescence analyzer 8 of the third embodiment, the total reflection X-ray fluorescence analyzer 10 further includes the X-ray irradiation angle to the sample substrate 15 and the sample substrate 15. Based on the critical angle calculation means 51 for calculating the critical angle of the X-ray irradiation angle φ by calculating the intensity of the fluorescent X-rays 17 generated more and the critical angle calculated by the critical angle calculation means 51, the sample 16 is applied. X-ray irradiation angle correction means 52 for correcting the X-ray irradiation angle.

  The operation of the total reflection X-ray fluorescence spectrometer 10 according to the fourth embodiment will be described. The total reflection X-ray fluorescence spectrometer 10 operates in the order of steps in the flowchart shown in FIG. Steps S1 to S8 are the same as steps S1 to S8 of the third embodiment, and steps SA1 to S10 are the same steps as steps SA1 to S10 of the second embodiment.

  In the operation of the total reflection X-ray fluorescence spectrometer 10 of the fourth embodiment, the automatic adjustment of the X-ray irradiation position and the irradiation angle to the sample at the time of unknown sample measurement is the same as steps S11 to S14 of the first embodiment. .

  According to the total reflection X-ray fluorescence analysis apparatus 10 of the fourth embodiment, the critical angle calculation means 51 and the X-ray irradiation angle correction means 52 are provided in addition to the total reflection X-ray fluorescence analysis apparatus 8 of the third embodiment. Therefore, in addition to the effects of the third embodiment, the critical angle calculated by the critical angle calculation means 51 is changed every time the X-ray source is replaced even when an X-ray tube selected from a plurality of X-ray sources is used. The X-ray irradiation angle is corrected and reset by the X-ray irradiation angle correction means 52, and the irradiation position and the irradiation angle of the X-ray irradiation 14 from the selected X-ray tube to the sample 16 are automatically adjusted. It is possible to perform analysis with higher sensitivity and higher accuracy.

  In FIGS. 1, 5, 8 and 10, the sample 16 is drawn with a thickness that can be visually observed for the sake of clarity. However, the actual sample is the substrate itself or is extremely thin so that it cannot be visually confirmed.

  In the total reflection X-ray fluorescence analyzers of the first to fourth embodiments, an unknown sample obtained by drip-drying a solution sample on a glass substrate 15 is measured. In the case of such a sample, since the sample is extremely thin, the sample surface of the glass substrate 15 can be regarded as the same height as the reference plane 160, but a sample such as a material such as a polymer film or a soft material that is difficult to determine the position of the surface. When these are placed on a glass substrate, the surface of these samples becomes higher than the reference plane 160, and such a sample can be made accurate only by automatically setting the optical axis by the operations from steps S11 to S14 in FIG. I can't analyze well.

  Accordingly, a total reflection X-ray fluorescence spectrometer that is a fifth embodiment capable of accurately analyzing a sample whose sample surface is higher than the reference plane 160 will be described below. The total reflection X-ray fluorescence analyzer of the fifth embodiment differs from the total reflection X-ray fluorescence analyzer of the first embodiment only in part of the control content of the control means 20, and uses a sample for automatic optical axis adjustment. After the automatic adjustment of the irradiation position and the irradiation angle of the primary X-ray to the sample, conditions for setting the optimal primary X-ray irradiation position according to the sample height are set in the analysis condition setting means. Thus, the apparatus automatically adjusts the irradiation position of the primary X-ray from the X-ray source to the sample so that the intensity of the fluorescent X-rays generated from the sample is maximized. Except for this point, the apparatus configuration is the same as that of the total reflection X-ray fluorescence spectrometer 1 of the first embodiment, and therefore the configuration of the apparatus will be described with reference to FIG.

First, the operation of the total reflection X-ray fluorescence spectrometer 1 will be described with reference to the flowchart of FIG. 12 in the case of analyzing chromium in the polymer film. In step S11, the glass substrate 15 on which the sample (polymer film) 16 is placed is placed on the sample stage. In step S12, the analysis condition setting means 26 selects an analysis condition for analysis. At this time, since the sample polymer film has the same thickness between samples, a flow for performing steps SS1 to SS3 shown in the flowchart of FIG. 12 once is selected even when a plurality of samples are analyzed. In step S13, each storage means 21, 24, 25 gives each offset amount t ₀ , s ₀ , ω ₀ stored in step S10 to the analysis condition setting means 26. In step S14, on the basis of each offset amount given to the analysis condition setting means 26, the mechanical parts such as the pulse motor drive circuit, pulse motor, and ball screw of each adjustment means 19, 22, 23 are controlled, and the copper X-ray tube 11 is controlled. And the position and rotation angle of the spectroscopic element 13 are set.

  In step SS1, the primary X-ray 12 from the copper X-ray tube 11 is made incident on the spectroscopic element 13 set at the diffraction angle and position to be monochromatized into Cu-Kα rays, and the monochromatized Cu- Irradiation of Kα rays is started. In step SS2, the measurement of the Cr-Kα ray 17 which is a fluorescent X-ray generated when the chromium contained in the sample is excited by the irradiated Cu-Kα ray is started by the SSD 18 as a detector.

  In step SS3, the X-ray tube position adjusting means 19 and the spectroscopic element position adjusting means 22 are controlled by the control means 20, whereby the copper X-ray tube 11 and the spectroscopic element 13 are simultaneously set at the same distance and centered at the set position. And move to a position where the intensity of the Cr-Kα line 17 measured by the SSD 18 becomes maximum. The irradiation position of the Cu—Kα ray on the sample 16 is adjusted by the linear parallel movement of the copper X-ray tube 11 and the spectroscopic element 13.

  Other analysis conditions are also set by the analysis condition setting means 26 in step S12. In step S15, the sample 16 arranged in step S11 is analyzed. In step S16, it is determined whether or not to analyze the next sample. When analyzing the next sample, the next sample is placed at the measurement position in step S17, and the process returns to step S15 to analyze the next sample. When the next sample is not analyzed, the operation of the total reflection fluorescent X-ray analyzer 1 is completed, and the X-ray irradiation and fluorescent X-ray measurement on the sample 16 of steps SS1 and SS2 are also completed.

  When analyzing a plurality of samples having the same thickness, such as the polymer film of this analysis example, the fluorescence X generated from the sample is performed only by performing steps SS1 to SS3 once as shown in the flowchart of FIG. The irradiation position of the primary X-ray from the X-ray source to the sample can be automatically adjusted so that the intensity of the line is maximized.

Next, the case of analyzing chromium in hair will be described with reference to the flowchart of FIG. In step S11, the glass substrate 15 on which the sample (hair) 16 is placed is placed on the sample stage. In step S12, the analysis condition setting means 26 selects an analysis condition for analysis. At this time, since the hair of the samples varies in thickness between the samples, a flow for performing steps SS1 to SS3 shown in the flowchart of FIG. 13 for each sample is selected. In step S13, each storage means 21, 24, 25 gives each offset amount t ₀ , s ₀ , ω ₀ stored in step S10 to the analysis condition setting means 26. In step S14, on the basis of each offset amount given to the analysis condition setting means 26, the mechanical parts such as the pulse motor drive circuit, pulse motor, and ball screw of each adjustment means 19, 22, 23 are controlled, and the copper X-ray tube 11 is controlled. And the position and rotation angle of the spectroscopic element 13 are set.

  In step SS1, the primary X-ray 12 from the copper X-ray tube 11 is made incident on the spectroscopic element 13 set at the diffraction angle and position to be monochromatized into Cu-Kα rays, and the monochromatized Cu- Irradiation of Kα rays is started. In step SS2, the measurement of the Cr-Kα ray 17 which is a fluorescent X-ray generated when the chromium contained in the sample is excited by the irradiated Cu-Kα ray is started by the SSD 18 as a detector.

  In step SS3, the X-ray tube position adjusting means 19 and the spectroscopic element position adjusting means 22 are controlled by the control means 20, whereby the copper X-ray tube 11 and the spectroscopic element 13 are simultaneously set at the same distance and centered at the set position. And move to a position where the intensity of the Cr-Kα line 17 measured by the SSD 18 becomes maximum. The irradiation position of the Cu—Kα ray on the sample 16 is adjusted by the linear parallel movement of the copper X-ray tube 11 and the spectroscopic element 13.

  Other analysis conditions are also set by the analysis condition setting means 26 in step S12. In step S15, the sample 16 arranged in step S11 is analyzed. In step S16, it is determined whether or not to analyze the next sample. When analyzing the next sample, the sample is placed at the measurement position in step S17, and the process returns to step SS1, and from steps X1 to SS3, the intensity of fluorescent X-rays generated from the sample is maximized. The irradiation position of the primary X-ray sample is automatically adjusted, and the sample is analyzed in step S15. In the same manner, the remaining samples are analyzed. When the next sample is not analyzed, the operation of the total reflection fluorescent X-ray analyzer 1 is completed, and the X-ray irradiation and fluorescent X-ray measurement on the samples of Steps SS1 and SS2 are also completed.

  When analyzing a plurality of samples having the same thickness, such as the polymer film of the above-described analysis example, fluorescence generated from the sample can be obtained by performing steps SS1 to SS3 only once as shown in the flowchart of FIG. Although the irradiation position of the primary X-ray sample from the X-ray source to the X-ray source can be automatically adjusted so as to maximize the X-ray intensity, Because the sample height differs, it is necessary to automatically adjust the irradiation position of the primary X-ray from the X-ray source to the sample so that the intensity of the fluorescent X-ray generated from the sample is maximized in steps SS1 to SS3 for each sample. There is.

  According to the total reflection X-ray fluorescence spectrometer of the fifth embodiment, the irradiation position and irradiation angle of the primary X-ray sample are automatically set according to the offset amount obtained using the optical axis automatic adjustment sample. Therefore, even if the sample surface is a sample such as a polymer film or hair whose surface is higher than the reference plane, the sample is irradiated with primary X-rays by linearly moving back and forth between the X-ray tube and the spectroscopic element without adjusting the irradiation angle. By adjusting the position, it can be adjusted to the optimal position and the optimal angle, and analysis with high sensitivity and high accuracy can always be performed in a short time.

  As an example of the device according to the fifth embodiment, a device in which a part of the control content of the device according to the first embodiment is changed has been described as an example. However, the control content of the device according to the second to fourth embodiments may be similarly changed. And similar effects can be obtained. In the first to fifth embodiments, the total reflection X-ray fluorescence analyzer has been described. However, the present invention can also be applied to an X-ray fluorescence analyzer other than the total reflection X-ray fluorescence analyzer.

1 is a schematic view of a total reflection X-ray fluorescence spectrometer that is a first embodiment of the present invention. FIG. It is a basic operation explanatory view of the X-ray source position, the spectroscopic element position and the angle adjustment of the total reflection fluorescent X-ray analyzer. It is a step operation | movement flowchart which memorize | stores the offset amount of the said total reflection X-ray fluorescence analyzer. It is an operation | movement flowchart at the time of unknown sample measurement of the said total reflection X-ray fluorescence analyzer. It is the schematic of the total reflection X-ray fluorescence spectrometer which is 2nd Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of the said total reflection X-ray fluorescence analyzer. It is explanatory drawing of the critical angle in the same total reflection fluorescent-X-ray-analysis apparatus. It is the schematic of the total reflection X-ray fluorescence spectrometer which is 3rd Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of the said total reflection X-ray fluorescence analyzer. It is the schematic of the total reflection X-ray fluorescence analyzer which is 4th Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of the said total reflection X-ray fluorescence analyzer. It is an operation | movement flowchart at the time of the polymer film measurement of the total reflection fluorescent-X-ray-analysis apparatus which is 5th Embodiment of this invention. It is an operation | movement flowchart at the time of the hair measurement of the total reflection X-ray fluorescence analyzer which is 5th Embodiment of this invention.

Explanation of symbols

1, 3, 8, 10 Total reflection fluorescent X-ray analyzer 11 Copper X-ray tube 12 Primary X-ray 13 Spectroscopic element 14 Cr-Kα ray (X-ray of a predetermined wavelength)
15 Sample substrate 16 Sample 17 X-ray fluorescence 18 Detector (SSD)
19 X-ray tube position adjustment means 20 Control means 21 X-ray tube offset distance storage means 22 Spectroscopic element position adjustment means 23 Spectroscopic element angle adjustment means 24 Spectroscopic element offset distance storage means 25 Spectroscopic element offset angle storage means 26 Analysis condition setting means 51 Critical angle calculation means 52 X-ray irradiation angle correction means 81 Molybdenum X-ray tube 82 Selection means

Claims (4)

A single X-ray source;
A spectroscopic element that divides X-rays generated from the X-ray source and irradiates a sample on a sample substrate with X-rays having a predetermined wavelength;
A detector for measuring the intensity of fluorescent X-rays generated from the sample;
An X-ray fluorescence analyzer comprising analysis condition setting means for setting analysis conditions,
X-ray source position adjusting means for adjusting the position of the X-ray source;
A spectroscopic element position adjusting means for adjusting the position of the spectroscopic element;
A spectral element angle adjusting means for adjusting a rotation angle of the spectral element;
Control means for controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means and the spectroscopic element angle adjusting means based on the intensity of fluorescent X-rays generated from the sample measured by the detector;
The distance between the X-ray source position adjusted by the X-ray source position adjusting means and the corresponding position on the mechanism of the X-ray source is stored as an X-ray source offset distance with respect to the X-ray source position origin, and the stored X-ray X-ray source offset distance storage means for providing a source offset distance to the analysis condition setting means;
The distance between the spectroscopic element position adjusted by the spectroscopic element position adjusting means and the corresponding position on the spectroscopic element mechanism is stored as a spectroscopic element offset distance with respect to the spectroscopic element position origin, and the stored spectroscopic element offset distance is stored as the analysis condition. A spectroscopic element offset distance storage means to be provided to the setting means;
The difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjusting means and the corresponding angle on the spectroscopic element mechanism is stored as a spectroscopic element offset angle with respect to a reference plane, and the stored spectroscopic element offset angle is set as the analysis condition setting. Spectroscopic element offset angle storage means to be provided to the means,
An X-ray fluorescence analyzer that automatically adjusts the irradiation position and the irradiation angle of primary X-rays from the X-ray source to the sample so that the intensity of fluorescent X-rays generated from the sample is maximized. In Claim 1, further, a critical angle calculation means for calculating a critical angle of the X-ray irradiation angle based on the X-ray irradiation angle to the sample substrate and the intensity of fluorescent X-rays generated from the sample substrate;
An X-ray fluorescence analyzer comprising: an X-ray irradiation angle correction unit that corrects an X-ray irradiation angle to the sample based on the critical angle calculated by the critical angle calculation unit. A plurality of x-ray sources;
Selecting means for selecting one X-ray source from the plurality of X-ray sources;
A spectroscopic element that divides X-rays generated from the X-ray source selected by the selection unit and irradiates the sample on the sample substrate with X-rays having a predetermined wavelength;
A detector for measuring the intensity of fluorescent X-rays generated from the sample;
An X-ray fluorescence analyzer comprising analysis condition setting means for setting analysis conditions,
X-ray source position adjusting means for adjusting the position of the selected X-ray source;
A spectroscopic element position adjusting means for adjusting the position of the spectroscopic element;
A spectral element angle adjusting means for adjusting a rotation angle of the spectral element;
Control means for controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means and the spectroscopic element angle adjusting means based on the intensity of fluorescent X-rays generated from the sample measured by the detector;
The distance between the X-ray source position adjusted by the X-ray source position adjusting means and the corresponding position on the mechanism of the X-ray source is stored as an X-ray source offset distance with respect to the X-ray source position origin, and the stored X-ray X-ray source offset distance storage means for providing a source offset distance to the analysis condition setting means;
The distance between the spectroscopic element position adjusted by the spectroscopic element position adjusting means and the corresponding position on the spectroscopic element mechanism is stored as a spectroscopic element offset distance with respect to the spectroscopic element position origin, and the stored spectroscopic element offset distance is stored as the analysis condition. A spectroscopic element offset distance storage means to be provided to the setting means;
The difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjusting means and the corresponding angle on the spectroscopic element mechanism is stored as a spectroscopic element offset angle with respect to a reference plane, and the stored spectroscopic element offset angle is set as the analysis condition setting. Spectroscopic element offset angle storage means to be provided to the means,
An X-ray fluorescence analyzer that automatically adjusts the irradiation position and the irradiation angle of primary X-rays from the X-ray source to the sample so that the intensity of fluorescent X-rays generated from the sample is maximized. In Claim 3, further, a critical angle calculation means for calculating a critical angle of the X-ray irradiation angle based on the X-ray irradiation angle to the sample substrate and the intensity of fluorescent X-rays generated from the sample substrate;
An X-ray fluorescence analyzer comprising: an X-ray irradiation angle correction unit that corrects an X-ray irradiation angle to the sample based on the critical angle calculated by the critical angle calculation unit.

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