JP4522438B2 - Oblique-incidence X-ray fluorescence spectrometer with sample holder - Google Patents

Description

  The present invention includes an X-ray source that irradiates a sample with primary X-rays, a detector that detects fluorescent X-rays generated from the sample irradiated with the primary X-rays, and a simple and inexpensive sample holder. Thus, even with samples of various shapes, the oblique X-ray fluorescence X-ray analyzer capable of setting an accurate sample position and the offset storage means further provide the maximum intensity of fluorescent X-rays generated from the sample. It is related with the oblique incidence fluorescent X-ray analyzer which adjusts automatically the irradiation position and irradiation angle of the primary X-ray from an X-ray source.

  In an oblique-incidence fluorescent X-ray analyzer, particularly a total reflection X-ray fluorescence analyzer, the irradiation angle of the primary X-ray irradiated to the sample is extremely high, for example, 0.05 ° to 0.25 °. If the angle is low and the sample position is not set to such a total reflection angle, the analysis sensitivity is greatly reduced, and analysis cannot be performed, or the accuracy and precision of the analysis are significantly reduced.

  In such a case, an XY stage that moves the sample stage on which the sample is placed in order to accurately set the sample position and a swivel stage that adjusts the X-ray incident angle on the sample analysis surface are provided. There is a total reflection fluorescent X-ray analyzer (see Patent Document 1). In addition, a total reflection fluorescent X-ray analysis that includes a control unit that controls the three-dimensional position and angle of the moving table according to the output of the second X-ray detection means that detects the reflected X-rays from the sample, and adjusts the sample position. There is a device (see Patent Document 2).

  Further, 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 the rotation angle of the spectral crystal A means for detecting the rotational position of the X-ray detector is provided, the position of the spectral crystal and the X-ray detector at which the detection output of the characteristic X-ray of the known element is maximized, and the X on the mechanism of the spectral crystal and the X-ray detector. There is a fluorescent X-ray analyzer that stores a difference from a position corresponding to a line wavelength as an offset amount and drives a spectroscopic crystal (see Patent Document 3).

Furthermore, in order to facilitate the fine alignment of the irradiation positions of the plurality of excitation X-rays on the sample surface, the irradiation position of the primary X-rays irradiated by each excitation X-ray on the sample surface and the origin of the sample stage The position deviation is obtained using a fluorescent plate, the obtained deviation amount is stored as an offset amount for each excitation X-ray source, and the sample stage is set so that the irradiation position and the origin of the sample stage coincide with each other using this offset amount. There is a fluorescent X-ray analyzer that corrects the position (see Patent Document 4).
Japanese Patent Laid-Open No. 10-185845 Japanese Patent Laid-Open No. 10-185846 JP-A 63-167250 JP 2003-149182 A

  However, in the conventional total reflection X-ray fluorescence analyzers described in Patent Documents 1 and 2, the sample solution is drip-dried on the surface of the silicon wafer, the impurities on the silicon wafer, the coating on the glass substrate, and the glass substrate. The thickness of the sample such as drip-dried traces is extremely thin, and it is designed to be compatible only with samples with a flat surface. For thick samples such as O-rings and pipes I can't respond.

  Further, in the conventional fluorescent X-ray analyzer described in Patent Document 3 and the like, the offset of the rotation mechanism of the spectral crystal, the X-ray detector, the sample stage, etc. is stored at the time of factory adjustment, and the stored offset is used. The position is set by driving these mechanisms, the offset amount is obtained as necessary at the time of measurement, the position is not set using the obtained offset amount, the position of the X-ray source and the position of the spectroscopic element The position and angle of primary X-rays from the X-ray source are automatically adjusted appropriately so that the intensity of fluorescent X-rays generated from the sample is maximized by controlling the angle. It does not maintain sensitivity and high accuracy. 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 analyzer, 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 or irradiation angle on the sample is shifted even a little, the sensitivity and analysis accuracy are greatly reduced. Therefore, even if the sample height is the same, such as a glass substrate on which a wafer or sample solution has been drip-dried, the sample stage is adjusted by a motor drive every time the measurement sample is replaced, and the irradiation position and irradiation angle are adjusted to the optimum conditions. 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.

  In addition, in a fluorescent X-ray analyzer that has a plurality of X-ray sources described in Patent Document 4 and selects and uses an X-ray source according to the purpose of analysis, the sample is irradiated every time the X-ray source is replaced. Since the measurer was performing the analysis while checking whether the position and the irradiation angle were not shifted, it took extra time to start the analysis.

  Therefore, in the present invention, a sample holder for fluorescent X-ray analysis that can deal with a thick sample, for example, a sample of various shapes such as an O-ring and a pipe, a sample contact portion that contacts the contact surface of the sample holder, Source position adjusting means, spectroscopic element position adjusting means, spectroscopic element angle adjusting means, etc., so that the X-ray source from the X-ray source can maximize the intensity of fluorescent X-rays generated from the sample even in various shapes. An oblique-incidence fluorescent X-ray analyzer that automatically adjusts the irradiation position of primary X-rays, and further includes an X-ray source position adjusting means, a spectroscopic element position adjusting means, and an offset storage means of a spectroscopic element angle adjusting means. Once a week, once a month, by automatically adjusting the irradiation position and angle of the primary X-ray from the X-ray source, even if you are not an expert in optical adjustment, it is always highly sensitive, Oblique incidence for high accuracy analysis And an object thereof is to provide an optical X-ray analyzer.

In order to achieve the above object, a first sample holder used in the present invention is a sample holder for a fluorescent X-ray analyzer having a sample contact portion for placing a sample at a predetermined height, and is a horizontal plane. A main body having an annular side portion and a bottom portion forming an abutting surface that abuts against the sample abutting portion, and a sample placed on the upper surface that is horizontally disposed inside the annular side portion. A sample mounting table to be placed, and a bottom end fixed to the bottom to support the sample mounting table and adjust at least three height adjusters.

According to the first sample holder used in the present invention , a surface that is the same height as the contact surface and is surrounded by the contact surface in plan view is a virtual analysis surface that is virtually assumed as the analysis surface of the sample. By adjusting the sample mounting table with the height adjusting tool, the analysis surface of the thick sample can be made the same height as this virtual analysis surface. When used in a grazing incidence X-ray fluorescence spectrometer, even on a thick sample, the surface of the silicon wafer, impurities on the silicon wafer, coating on the glass substrate, drip drying traces obtained by drip drying the sample solution on the glass substrate, etc. As in the case of a sample having a very thin sample thickness, the irradiation position and irradiation angle of the primary X-ray sample from the X-ray source can be adjusted.

The second sample holder used in the present invention is a sample holder for a fluorescent X-ray analyzer having a sample contact portion for arranging a sample at a predetermined height, and the upper surface which is a horizontal plane is the sample contact surface. A main body having an annular side part and a bottom part that form an abutting surface that comes into contact with the part, and a plastic material having an adhesive force in which the lower surface is attached to the inner surface of the bottom part and the lower surface of the sample is attached to the upper surface.

According to the second sample holder used in the present invention , the analysis surface of an irregular sample having a non-constant shape or a sample having a large thickness is made to be an analysis surface of a sample having a large thickness by the plastic material having adhesive force. Can be the same height. When used in a grazing incidence X-ray fluorescence spectrometer, even on a thick sample, the surface of the silicon wafer, impurities on the silicon wafer, coating on the glass substrate, drip drying traces obtained by drip drying the sample solution on the glass substrate, etc. As in the case of a sample having a very thin sample thickness, the irradiation position and irradiation angle of the primary X-ray sample from the X-ray source can be adjusted. The first and second sample holders are sample holders for a fluorescent X-ray analyzer having a sample contact portion for placing a sample at a predetermined height, and the upper surface which is a horizontal plane is the sample contact surface. This is common in that it has a main body having an annular side part and a bottom part that form a contact surface that contacts the part.

The oblique incidence fluorescent X-ray analyzer according to the first configuration of the present invention is a sample holder for a fluorescent X-ray analyzer having a sample contact portion for arranging a sample at a predetermined height, and is a horizontal plane. It has a sample holder having a body whose upper surface has a side and bottom of the annular forming an abutment surface which abuts on the sample contact portion, and a holding portion for holding the sample contact portion and the sample contact portion Contact means, pressing means for pressing the contact surface of the sample holder against the sample contact portion, an X-ray source, and X-rays generated from the X-ray source are dispersed to generate X-rays having a predetermined wavelength. Reflected by the X-rays of the predetermined wavelength and the sample in the gap between the spectroscopic element for irradiating the sample placed on the sample holder, and the contact surface of the sample holder and the sample facing surface of the holding unit of the contact means X-ray passage for allowing reflected X-rays to pass through, and fluorescence X generated from the sample A detector that measures the intensity of the X-ray, an X-ray source position adjusting unit that adjusts the position of the X-ray source, a spectral element position adjusting unit that adjusts the position of the spectral element, and a rotation angle of the spectral element Control 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 spectroscopic element angle adjusting means and the sample measured by the detector. Means for automatically adjusting the irradiation position of the primary X-ray from the X-ray source onto the sample so that the intensity of fluorescent X-rays generated from the sample is maximized.

  The oblique-incidence X-ray fluorescence analyzer of the present invention has a primary X-ray irradiation angle (also referred to as a viewing angle) of 6 ° or less, preferably 2 ° or less, and the irradiation angle is a total reflection critical angle. A total reflection X-ray fluorescence analyzer is included.

According to the oblique-incidence X-ray fluorescence spectrometer according to the first configuration, the analysis surface of various shapes such as an indeterminate shape sample and a thick sample is flush with the contact surface of the sample holder. A sample holder that can be substantially adjusted to the height of the virtual analysis surface, a sample abutting portion that abuts on the abutting surface of the sample holder, an X-ray source position adjusting unit, a spectroscopic element position adjusting unit, a spectroscopic element angle adjusting unit, and the like. Therefore, even if the sample has various shapes, it is a flat sample with a very thin sample thickness, such as the surface of a silicon wafer, a coating on a glass substrate, or a drip-dried trace in which a sample solution is drip-dried on a glass substrate. In the same manner as described above, the contact surface of the sample holder is in contact with the sample contact portion, and the analysis surface of the sample is always set to a substantially constant inter-surface distance with respect to the light receiving surface of the detector. Primary from the X-ray source so that the intensity of It can be accurately in a short time automatic adjustment of the irradiation position of the line.

The oblique incidence fluorescent X-ray analyzer according to the second configuration of the present invention is a sample holder for a fluorescent X-ray analyzer having a sample contact portion for arranging a sample at a predetermined height, and is a horizontal plane. A sample holder having a main body having an annular side portion and a bottom portion, the upper surface of which forms an abutting surface that abuts against the sample abutting portion; and a holding portion for holding the sample abutting portion and the sample abutting portion An abutting means, an X-ray source, an analysis surface of a reference substrate or a contact surface of the sample holder as a reference for automatically adjusting the irradiation position and the irradiation angle of the primary X-ray from the X-ray source to the sample A pressing means that presses the sample against the sample abutting portion, and a sample placed on the reference substrate or the sample holder by dispersing X-rays generated from the X-ray source and emitting X-rays having a predetermined wavelength. And the spectroscopic element for irradiating the sample, the analysis surface of the reference substrate or the sample An X-ray path through which X-rays of the predetermined wavelength and reflected X-rays reflected by the sample pass in a gap between the contact surface of the rudder and the sample-facing surface of the holding unit of the contact means, and fluorescence X generated from the sample Analysis conditions are set using a detector that measures the intensity of the line and the contact surface of the sample holder that is the same height as the contact surface of the sample holder and that is surrounded by the contact surface in a plan view. An oblique-incidence X-ray fluorescence analysis apparatus comprising: an analysis condition setting unit that performs an X-ray source position adjustment unit that adjusts the position of the X-ray source; and a spectral element position adjustment unit that adjusts the position of the spectral element And a spectral element angle adjusting means for adjusting the rotation angle of the spectral element.

  Furthermore, based on the intensity of fluorescent X-rays generated from the sample measured by the detector, control means for controlling the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means, By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 set. X-ray source offset distance with respect to the X-ray source position origin, X-ray source offset distance storage means for giving the stored X-ray source offset distance to the analysis condition setting means, and a predetermined sample on the reference substrate By irradiating the wavelength X-ray, 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 set as the spectroscopic element offset with respect to the spectroscopic element position origin. Stored as preparative distance, and a spectroscopic element offset distance storage means for imparting a spectral element offset distance described above stored in the analysis condition setting unit.

Further, by irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 determined. Spectroscopic element offset distance storage means for storing the spectral element offset distance with respect to the position origin, and applying the stored spectral element offset distance to the analysis condition setting means, and irradiating the sample on the reference substrate with X-rays of a predetermined wavelength Thus, the angle 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 stored. the provided spectral element offset angle storage means for imparting to said analysis condition setting means, said control means, on the reference substrate The irradiation position and the irradiation angle of the primary X-ray from the X-ray source to the sample are automatically adjusted so that the intensity of the fluorescent X-ray generated from the sample is maximized, or the fluorescence X generated from the sample on the sample holder The irradiation position of the primary X-ray from the X-ray source onto the sample is automatically adjusted so that the intensity of the line is maximized.

According to the oblique-incidence fluorescent X-ray analyzer according to the second configuration, in addition to the oblique-incidence fluorescent X-ray analyzer according to the first configuration, the X-ray source position adjusting means, the spectroscopic element position adjusting means, and the spectroscopic element angle adjusting means In addition to the same effects as the first configuration of the oblique-incidence fluorescent X-ray analyzer, the X-ray source is appropriately selected, for example, once a week or once a month. By automatically adjusting the irradiation position and irradiation angle of the primary X-ray based on the offset amount given by the offset storage means, high-sensitivity and high-accuracy analysis can always be performed in a short time even for those who are not skilled in optical adjustment. It can be carried out.

  Calculate the critical angle so that the irradiation position and irradiation angle of the primary X-rays from the X-ray source to the sample can be automatically adjusted appropriately and more sensitive and accurate analysis can be performed. It is preferable to further include means and X-ray irradiation angle correction means.

The oblique incidence fluorescent X-ray analyzer according to the third configuration of the present invention is a sample holder for a fluorescent X-ray analyzer having a sample contact portion for arranging a sample at a predetermined height, and is a horizontal plane. A sample holder having a main body having an annular side portion and a bottom portion, the upper surface of which forms an abutting surface that abuts against the sample abutting portion; and a holding portion for holding the sample abutting portion and the sample abutting portion Contact means, a plurality of X-ray sources, a selection means for selecting one X-ray source from the plurality of X-ray sources, and a primary X-ray sample from the X-ray source selected by the selection means A pressing means for pressing the analysis surface of the reference substrate or the contact surface of the sample holder as a reference for automatically adjusting the irradiation position and the irradiation angle to the sample, and the X selected by the selection means Spectral X-rays generated from the radiation source to obtain X-rays of a predetermined wavelength A spectroscopic element for irradiating a sample on a reference substrate or a sample placed on the sample holder, an analysis surface of the reference substrate or a contact surface of the sample holder, and a sample facing surface of a holding portion of the contact means An X-ray path through which the X-ray having the predetermined wavelength and the reflected X-ray reflected by the sample pass in a gap, a detector for measuring the intensity of fluorescent X-rays generated from the sample, and a contact surface of the sample holder An oblique-incidence fluorescent X-ray analysis apparatus comprising analysis condition setting means for setting an analysis condition with the same height and a plane surrounded by the contact surface in plan view as a virtual sample analysis plane , X-ray source position adjusting means for adjusting the position of the X-ray source, and spectroscopic element position adjusting means for adjusting the position of the spectroscopic element.

  In addition, based on the intensity of fluorescent X-rays generated from the sample measured by the detector, the X-ray source position adjusting means, the spectroscopic element position based on the spectroscopic element angle adjusting means for adjusting the rotation angle of the spectroscopic element An X-ray source adjusted by the X-ray source position adjusting unit by irradiating the sample on the reference substrate with X-rays having a predetermined wavelength by controlling the adjusting unit and the spectroscopic element angle adjusting unit The distance between the position 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 source offset distance is given to the analysis condition setting means The source offset distance storage means and the spectroscopic element position adjusted by the spectroscopic element position adjusting means and the spectroscopic element mechanism by irradiating the sample on the reference substrate with X-rays of a predetermined wavelength Storing the distance between the response position as a spectroscopic element offset distance with respect to the spectroscopic element position origin, and a spectroscopic element offset distance storage means for imparting a spectral element offset distance described above stored in the analysis condition setting unit.

Further, by irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, the angle difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjusting means and the corresponding angle on the spectroscopic element mechanism is used as a reference. A spectroscopic element offset angle storage unit that stores the spectroscopic element offset angle with respect to a plane and applies the stored spectroscopic element offset angle to the analysis condition setting unit; and the control unit generates fluorescence from the sample on the reference substrate. The irradiation position and irradiation angle of the primary X-ray from the X-ray source to the sample are automatically adjusted so that the X-ray intensity is maximized, or the fluorescent X-ray intensity generated from the sample on the sample holder is maximized. The irradiation position of the X-ray source from the X-ray source onto the sample is automatically adjusted.

According to the oblique incidence X-ray fluorescence spectrometer according to a third configuration, the grazing incidence X-ray fluorescence spectrometer and the same operational effects of the second configuration is obtained from a plurality of X-ray source in accordance with the analytical purposes Even when the selected X-ray source is used, the intensity of fluorescent X-rays generated from the sample without the operator confirming that the irradiation position and angle of the sample are not shifted each time the X-ray source is replaced. The irradiation position and the irradiation angle of the primary X-ray from the selected X-ray source to the sample can be automatically and appropriately adjusted so that the analysis is always performed in a short time with high sensitivity and high accuracy. be able to.

  Calculate the critical angle so that the irradiation position and irradiation angle of the primary X-rays from the X-ray source to the sample can be automatically adjusted appropriately and more sensitive and accurate analysis can be performed. It is preferable to further include means and X-ray irradiation angle correction means.

In the oblique-incidence X-ray fluorescence analyzer of the first to third configurations, the primary X-ray from the X-ray source, the fluorescent X-ray generated on the reference substrate, the reflected X-ray reflected on the reference substrate, etc. It is preferable that the contact portion of the contact means is disposed outside the visual field region of the detector so that the contact portion is irradiated and the scattered X-rays do not enter the X-ray detector. In order for the analysis surface of the reference substrate to be always set to a constant inter-surface distance with respect to the light receiving surface of the detector, the influence of the thermal expansion of the abutting portion due to fluctuations in the ambient temperature due to primary X-ray irradiation etc. is minimized Therefore, it is preferable to be made of ceramics with low thermal expansion. In addition, in order to prevent the contact portion from corroding due to the corrosive components contained in the sample and the corrosive material from adhering to the reference substrate or the measurement portion of the oblique incidence fluorescent X-ray analyzer, the contact means is applied. The contact portion is preferably made of ceramic, and more preferably a ceramic ball.

  A sample holder according to a first embodiment of the present invention will be described with reference to FIGS. 1A, 1B, and 1C. As shown in FIG. 1A, the sample holder 1 is formed by a square annular side portion 11 and a bottom portion 13 that form a contact surface with which the upper surface, which is a horizontal plane, contacts the sample contact portion of the fluorescent X-ray analyzer. A sample is placed horizontally inside the main body 18 and the side 11 of the square ring shape, and a sample is placed on the horizontal upper surface, and a lower end 142a (see FIG. 1C) is fixed to the bottom 13 and the sample. It has at least three height adjusters 15 that support the mounting table 14 and adjust its height.

  The square annular portion 101 and the bottom portion 13 are formed of integral aluminum, and a stainless steel square annular plate 102 having a horizontal upper surface forming a contact surface 104 is fixed to the upper portion of the square annular portion 101 by a fixing screw 103. The outer dimensions of the square annular plate 102 are, for example, 100 mm in width, 100 mm in length, 4 mm in thickness, the inner dimensions are 80 mm in width and 80 mm in length, and a notch 105 having a width of 40 mm and a depth of 1 mm is provided on one side. Have. At the time of sample measurement, the notch 105 is arranged on the sample stage so as to be in the incident direction of the primary X-ray. The square annular portion 101 and the square annular plate 102 form a square annular side portion 11. The external dimensions of the main body 18 are, for example, 100 mm in width, 100 mm in length, and 10 mm in height.

  The upper surface of the square annular plate 102 acts as the contact surface 104 and contacts the sample contact portion of the fluorescent X-ray analyzer at the time of analysis, whereby the sample holder 1 is held at a predetermined height. In the sample holder 1, the surface that is the same height as the contact surface 104 and is surrounded by the contact surface 104 in plan view is the above-described virtual analysis surface. The contact surface 104 of the sample holder 1 has a polished flatness, and is a material that is not easily deformed or worn by repeated contact with the sample contact portion of the fluorescent X-ray analyzer, Materials that are resistant to corrosion by acids and the like are required. In the present embodiment, the square annular portion 101 and the bottom portion 13 are integrally formed, but may be separate. Although the annular side portion is divided into the square annular portion 101 and the square annular plate 102 and formed separately, they may be integrated.

  As shown in FIG. 1C, which is a cross-sectional view taken along the line I-I of FIG. 1B, the sample mounting table 14, which is a square stainless steel plate on which the sample is mounted, is supported by four height adjusters 15. The height adjustment tool 15 is fixed to the bottom 13. The four height adjusters 15 are respectively provided at the four corners of the square of the sample mounting table 14, and the lower end 142 a is formed at the bottom 13 through the screw holes respectively provided at the four corners of the square of the sample mounting table 14. The fixed adjustment screw 142 and the adjustment screw 142 are inserted inside, the compression coil spring 143 disposed between the lower surface and the bottom portion 13 of the sample mounting table 14, and the adjustment screw 142 inserted on the upper surface of the sample mounting table 14. A spherical washer 145 and a nut 144 that is in contact with the upper surface of the spherical washer 145 and screwed with the adjusting screw 142 are configured. By rotating the nut 144, the sample mounting table 14 is moved up and down, and the height of the sample mounting table 14 is adjusted. By appropriately selecting the length of the square annular side portion 11 and the adjusting screw 142, it is possible to cope with various sample shapes. The height adjuster is not limited to four, but may be at least three.

  For example, when the sample holder 1 is used with an O-ring as a sample, first, the O-ring is mounted so that the ring portion is positioned at the approximate center of the sample mounting table 141, and the nuts 144 at the four corners are rotated. Adjust the upper surface of the O-ring visually so that it is flush with the virtual analysis surface. In addition, you may hold | maintain with a double-sided adhesive tape etc. so that a sample may not move on the sample mounting base 141. FIG.

  For example, when O-rings having the same dimensional standard are continuously analyzed, the height of the analysis surface of the O-ring placed on the sample mounting table 141 is the same, so the height of the sample mounting table 141 needs to be adjusted. There is no. When analyzing samples with different analysis surface heights, the upper surface of the sample is adjusted to be flush with the virtual analysis surface in the same manner as described above.

  According to the sample holder 1 of the first embodiment, the analysis surface of samples of various shapes can be adjusted to a virtual analysis surface, which is the same as the fluorescent X-ray analysis using the surface of a silicon wafer or a film of a glass substrate as a sample. In addition, the irradiation position of the primary X-ray from the X-ray source can be easily and automatically adjusted so that the intensity of the fluorescent X-ray generated from the sample is maximized.

  A sample holder according to a second embodiment of the present invention will be described with reference to FIG. As shown in FIG. 2, the sample holder 2 has a square-shaped side portion 21 and a bottom portion 23 formed of aluminum, which form a contact surface 204 whose upper surface, which is a horizontal surface, contacts the sample contact portion of the fluorescent X-ray analyzer. It has a main body 28 formed integrally, and a plastic material 24 having an adhesive force in which the lower surface is attached to the inner surface 23a of the bottom 23 and the lower surface of the sample is attached to the upper surface. Further, similarly to the sample holder 1, a cutout portion 206 is provided on one side of the upper surface of the square annular side portion 21. The upper surface of the square annular side portion 21 acts as the contact surface 204 and contacts the sample contact portion of the fluorescent X-ray analyzer during analysis. In the sample holder 2, the surface that is the same height as the contact surface 204 and is surrounded by the contact surface 204 in plan view is the above-described virtual analysis surface.

  For example, three screw holes 205 for the sample fixing screw 203 for fixing the sample attached to the gel clay 24 are provided on each surface of the square annular side portion 21. One or a plurality of screw holes 205 may be used, and may be appropriately selected according to the shape of the sample. The fixing screw 203 does not have to be attached to all the screw holes 205, and may be appropriately selected according to the shape of the sample. . As a method for fixing the sample attached to the gel clay 24, a flat plate may be provided at the tip of the fixing screw, and the sample may be sandwiched between the flat plates like a vise. By appropriately selecting the height of the square ring-shaped side portion 21 and the amount of the gel clay 24, it is possible to cope with various sample shapes such as glass pieces and quartz pieces.

  For example, in the case of using the sample holder 2 with a glass piece as a sample, first, the lower surface of the glass piece is attached to the gel clay 24 at substantially the center position of the inner surface 23a of the bottom, and the upper surface of the glass piece is visually determined as the virtual analysis surface. Adjust to be flush. Since the gel clay is plastic, when analyzing other samples, the same gel clay may be used, or the gel clay 24 used in the previous sample may be removed and replaced with a new gel clay 24. . In either case, the upper surface of the sample is adjusted to be flush with the virtual analysis surface in the same manner as described above.

  According to the sample holder 2 of the second embodiment, it is possible to adjust the analysis surface of a sample of various shapes such as a sample whose analysis surface and adhesion surface are not parallel to the virtual analysis surface, and the surface of the silicon wafer or the coating of the glass substrate As in the total reflection X-ray fluorescence analysis using the sample, the irradiation position of the primary X-ray from the X-ray source can be easily and automatically adjusted so that the intensity of the fluorescent X-ray generated from the sample is maximized.

  In the sample holders 1 and 2 of the first and second embodiments, the main bodies 18 and 28 have square annular side portions and bottom portions, but rectangular annular side portions and bottom portions, annular annular side portions and bottom portions. And so on.

  The oblique incidence fluorescent X-ray analyzer according to the third embodiment of the present invention will be described below with reference to FIGS. As shown in FIG. 3, the oblique incidence fluorescent X-ray analyzer 6 includes an X-ray source 3 including a copper X-ray tube 31 and a spectroscopic element 33 formed of, for example, a cumulative multilayer film, a measurement unit 4, and a control unit 5. It consists of and. A primary X-ray 34 obtained by monochromatizing the X-ray 32 from the copper X-ray tube 31 into a Cu-Kα ray by the spectroscopic element 33 is applied to the sample S placed on the sample holder 1, for example, a semiconductor detector (SSD, The X-ray tube position adjusting means 55, the spectroscopic element position adjusting means 57, and the spectroscopic element angle adjusting means 58 based on the intensity 36 of fluorescent X-rays generated from the sample S measured by the detector 37 which is SDD, Si / PIN, etc. The position of the primary X-ray irradiated from the X-ray source 3 to the sample S is automatically adjusted by the control unit 5 including the control means 56 for controlling the intensity so that the intensity of the fluorescent X-rays 36 generated from the sample S is maximized. The components contained in the sample S are quantitatively and qualitatively analyzed.

  At the time of sample measurement, as shown in the measurement unit 4 of FIG. 4, the sample holder 1 is placed on a sample stage 50 having a structure having a pressing means passage hole 52 through which the pressing means 40 passes, and the bottom 13 of the sample holder 1 is placed. Is pressed by the pressing means 40, and the contact surface 104 of the holder contact portion of the sample holder 1 contacts the ceramic ball 47 made of alumina which is the sample contact portion held by the holding portion 46 of the contact means 45. In contact with each other, the sample S is set at a predetermined position. When the contact surface 104 of the sample holder 1 contacts the ceramic ball 47, the gap between the contact surface 104 of the sample holder 1 and the sample facing surface of the holding portion 46 of the contact means 45 becomes the primary X-ray 34 and It becomes the X-ray passage 39 of the reflected X-ray 38 reflected by the sample S. The reflected X-rays 38 reflected by the sample S travel in the right direction of the page as shown in FIG.

  As shown in FIG. 4, the pressing means 40 includes, for example, a rubber ring 41 that is an elastic body fixed on the pressing block 42, a pressing block 42, and a pivot 43. 43 is fitted. The pressing means 40 is driven up and down to press the contact surface 104 of the sample holder 1 against the ceramic ball 47 and presses the outer surface of the bottom 13 of the sample holder 1. The vertical driving of the pressing means 40 is driven and controlled to a predetermined position by a stepping motor, a gear mechanism, a drive control unit, etc. (not shown).

  When the rubber ring 41 presses the outer surface of the bottom portion 13 of the sample holder 1, the rubber ring 41 can alleviate the impact when the pressing means 40 hits, prevent the sample holder 1 from slipping, and set the sample holder 1 at a predetermined position. I am doing so. The rubber ring 41, which is an elastic body, may be a ring shape or a plate shape formed of a plate rubber or an elastic resin. The pivot 43 is configured to be fitted to the pressing block 42 in order to prevent the pressing force in the side-sliding direction from being applied to the sample holder 1. However, even if the fitting structure is not such, the sample holder 1 is prevented from sliding. Any structure can be used.

  As shown in the measurement unit 4 of FIG. 5, the contact means 45 includes a ceramic ball 47 that is a sample contact portion, and a holding unit 46 that holds the ceramic ball 47 so as to protrude from a surface 46 a facing the sample S. Have For example, an alumina ball having a diameter of 7 mm, which is a ceramic ball, is fixed to the stainless steel holding portion 46 with an adhesive so as to protrude 2 mm from the sample facing surface 46a of the holding portion 46. The diameter of the ceramic ball is preferably 2 to 10 mm, and the protruding dimension of the holding portion 46 from the sample facing surface 46a is preferably 1 to 2 mm. The sample contact portion is not limited to the ball shape, and may be a disc shape, a ring shape, an arc shape, a rectangular shape, or the like.

  The sample abutting portion abuts on the abutting surface 104 of the sample holder 1, and the analysis surface of the sample S needs to be always set to a constant plane height with high accuracy with respect to the light receiving surface of the light receiving element 37a of the detector. Alumina is a preferred material for the sample abutting portion because it does not deform or wear due to repeated contact with the abutting surface 104 of the sample holder. Alumina is a preferred material because it is not easily corroded. The ceramic of the contact portion is not limited to alumina, but may be other ceramics.

  In the third embodiment, a ceramic ball is used for the sample contact portion 47, but it can be appropriately configured such as using artificial diamond.

  The detector 37 is disposed through the center of the contact means 45 so that the light receiving surface of the light receiving element 37 a faces the sample S, and a detector holder 48 is provided above the holding portion 46 of the contact means 45. (See FIG. 4). The contact means 45 is held by a holding mechanism (not shown). In the present embodiment, the detector 37 is held by the holding portion 46 of the contact means, but may be held by a separate holder.

  As shown in FIG. 5, the detector 37 includes a light receiving element 37a that detects incident X-rays in a light receiving portion, a collimator 37b having a light receiving opening 37c that is an X-ray incident opening, and a cylinder that holds the light receiving element 37a and the collimator 37b. A beryllium window (not shown) is provided on the portion 37d and the light receiving opening 37c. The structural dimensions of the light receiving element 37a of the detector, the structural dimensions of the collimator 37b such as the light receiving opening 37c, the distance between the sample facing surface of the light receiving opening 37c and the virtual analysis surface of the sample holder 1, and the light receiving surface of the light receiving element 37a and the sample holder 1 As shown in FIG. 5, the visual field region R of the detector 37 surrounded by the visual field line A and the visual field line B can be obtained from the distance to the virtual analysis plane. In this embodiment, the light receiving element 37a receives light. The surface is circular, the light receiving opening 37c is a cylindrical space, and the visual field region R is circular with a diameter of 9 mm.

  Further, the gap between the contact surface 104 of the sample holder 1 and the analysis surface of the sample S and the sample facing surface of the holding unit 46 of the contact means is the primary X-ray 34 (FIG. 3) from the X-ray source 3 (FIG. 3). 4) and an X-ray passage L through which the reflected X-rays 38 (FIG. 4) reflected by the contact surface 104 and the analysis surface of the sample S pass, and the surface 37e facing the sample S of the detector 37 also holds the contact means. The portion 46 is substantially at the same height as the sample facing surface 46a and forms part of the X-ray passage L. In the present embodiment, the X-ray path L is a very narrow gap of about 2 mm, and the field of the detector 37 has a 9 mm diameter circle (field region R) on the virtual analysis surface of the sample holder 1 as the bottom surface. Since it is in a truncated cone having a height of about 2 mm with B as the ridgeline, scattered X-rays do not enter the detector 37.

  The ceramic balls 47 are irradiated with primary X-rays 34 irradiated to the sample S of the sample holder 1, reflected X-rays 38 reflected from the sample S and the sample holder 1, fluorescent X-rays 36 generated from the sample S, and the like. Scattered X-rays from the ceramic balls 47 are generated. At this time, if the ceramic ball 47, which is the sample contact portion, is in the visual field region, this scattered X-ray enters the detector 37, and an analysis error is generated. Therefore, in the present invention, the ceramic balls 47 which are contact portions are arranged outside the visual field region R of the detector as shown in FIG. 6 (a plane below the detector holder 48 is shown).

  In order to bring the sample holder 1 into contact with the sample holder 1 stably and accurately, two ceramic balls 47a to 47c are arranged on the incident X-ray side and one on the reflected X-ray side at the apex position of the isosceles triangle as shown in FIG. 3 points are supported. Further, ceramic balls 47d to 47f for supporting three reference substrates described later are further provided inside the ceramic balls 47a to 47c in the same isosceles triangle arrangement. When the ceramic balls 47 are arranged in this way, incident X-rays do not hit the ceramic balls 47a, 47b, 47d, 47e, but reflected X-rays 38 hit the ceramic balls 47f. However, since the ceramic balls 47a to 47f are arranged outside the visual field region R of the detector, the scattered X-rays by the reflected X-ray 38 do not enter the detector. In the present embodiment, the three ceramic balls are arranged at the vertex positions of the isosceles triangle, but may be arranged at the vertex positions of an equilateral triangle or an unequal triangle. Further, any of the ceramic balls 47a to 47f may be arranged so as not to hit the incident X-ray and the reflected X-ray.

  Next, the control unit 5 shown in FIG. 3 will be described. The X-ray tube position adjusting means 55, which is an X-ray source position adjusting means, is operated by an electric signal from the control means 56, for example, a copper X-ray by a pulse motor, a pulse motor drive circuit, a ball screw mechanism (or a rack and pinion mechanism), etc. This is a position adjusting means for linearly moving the tube 31 from the X-ray source position origin. The spectroscopic element position adjusting unit 57 is a position adjusting unit that linearly moves the spectroscopic element 33 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 electric signal from the control unit 56. The spectroscopic element 33 rotates about a rotation axis 138 that is on the reflecting 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 58 is a rotation adjusting means for rotating the spectroscopic element 33 from the reference plane by, for example, a pulse motor, a pulse motor drive circuit, a gear mechanism, or the like by an electric signal from the control means 56.

  The control means 56 is composed of, for example, a computer, and based on the fluorescent X-ray intensity measured by the detector 37, the control position of the copper X-ray tube 31 and the spectroscopic element 33 are added to the pulse motor drive circuit of each adjustment means 55, 57, 58. A control pulse signal corresponding to the control position and control angle is sent to control the control position of the copper X-ray tube 31 and the control position and control angle of the spectroscopic element 33.

  Next, the geometric positional relationship of each part in the oblique incidence fluorescent X-ray analyzer 6 of the third embodiment will be described.

  As shown in FIG. 7, the reference plane 160 is a plane including the contact surface 104 and the virtual analysis surface of the sample holder 1. The X-ray irradiation position 162 on the sample of the primary X-ray 34 obtained by monochromatizing the primary X-ray 32 from the copper X-ray tube 31 into Cu-Kα rays by the spectroscopic element 33 is such that the copper X-ray tube 31 is perpendicular to the reference plane 160. The first intersection 112 of the X-ray tube movement linear axis 111 that moves to the reference plane 160 and the reference plane 160, and the second intersection 132 of the spectroscopic element movement linear axis 131 that moves the spectroscopic element 33 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 S 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 34 is the sample. An angle between a straight line 161 that is an irradiation angle with which the irradiation surface is irradiated and the primary X-ray 34 is φ, and an angle formed between the reflection surface 136 of the spectroscopic element 33 and the reference plane 160 is a rotation angle Ω of the spectroscopic element 33. The viewing angle of the primary X-ray 32 from the copper X-ray tube 31 to the spectroscopic element 33, that is, the diffraction angle of the diffracted X-ray 34 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 tube position adjusting means 55 and the X-ray source position origin 112.

  In FIG. 7, 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 31 and the spectroscopic element 33 for changing the irradiation angle φ of the primary X-ray 34 to the sample S 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 33 and the wavelength of the Cu-Kα ray 34 which is a diffracted X-ray, and the distance between L1 and L2 is a fixed distance of the oblique incidence fluorescent X-ray analyzer 6. 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 31 and the spectroscopic element 33 are linearly moved by the position adjusting means 55 and 57 to appropriately change T and S, and the spectroscopic element angle adjusting means 58 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.

  Next, the operation when the sample holder 1 is used with the O-ring as a sample in the oblique incidence X-ray fluorescence spectrometer 6 of the third embodiment will be described with reference to the flowchart of FIG. The measurement operator operates the adjustment of the sample height of the sample holder 1 in step S1 to the virtual analysis surface, the arrangement of the sample holder 1 in step S2 and the automatic adjustment in step S3, and the oblique incident fluorescent X-ray analyzer 6 is It starts automatically from step S4. In step S 1, the O-ring is mounted so that the ring portion is positioned substantially at the center of the sample mounting table 14, and the nuts 144 at the four corners are rotated so that the upper surface of the O-ring is visually flush with the virtual analysis surface. (See FIGS. 1A and 1B). In step S2, it sets to the sample stand 50 so that the notch part 105 of the sample holder 1 in which the O-ring was mounted becomes the incident direction of a primary X-ray. In step S3, automatic adjustment of the irradiation position of the primary X-ray 34 from the X-ray source 3 to the sample S is selected.

  When measurement is started in step S4, the pressing means 40 driven by the drive controller passes through the pressing means passage hole 52 of the sample stage 50 and presses the lower surface of the bottom 13 of the sample holder 1 set on the sample stage 50. However, when the contact surface 104 of the sample holder contacts the ceramic ball 47, the stepping motor that drives the pressing means 40 stops, and the sample holder 1 is disposed at a predetermined position and held at that position. When the sample holder 1 is held at a predetermined position, the analysis surface of the sample S is always set to a substantially constant plane height with respect to the light receiving surface of the light receiving element 37a.

  In step S5, for example, the irradiation position of the primary X-ray 34 to the sample S is set near the center position where the sample S is initially set, and the irradiation angle is set to 0.05 °, for example, by each adjusting means 55, 57, 58. Is set. The irradiation angle can be set to any angle such as 0.05 °, 0.10 °, 0.20 °, and 2 °. In step S6, the X-ray 32 from the copper X-ray tube 31 is incident on the spectroscopic element 33 set at the diffraction angle and position for monochromatizing the Cu-Kα ray, and the sample S is monochromated Cu-Kα. The irradiation of the line 34 is started. In step S7, measurement of Cr-Kα ray 36, which is a fluorescent X-ray generated when chromium contained in sample S is excited by the irradiated Cu-Kα ray, is a detector, for example, SSD 37.

  In step S8, the X-ray tube position adjusting means 55 and the spectroscopic element position adjusting means 57 are controlled by the control means 56, so that the copper X-ray tube 31 and the spectroscopic element 33 are simultaneously set at the same distance and centered at the set position. To the position where the intensity of the Cr-Kα line 36 measured by the SSD 37 is maximized. The irradiation position of the Cu-Kα ray on the sample S is adjusted by the linear parallel movement of the copper X-ray tube 31 and the spectroscopic element 33.

  In step S9, the copper X-ray tube 31 is moved forward and backward by the X-ray tube position adjusting means 55 along the X-ray tube moving linear axis 111 around the position adjusted in step S8, and the Cr-Kα ray measured by the SSD 37 is measured. It adjusts to the position of the copper X-ray tube 31 where the intensity | strength of 36 becomes the maximum.

  In step S11, it is determined whether or not the steps S8 to S9 have been performed twice. If YES, the process proceeds to step S12 and the sample S is measured. If NO, the process returns to step S8. When the measurement is completed, the stepping motor driving the pressing unit 40 starts rotating, the pressing unit 40 is lowered, and the sample holder 1 is accommodated in the sample stage 50. Sequentially, the same number of samples are analyzed by the same operation. When the sample measurement is not continued, the operation of the oblique incidence fluorescent X-ray analyzer 6 is finished, and the X-ray irradiation and the fluorescent X-ray measurement on the sample S in steps S6 and S7 are also finished. In the present embodiment, steps S8 to S9 are performed twice, but may be one or three rounds as long as the number of times is appropriate.

  As described above, according to the apparatus of the third embodiment, the center of the light receiving surface of the light receiving element 37a of the detector, the center of the sample S, and the axis of the pivot 43 of the pressing means are located near the center line C shown in FIG. The sample holder 1 is set at a predetermined position, and the contact surface 104 of the sample holder 1 pressed by the pressing means 40 is in contact with the ceramic ball 47 so that the sample S is analyzed. The face is always set to a substantially constant height.

  As described above, the analysis surface of the sample S having various shapes such as an irregular sample having a non-uniform shape or a sample having a large thickness can be adjusted to substantially the same height as the virtual analysis surface of the sample holder 1, and the sample holder 1 Since the sample abutting portion 47 that abuts against the abutting surface 104, the X-ray source position adjusting means 55, the spectroscopic element position adjusting means 57, the spectroscopic element angle adjusting means 58 and the like are provided, the sample S can be variously shaped. In addition, the contact surface 104 of the sample holder 1 is similar to a sample having a very thin planar shape such as a silicon wafer surface, a coating on a glass substrate, and a drip drying trace obtained by drip drying a sample solution on a glass substrate. Abutting on the sample abutting portion 47, the analysis surface of the sample S is always set to a substantially constant distance from the light receiving surface of the detector 37, and the intensity of the fluorescent X-rays 36 generated from the sample S is maximized. Primary X from X-ray source 3 Automatic adjustment of 34 irradiation position can be accurately in a short time.

  As the X-ray source 3, an X-ray tube such as tungsten, copper, chromium, molybdenum, platinum, rhodium, or palladium, a rotor target X-ray tube, or the like is used according to the analysis purpose. In addition, it can be appropriately configured by using a crystal such as germanium or graphite, a cumulative multilayer film, or the like.

  The oblique incidence fluorescent X-ray analyzer of the fourth embodiment will be described. As shown in FIG. 9, the oblique-incidence fluorescent X-ray analyzer 7 of the fourth embodiment is further added to the oblique-incidence fluorescent X-ray analyzer 6 of the third embodiment in addition to an X-ray tube offset as X-ray source offset distance storage means. A distance storage unit 61, a spectroscopic element offset distance storage unit 62, a spectroscopic element offset angle storage unit 63, an analysis condition setting unit 60, a reference substrate 70, and a sample turret 80 on which the reference substrate 70 is placed. A sample turret 80 shown in FIGS. 10A and 10B is provided above the sample stage 50 of the oblique incidence fluorescent X-ray analyzer 6 of the third embodiment. The disc-shaped sample turret 80 has 16 substrate mounting grooves 81 and pressing means passage holes 82 in the circumferential direction on the substrate mounting table 83, and 16 reference substrates 70 and 16 glass substrates as sample substrates are mounted. When the measurement of the first sample is completed by a sample turret control unit (not shown), the sample turret 80 rotates in the circumferential direction, the second sample is set at the measurement position, and the placed sample is sequentially set at the measurement position. To do. The analysis surface of the reference substrate 70 becomes a reference plane 160 (see FIG. 7) for automatically adjusting the irradiation position and the irradiation angle of the primary X-ray 34 from the X-ray source 3 to the sample S.

  In FIG. 9, the X-ray tube offset distance storage means 61 uses the distance difference between the X-ray tube position adjusted by the X-ray tube position adjusting means 55 and the corresponding position on the mechanism of the X-ray tube as the X-ray tube position origin. The stored X-ray tube offset distance is stored, and the stored X-ray tube offset distance is given to the analysis condition setting means 60. The spectroscopic element offset distance storage means 62 stores the distance difference between the spectroscopic element position adjusted by the spectroscopic element position adjustment means 57 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 60. The spectroscopic element offset angle storage means 63 is a reference plane 160 which is a plane including the analysis surface of the reference substrate, which is an angular difference between the spectroscopic element rotation angle adjusted by the spectroscopic element angle adjustment means 58 and the corresponding angle on the mechanism of the spectroscopic element. Is stored as a spectral element offset angle, and the stored spectral element offset angle is applied to the analysis condition setting means 60. The X-ray tube position storage unit 61, the spectroscopic element offset distance storage unit 62, and the spectroscopic element offset angle storage unit 63 are configured by a computer, for example.

  Based on the X-ray tube offset distance, the spectroscopic element offset distance, and the spectroscopic element offset angle given from the storage units 61, 62, and 63, the analysis condition setting unit 60 applies the primary X-ray 34 to the sample S on the reference substrate. By setting the irradiation position and the irradiation angle, X-rays 32 from the copper X-ray tube 31 are Cu− with the spectroscopic element 33 so that the intensity of the fluorescent X-rays 36 generated from the sample S on the reference substrate is maximized. The irradiation position and the irradiation angle of the sample S on the reference substrate of the primary X-ray 34 monochromatic to Kα rays are automatically adjusted.

  The geometric positional relationship of each part in the oblique incidence X-ray fluorescence analyzer 7 of the fourth embodiment is the same as that of the oblique incidence X-ray fluorescence analyzer 6 of the third embodiment.

  The copper X-ray tube position 113, the spectroscopic element position 133, and the spectroscopic element rotation angle represented by T, S, and Ω in the above formulas 1 to 3 are the position and angle on the apparatus mechanism theoretically determined by the apparatus design. It is. 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 55, 57 and 58 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)

  The oblique incidence fluorescent X-ray analyzer 7 of the fourth embodiment is further added to the oblique incident fluorescent X-ray analyzer 6 of the third embodiment in addition to an X-ray tube offset distance storage means 61, a spectroscopic element offset distance storage means 62, and a spectroscopic element. Since the apparatus has the offset angle storage means 63, the analysis condition setting means 60, the reference substrate 70, and the sample turret 80, each adjustment is performed in the operation of the oblique incidence fluorescent X-ray analysis apparatus 7 using the flowchart of FIG. A step in which the means 55, 56, and 57 store each offset will be described.

  The measurement operator operates the arrangement of the reference substrate 70 in step S2A and the selection of the automatic optical axis adjustment in step S3, and the oblique incidence fluorescent X-ray analyzer 7 automatically operates from step S4A. In step S2A, for example, 50 μl of a solution sample containing chromium is collected with a micropipette, drip-dried onto a glass substrate to obtain a sample, and a sample placement groove 81 of the sample turret 80 as a reference substrate 70 for automatic optical axis adjustment. To place. In step S3, automatic adjustment of the irradiation position and irradiation angle of the sample S on the reference substrate 70 of the primary X-ray 34 from the X-ray source 3 is selected.

  When measurement is started in step S4A, the pressing means 40 driven by the drive control unit passes through the pressing means passage hole 52 of the sample stage 50, and the lower surface of the reference substrate 70 set in the sample mounting groove 81 of the sample turret 80. When the analysis surface of the reference substrate 70 is brought into contact with the ceramic balls 47 while pressing the stepping motor, the stepping motor driving the pressing means 40 stops, and the reference substrate 70 is disposed at a predetermined position and held at that position. When the reference substrate 70 is held at a predetermined position, the analysis surface of the reference substrate 70 is always set to a constant plane height with respect to the light receiving surface (see FIG. 5) of the light receiving element 37a. Steps S5 to S9 proceed in the same steps as the flowchart of FIG. 8 of the apparatus of the third embodiment.

  In step S10, the irradiation angle set to 0.05 ° in step S5 is adjusted. As described above, the copper X-ray tube 31 and the spectroscopic element 33 are linearly moved by the position adjusting means 55 and 57 to change T and S according to the relationship of Expressions 1 to 3, and the spectroscopic element angle adjusting means 58 is used to change the spectroscopic element. By changing the 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 55 and 57 and the spectroscopic element angle adjusting means 58 so that the irradiation angle φ changes in steps of 0.005 ° around the set 0.05 °. The irradiation angle φ is adjusted so that the intensity of the Cr-Kα line 36 is maximized. The irradiation angle φ may be changed in 0.01 ° steps.

  In step S11A, it is determined whether or not the steps S8 to S10 have been performed twice. If YES, the process proceeds to step S13, and the sample S is measured. If NO, the process returns to step S8. When the measurement is completed, the stepping motor driving the pressing unit 40 starts rotating, the pressing unit 40 is lowered, and the sample holder 1 is accommodated in the sample stage 50. Sequentially, the same number of samples are analyzed by the same operation. When the sample measurement is not continued, the operation of the oblique incidence fluorescent X-ray analyzer 6 is finished, and the X-ray irradiation and the fluorescent X-ray measurement on the sample S in steps S6 and S7 are also finished. In the present embodiment, steps S8 to S10 are performed twice, but may be one or three rounds as long as the number of times is appropriate.

In step S13, 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 in step S11A as X-ray tube offset distance t ₀ with respect to the X-ray tube position origin Store in the means 61. Further, until the YES determination in step S11A, the distance between the adjusted spectral element position 133 and the corresponding position on the mechanism is stored in the spectral element position storage means 62 as the spectral element offset distance s _{0 with} respect to the spectral element position origin. Further, until the YES determination in step S11A, the angle difference between the adjusted spectral element rotation angle Ω and the corresponding angle on the mechanism of the spectral element is stored in the spectral element angle storage unit 63 as a spectral element offset angle ω _{0 with} respect to the reference plane 160. Remember.

Next, automatic adjustment of the X-ray irradiation position and irradiation angle on the sample during unknown sample measurement in the operation of the oblique incidence fluorescent X-ray analyzer 7 of the fourth embodiment will be described with reference to the flowchart of FIG. Steps S1 to S4 are the same as those in FIG. 8, and the sample holder 1 on which the sample is placed is placed at the measurement position. In step S14, the analysis condition setting means 60 selects an analysis condition for analysis. In step S15, each storage means 61, 62, 63 gives each offset amount t ₀ , s ₀ , ω ₀ stored in step S13 to the analysis condition setting means 60. In step S16, on the basis of the offset amounts given to the analysis condition setting means 60, the mechanical sections such as the pulse motor drive circuit, pulse motor, and ball screw of the adjustment means 55, 57, and 58 are controlled to obtain a copper X-ray tube. The position 31 and the position and rotation angle of the spectroscopic element 33 are set. In steps S17, 18, and 19, as in steps S8, 9, and 11 of FIG. 8, the copper X-ray tube 31 and the spectroscopic element 33 are moved back and forth so that the intensity of the Cr-Kα line 36 is maximized. .

  Other analysis conditions are also set by the analysis condition setting means 60 in step S14. In step S17, the sample S of the sample holder 1 arranged in step S4 is measured. When the measurement of the sample S is finished, the operation of the oblique incidence fluorescent X-ray analyzer 7 is also finished, and the X-ray irradiation and the fluorescent X-ray measurement to the sample S in steps S6 and S7 are also finished. When the unknown sample measurement is not continuously performed, the operation of the oblique incidence fluorescent X-ray analyzer 7 is finished, and the X-ray irradiation and the fluorescent X-ray measurement to the sample S in steps S6 and S7 are also finished.

  According to the apparatus of the fourth embodiment, in addition to the operational effects of the apparatus of the third embodiment, even if distortion or deviation on the apparatus mechanism due to temperature change of the apparatus installation chamber or time-dependent change of the apparatus occurs, An offset amount for correcting a deviation in the mechanism of the apparatus is automatically obtained so that the intensity of the fluorescent X-ray 36 generated from the sample S is maximized, and the primary X-ray from the X-ray source 3 is obtained based on the offset amount. Since the irradiation position and the irradiation angle on the sample S of 34 are automatically set, the optical axis automatic adjustment may be appropriately performed even if there is no expert in optical adjustment, for example, once a week, one per month. If performed frequently, analysis with high sensitivity and high accuracy can always be performed in a short time.

  In the fourth embodiment, a rectangular glass substrate of 26 mm × 76 mm × 1.5 mm is used as the reference substrate 70, but a rectangular shape having a width of 10 to 30 mm, a length of 40 to 80 mm, and a thickness of 0.5 to 5 mm. A thing or a disk-like thing with a diameter of 20-50 mm may be sufficient. Moreover, not only a glass substrate but a silicon substrate may be used, and the amount of drip is not limited to 50 μl, but may be an amount of about 10 to 100 μl. The setting of the irradiation angle is not limited to 0.05 °, 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 55, 57, and 58 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 60, they may be independent of each other.

  The oblique incidence fluorescent X-ray analyzer of the fifth embodiment will be described below. As shown in FIG. 13, the oblique incidence fluorescent X-ray analysis apparatus 8 of the fifth embodiment is different from the oblique incidence fluorescent X-ray analysis apparatus 7 of the fourth embodiment in that the X-ray irradiation angle to the reference substrate 70 and the reference substrate 70 are further increased. Based on the critical angle calculation means 65 for calculating the critical angle of the X-ray irradiation angle by calculating the intensity of the fluorescent X-rays 36 generated more and the critical angle calculated by the critical angle calculation means 65, X-ray irradiation angle correction means 66 for correcting the X-ray irradiation angle is provided.

  The critical angle calculation means 65 measures the intensity of the fluorescent X-rays 36 generated from the reference substrate 70 at each X-ray irradiation angle by the detector 37, and the gradient of the change in the fluorescent X-ray intensity 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 tube position adjusting unit 55, the spectroscopic element position adjusting unit 57, and the spectroscopic element angle adjusting unit 58 are driven to change the X-ray irradiation angle to the reference substrate 70 from 0 ° to, for example, 0.005 °. The intensity of the fluorescent X-ray Si-Kα ray 36 generated from the reference substrate 70 which is a glass substrate corresponding to each X-ray irradiation angle is measured by the detector 37 while being changed in steps, and the Si-Kα with respect to 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 change in the intensity of the line is maximized.

  The X-ray irradiation angle correction means 66 calculates a difference between the critical angle calculated by the critical angle calculation means 65 and the theoretical critical angle calculated based on the refractive index of the reference substrate 70 that is a glass substrate and the energy of the primary X-ray 34. The X-ray irradiation angle φ (see FIG. 7) is corrected as the irradiation angle offset angle with respect to the reference plane 160 (see FIG. 7).

  The operation of the oblique incidence fluorescent X-ray analyzer 8 of the fifth embodiment will be described. The oblique incidence X-ray fluorescence spectrometer 8 operates in the order of steps in the flowchart shown in FIG. Since steps SA1 and SA2 between steps S10 and S11B are different from the flowchart of FIG. 11, the two steps SA1 and SA2 will be described.

  In step SA1, the critical angle of the X-ray irradiation angle to the reference substrate 70 is calculated using the critical angle calculation means 65 while changing the X-ray irradiation angle to the reference substrate 70 as in step S8 of the fourth embodiment described above. To do. The X-ray tube position adjusting means 55, the spectroscopic element position adjusting means 57 and the spectroscopic element angle adjusting means 58 are driven, and the X-ray irradiation angle to the reference substrate 70 is sequentially changed from 0 °, for example, in 0.005 ° steps. The intensity of the fluorescent X-ray Si-Kα ray 36 generated from the reference substrate 70 corresponding to each X-ray irradiation angle is measured by the detector 37, and the gradient of the intensity change of the Si-Kα ray 36 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. When the X-ray irradiation angle is changed, the intensity of the Si—Kα line 36 generated from the reference substrate 70 is changed to a curve as shown in FIG. 15, so that the gradient of the intensity change of the Si—Kα line is maximized. The critical angle calculation means 65 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 φ to the sample S is corrected by the X-ray irradiation angle correction means 66 based on the critical angle calculated in step SA1. The X-ray irradiation angle correction means 66 is calculated from, for example, the refractive index of the glass substrate that is the reference substrate 70 used in the fifth embodiment and the energy of the Cu-Kα line 36 that is the characteristic X-ray irradiated to the reference substrate 70. The theoretical critical angle is stored, and the difference between the stored theoretical critical angle and the critical angle calculated by the critical angle calculating means 65 is stored as an irradiation angle offset angle with respect to the reference plane 160 (see FIG. 7). Based on the stored irradiation angle offset angle, the X-ray irradiation angle is reset to 0.05 ° 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 66 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 oblique incidence fluorescent X-ray analyzer 8 of the fifth 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 the step of FIG. 12 of the fourth embodiment. It is.

  According to the oblique incidence fluorescent X-ray analysis apparatus 8 of the fifth embodiment, the critical angle calculation means 65 and the X-ray irradiation angle correction means 66 are provided in addition to the oblique incidence fluorescence X-ray analysis apparatus 7 of the fourth embodiment. Therefore, in addition to the function and effect of the fourth embodiment, the X-ray irradiation angle is corrected and reset by the X-ray irradiation angle correction means 66 using the critical angle calculated by the critical angle calculation means 65, and the copper X is more precisely set. It is possible to automatically adjust the irradiation position and irradiation angle of the irradiation X-ray 34 from the ray tube 31 onto the sample S, and to perform analysis with higher sensitivity and higher accuracy.

  Next, an oblique incidence X-ray fluorescence analyzer that is a sixth embodiment will be described. As shown in FIG. 16, the oblique incidence X-ray fluorescence analyzer 9 includes a copper X-ray tube 31 and a molybdenum X-ray tube 91 in addition to the oblique incidence X-ray fluorescence analyzer 7 of the fourth embodiment. Selecting means 92 for selecting any one of the X-ray tubes.

  The copper X-ray tube 31 and the molybdenum X-ray tube 91 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 92. When the copper X-ray tube 31 is selected by the operator's selection and the selection means 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 Tube 31 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 oblique incidence fluorescent X-ray analyzer 9 of the sixth embodiment will be described. The oblique incidence X-ray fluorescence analyzer 9 operates in the order of steps in the flowchart shown in FIG. Since steps SB1 and SB2 between steps S2A and S4A are different from the flow chart of FIG. 11, the two steps SB1 and SB2 will be described.

  In step SB1, when the copper X-ray tube 31 to be used is selected by the selection unit 92, the selection control unit of the selection unit 92 sets the mounting plate as the X-ray tube replacement unit to a pulse motor drive circuit, a pulse motor, a ball screw, and the like. The X-ray tube mounting plate is moved, the selected copper X-ray tube 31 is set to the measurement position, and the control unit of the selection unit controls the pulses of the spectroscopic element position adjusting unit 57 and the spectroscopic element angle adjusting unit 58. Drive units of the motor drive circuit, pulse motor, ball screw, and other mechanisms are controlled to set the spectroscopic element 33 to the measurement angle of the Cr-Kα ray, and the process automatically proceeds to the next step SB2. In step SB2, automatic adjustment of the irradiation position and irradiation angle of the primary X-ray 34 from the X-ray source 3 to the sample S is automatically selected.

  When the molybdenum X-ray tube 91 is replaced, if the molybdenum X-ray tube 91 is selected in step SB1 of the flowchart shown in FIG. 17, the measurement position and measurement of the molybdenum X-ray tube 91 are the same as the copper X-ray tube 31 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 34 from the X-ray source 3 to the sample S 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 S17 (see FIG. 12) immediately after step SB1 ends.

  In the operation of the oblique incidence fluorescent X-ray analyzer 9 of the sixth 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 the step of FIG. 12 of the fourth embodiment. It is.

  According to the oblique incidence fluorescent X-ray analysis apparatus 9 of the sixth embodiment, the same operational effects as those of the oblique incidence fluorescent X-ray analysis apparatus of the fourth embodiment can be obtained, and a plurality of X-ray tubes 31 can be used depending on the analysis purpose. Even when using the X-ray tube 31 or 91 selected from among them, the X-ray irradiation position or irradiation angle on the sample S is not shifted every time the X-ray tube 31 or 91 is replaced. Without confirmation, the X-rays from the X-ray source 3 including the selected X-ray tube 31 or 91 to the sample S so as to maximize the intensity of the fluorescent X-rays 36 generated from the sample S. Since the irradiation position and the irradiation angle are automatically set, analysis with high sensitivity and high accuracy can always be performed in a short time.

  The oblique incidence fluorescent X-ray analyzer 9 of the sixth embodiment includes selection means 92 for selecting one of the copper X-ray tube 31 and the molybdenum X-ray tube 91. In addition to the X-ray tube, 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, an oblique incidence fluorescent X-ray analyzer as a seventh embodiment will be described. As shown in FIG. 18, the oblique incidence fluorescent X-ray analyzer 10 further includes the X-ray irradiation angle to the reference substrate 70 and the reference substrate 70 in addition to the oblique incident fluorescent X-ray analyzer 9 of the sixth embodiment. Based on the critical angle calculating means 65 for calculating the critical angle of the X-ray irradiation angle φ by calculating the intensity of the fluorescent X-rays 36 generated more and the critical angle calculated by the critical angle calculating means 65 to the sample S X-ray irradiation angle correction means 66 for correcting the X-ray irradiation angle.

  The operation of the oblique incidence fluorescent X-ray analyzer 10 according to the seventh embodiment will be described. The oblique incidence X-ray fluorescence analyzer 10 operates in the order of steps in the flowchart shown in FIG. Steps S2A to S10 are the same steps as in FIG. 17, and steps SA1 to S13 are the same steps as in FIG.

  In the operation of the oblique incidence fluorescent X-ray analyzer 10 of the seventh embodiment, the automatic adjustment of the X-ray irradiation position and the irradiation angle to the sample at the unknown sample measurement is the same as the step of FIG. 12 of the fourth embodiment. It is.

  According to the oblique incidence fluorescent X-ray analysis apparatus 10 of the seventh embodiment, the critical angle calculation means 65 and the X-ray irradiation angle correction means 66 are provided in addition to the oblique incidence fluorescence X-ray analysis apparatus 9 of the sixth embodiment. Therefore, in addition to the function and effect of the sixth embodiment, even when the X-ray tube 31 or 91 selected from the plurality of X-ray tubes 31 and 91 is used, the critical angle calculating means is used every time the X-ray tube 31 or 91 is replaced. By correcting and resetting the X-ray irradiation angle by the X-ray irradiation angle correcting means 66 using the critical angle calculated by 65, the sample S of the irradiation X-ray 34 from the X-ray tube 31 or 91 selected more precisely. It is possible to automatically adjust the irradiation position and the irradiation angle of the lens, and to perform analysis with higher sensitivity and higher accuracy.

  Although the sample holder 1 is provided in the oblique incidence X-ray fluorescence spectrometer of the third to seventh embodiments described above, the sample holder 2 may be provided instead of the sample holder 1, and the same operational effects can be obtained. it can.

It is a perspective view of the sample holder of 1st Embodiment of this invention. It is a top view of the sample holder. It is the II sectional view taken on the line of FIG. 1B. It is a schematic perspective view of the sample holder of 2nd Embodiment of this invention. It is the schematic which shows the oblique incidence fluorescent-X-ray-analysis apparatus of 3rd Embodiment of this invention. It is the schematic which shows the measurement part of an analyzer same as the above. It is front sectional drawing of the measurement part of an analyzer same as the above. It is a top view of the lower part from the detector holding part of the measurement part of an analyzer same as the above. It is a basic operation explanatory view of the X-ray source position, spectroscopic element position, and angle adjustment of the analyzer same as above. It is a step operation | movement flowchart which adjusts automatically the irradiation position and irradiation angle to the sample of the primary X-ray of an analyzer same as the above. It is the schematic which shows the oblique incidence fluorescent-X-ray-analysis apparatus of 4th Embodiment of this invention. It is a top view of the sample turret of an analyzer same as the above. It is II-II sectional view taken on the line of FIG. 10A of the analyzer same as the above. It is a step operation | movement flowchart which memorize | stores the offset amount of an analyzer same as the above. It is an operation | movement flowchart at the time of unknown sample measurement of the analyzer same as the above. It is the schematic which shows the oblique incidence fluorescent-X-ray-analysis apparatus of 5th Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of an analyzer same as the above. It is explanatory drawing of the critical angle in an analyzer same as the above. It is the schematic which shows the oblique incidence fluorescent-X-ray-analysis apparatus of 6th Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of an analyzer same as the above. It is the schematic which shows the oblique incidence fluorescent-X-ray-analysis apparatus of 7th Embodiment of this invention. It is a step operation | movement flowchart which memorize | stores the offset amount of an analyzer same as the above.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 Sample holder 3 X-ray source 4 Measuring part 6, 7, 8, 9, 10 Oblique incidence X-ray fluorescence analyzer 11, 21 Annular side parts 13, 23 Bottom part 14 Sample mounting table 15 Height adjustment tool 18, 28 Main body 24 Gel clay (plastic material having adhesive force)
33 Spectroscopic element 32 X-ray 34 Primary X-ray 36 Fluorescent X-ray 37 Detector 38 Reflected X-ray 40 Press means 45 Contact means 46 Holding part 47 Sample contact part (ceramic ball)
55 X-ray tube position adjusting means 56 Control means 57 Spectroscopic element position adjusting means 58 Spectroscopic element angle adjusting means 60 Analysis condition setting means 61 X-ray tube offset distance storage means 62 Spectroscopic element offset distance storage means 63 Spectroscopic element offset angle storage means 65 Critical angle calculation means 70 Reference substrate
92 Selection means 104, 204 Contact surface L X-ray path R Detector field of view S Sample

Claims (7)

A sample holder for a fluorescent X-ray analyzer having a sample abutting portion for arranging a sample at a predetermined height, wherein an upper surface that is a horizontal surface forms an abutting surface that abuts on the sample abutting portion A sample holder having a body having a side and a bottom of
A contact means having the sample contact portion and a holding portion for holding the sample contact portion;
A pressing means for pressing the contact surface of the sample holder against the sample contact portion;
An X-ray source;
A spectroscopic element that divides X-rays generated from the X-ray source and irradiates a sample placed on the sample holder with X-rays having a predetermined wavelength;
An X-ray path through which X-rays of the predetermined wavelength and reflected X-rays reflected by the sample pass in a gap between the contact surface of the sample holder and the sample-facing surface of the holding unit of the contact means;
A detector for measuring the intensity of fluorescent X-rays generated from the sample;
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;
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 to be measured by the detector;
The oblique-incidence fluorescent X-ray analysis apparatus in which the control means automatically adjusts the irradiation position of the primary X-ray from the X-ray source onto the sample so that the intensity of the fluorescent X-ray generated from the sample is maximized. A sample holder for a fluorescent X-ray analyzer having a sample abutting portion for arranging a sample at a predetermined height, wherein an upper surface that is a horizontal surface forms an abutting surface that abuts on the sample abutting portion a sample holder having a body with a side and a bottom,
A contact means having the sample contact portion and a holding portion for holding the sample contact portion;
An X-ray source;
Press for pressing the analysis surface of the reference substrate or the contact surface of the sample holder as a reference for automatically adjusting the irradiation position and the irradiation angle of the primary X-ray from the X-ray source to the sample contact portion Means,
A spectroscopic element that divides X-rays generated from the X-ray source and irradiates a sample on the reference substrate or a sample placed on the sample holder with X-rays having a predetermined wavelength;
X-rays that pass X-rays of the predetermined wavelength and reflected X-rays reflected by the sample in the gap between the analysis surface of the reference substrate or the contact surface of the sample holder and the sample-facing surface of the holding unit of the contact means A passage,
A detector for measuring the intensity of fluorescent X-rays generated from the sample;
Incident incidence comprising analysis condition setting means for setting an analysis condition with the same height as the contact surface of the sample holder and surrounded by the contact surface in plan view as a virtual sample analysis surface An X-ray fluorescence analyzer,
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;
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 set. X-ray source offset distance storage means for storing the stored X-ray source offset distance with respect to the X-ray source position origin, and applying the stored X-ray source offset distance to the analysis condition setting means;
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 set as the spectroscopic element position origin. A spectroscopic element offset distance storage unit that stores the spectroscopic element offset distance for the analysis condition setting unit.
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, the angle difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjusting means and the corresponding angle on the spectroscopic element mechanism is determined with respect to the reference plane. A spectral element offset angle storage unit that stores the spectral element offset angle as a spectral element offset angle and applies the stored spectral element offset angle to the analysis condition setting unit.
The control means automatically adjusts the irradiation position and the irradiation angle of the primary X-ray sample from the X-ray source so that the intensity of fluorescent X-rays generated from the sample on the reference substrate is maximized, or An oblique-incidence fluorescent X-ray analyzer that 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-ray generated from the sample on the sample holder is maximized. In Claim 2 , 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 reference substrate and the intensity of fluorescent X-rays generated from the reference substrate;
An oblique incidence fluorescent X-ray analyzer comprising: an X-ray irradiation angle correction unit that corrects an X-ray irradiation angle to the reference substrate based on the critical angle calculated by the critical angle calculation unit. A sample holder for a fluorescent X-ray analyzer having a sample abutting portion for arranging a sample at a predetermined height, wherein an upper surface that is a horizontal surface forms an abutting surface that abuts on the sample abutting portion a sample holder having a body with a side and a bottom,
A contact means having the sample contact portion and a holding portion for holding the sample contact portion;
A plurality of x-ray sources;
Selecting means for selecting one X-ray source from the plurality of X-ray sources;
The analysis surface of the reference substrate or the contact surface of the sample holder, which serves as a reference for automatically adjusting the irradiation position and irradiation angle of the primary X-ray from the X-ray source selected by the selection means, is applied to the sample. A pressing means for pressing the contact portion;
A spectroscopic element that divides X-rays generated from the X-ray source selected by the selection means and irradiates a sample on the reference substrate or a sample placed on the sample holder with X-rays having a predetermined wavelength;
X-rays that pass X-rays of the predetermined wavelength and reflected X-rays reflected by the sample in the gap between the analysis surface of the reference substrate or the contact surface of the sample holder and the sample-facing surface of the holding unit of the contact means A passage,
A detector for measuring the intensity of fluorescent X-rays generated from the sample;
Incident incidence comprising analysis condition setting means for setting an analysis condition with the same height as the contact surface of the sample holder and surrounded by the contact surface in plan view as a virtual sample analysis surface An X-ray fluorescence analyzer,
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;
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 set. X-ray source offset distance storage means for storing the stored X-ray source offset distance with respect to the X-ray source position origin, and applying the stored X-ray source offset distance to the analysis condition setting means;
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, 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 set as the spectroscopic element position origin. A spectroscopic element offset distance storage unit that stores the spectroscopic element offset distance for the analysis condition setting unit.
By irradiating the sample on the reference substrate with X-rays having a predetermined wavelength, the angle difference between the spectroscopic element angle adjusted by the spectroscopic element angle adjusting means and the corresponding angle on the spectroscopic element mechanism is determined with respect to the reference plane. A spectral element offset angle storage unit that stores the spectral element offset angle as a spectral element offset angle and applies the stored spectral element offset angle to the analysis condition setting unit.
The control means automatically adjusts the irradiation position and the irradiation angle 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 on the reference substrate is maximized, or An oblique-incidence fluorescent X-ray analyzer that 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-ray generated from the sample on the sample holder is maximized. According to claim 4, based further on the intensity of X-ray irradiation angle and the fluorescent X-ray generated from the reference board to the reference substrate, a critical angle calculating means for calculating the critical angle of the X-ray irradiation angle,
An oblique incidence fluorescent X-ray analyzer comprising: an X-ray irradiation angle correction unit that corrects an X-ray irradiation angle to the reference substrate based on the critical angle calculated by the critical angle calculation unit. In any one of Claims 1-5 ,
The oblique incidence fluorescent X-ray analysis apparatus in which the sample contact portion is disposed outside the field of view of the detector. In any one of Claims 1-6 ,
The oblique incidence fluorescent X-ray analyzer in which the sample contact portion is made of ceramics.

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