JP4884553B1 - X-ray analysis apparatus and method - Google Patents

Abstract

The present invention provides an X-ray analysis apparatus and method capable of suppressing scattered radiation and impurity lines generated from a sample having a crystal structure and avoiding diffracted X-rays.
An X-ray analyzer includes a control means 15 for storing a diffraction pattern obtained by irradiating a primary S-ray 2 while rotating the specimen S around a predetermined point of the specimen 360 °, and an R− of the specimen S. The calculation storage means 17 for calculating and / or storing the upper and lower limit values of the parallel movement range of the sample that can be positioned on the measurement surface of the sample in the θ coordinate, and the calculated and / or stored θ coordinate And a selection means for selecting an avoidance angle at which the adjacent interval is an angle within the upper and lower limit value range of the θ coordinate based on the upper and lower limit values and the diffraction pattern and can avoid the diffracted X-ray, 15 reads out the avoidance angle closest to the coordinates of the measurement point from the avoidance angles according to the coordinates of the measurement points of the sample, and sets the sample to the read avoidance angle.
[Selection] Figure 1

Description

  The present invention relates to an X-ray analysis apparatus and method for measuring an arbitrary measurement site of a disk-shaped sample such as a wafer.

  Conventionally, for example, in wafer analysis, primary X-rays are irradiated on a sample surface, and the intensity of secondary X-rays generated from the sample surface is detected and analyzed. When a sample having a crystal structure such as a wafer is irradiated with X-rays, secondary X-rays such as fluorescent X-rays and diffraction X-rays are generated. In fluorescent X-ray analysis, this diffracted X-ray may be an obstacle to measurement. Diffracted X-rays are generated at different angular positions depending on the cut surface of the sample, such as the (110) plane and (111) plane, which are crystal structures.

  Therefore, prior to fluorescent X-ray analysis of the sample, the sample is irradiated with primary X-rays while rotating the sample around a predetermined point of 180 ° or more, and fluorescent X-rays and diffraction X-rays generated from the sample. Secondary X-rays are detected, and the sample is positioned at the rotational direction position where the obtained secondary X-ray intensity shows the minimum value. In this state, the samples are orthogonal to each other in a plane parallel to the measurement surface. There is a fluorescent X-ray analysis method in which the entire measurement surface of the sample is analyzed by moving in the XY direction (Patent Document 1).

  Further, as shown in FIG. 11, in measurement of a desired measurement site near the edge of the sample, the primary X-ray 2 is irradiated from outside the region above the sample S so as to be totally reflected to the region. As a result, a part of the primary X-ray 2 is irradiated onto the vertical end surface of the plate-like sample S, and strong scattered rays 9 are generated in all directions. A part of the scattered radiation 9 becomes a large background with respect to the fluorescent X-ray to be measured.

  Therefore, an arbitrary measurement site near the edge of the sample is positioned so that the primary X-ray is irradiated from the region above the sample and totally reflected outside the region, thereby suppressing scattered radiation generated from the end surface of the sample. Thus, there is a total reflection fluorescent X-ray analysis apparatus (Patent Document 2).

JP-A-5-126768 Japanese Patent Laid-Open No. 2002-5858

  The fluorescent X-ray analysis method described in Patent Document 1 can avoid diffracted X-rays generated from a sample whose crystal structure is rotationally symmetric, but avoid diffracted X-rays generated from a sample whose crystal structure is not rotationally symmetric. I couldn't.

  The total reflection X-ray fluorescence analyzer described in Patent Document 2 can suppress the influence of scattered radiation generated from the vicinity of the edge of the sample, but avoids diffracted X-rays generated from a sample whose crystal structure is not rotationally symmetric. Therefore, even if the sample is set at a position where the influence of scattered radiation can be eliminated, diffracted X-rays cannot be avoided, and depending on the sample, accurate analysis cannot be performed.

  Therefore, the present invention has been made in view of the above-described conventional problems, and suppresses and avoids scattered rays and impurity lines generated from the vicinity of the edge of a disk-shaped sample having a crystal structure and an apparatus structure in the vicinity of the sample, An object of the present invention is to provide an X-ray analysis apparatus and method capable of easily performing accurate analysis by avoiding diffracted X-rays generated from a sample.

  In order to achieve the above object, an X-ray analyzer according to a first configuration of the present invention includes a sample stage on which a disk-shaped sample having a crystal structure is placed, and an X-ray that irradiates the sample with primary X-rays. A source, a detector for detecting secondary X-rays generated from the sample, translation means for translating the sample stage so as to irradiate the primary X-ray at an arbitrary position on the sample measurement surface, and a sample measurement surface Rotating means for rotating the sample stage around an axis perpendicular to the surface, and the primary X-ray is irradiated from the region above the sample to the outside of the region at any measurement site near the edge of the sample Measured with reflection.

Further, the X-ray analyzer irradiates the sample with a primary X-ray from the X-ray source while rotating the sample around a predetermined point of the sample by the rotation means by 360 °, and generates the sample to enter the detector. The display unit displays a diffraction pattern in which the intensity of the secondary X-ray corresponds to the rotation angle of the sample, and stores the diffraction pattern, the radius R of the sample, and the field of view of the detector on the measurement surface of the sample Calculation storage means for calculating and / or storing the angle range 2θ1 obtained from the following equation (1) based on the radius T of each of the sample diameters;
sin θ1 = (R−T) / R (1)
Based on the angle range 2θ1 calculated and / or stored by the calculation storage means by the measurer and the diffraction pattern displayed on the display means , there are a plurality of avoidance angles that can avoid the diffracted X-rays. comprising selecting means for spacing adjacent to each other to select the avoidance angle is within the angular range 2.theta.1, the said control means stores the avoidance angle selected using the selection means by the measurer, According to the coordinates of the measurement point of the sample, the avoidance angle closest to the coordinate of the measurement point is read out from the stored avoidance angles, the sample is set to the read avoidance angle by controlling the rotating means, The translation point is controlled to set the measurement point of the sample as the primary X-ray irradiation position.

  According to the X-ray analyzer of the first configuration of the present invention, while suppressing and avoiding scattered rays and impurity lines generated from the vicinity of the edge of the disk-shaped sample having a crystal structure and the device structure in the vicinity of the sample, By avoiding the generated diffracted X-rays, it is possible to easily analyze with high accuracy.

  The X-ray analyzer of the second configuration of the present invention includes a sample stage on which a disk-shaped sample having a crystal structure is placed, an X-ray source that irradiates the sample with primary X-rays, and 2 generated from the sample. A detector for detecting a secondary X-ray, a translation means for translating the sample stage so as to irradiate the primary X-ray at an arbitrary position on the sample measurement surface, and the axis about the axis perpendicular to the sample measurement surface. Rotating means for rotating the sample stage, and measuring an arbitrary measurement site near the edge of the sample so that the primary X-ray is irradiated from the region above the sample and reflected outside the region. To do.

Further, the X-ray analyzer irradiates the sample with a primary X-ray from the X-ray source while rotating the sample around a predetermined point of the sample by the rotation means by 360 °, and generates the sample to enter the detector. The display unit displays a diffraction pattern in which the intensity of the secondary X-ray corresponds to the rotation angle of the sample, and the control selection unit that stores the diffraction pattern, the radius R of the sample, and the detector on the measurement surface of the sample Calculation storage means for calculating and / or storing the angle range 2θ1 obtained from the following formula (1) based on the radius T of the visual field for each diameter of the sample;
sin θ1 = (R−T) / R (1)
Based on the angle range 2θ1 calculated and / or stored by the calculation storage means and the diffraction pattern displayed on the display means, the control selection means has an X-ray intensity below a predetermined threshold in the diffraction pattern. A plurality of avoidance angles that can avoid the diffracted X-rays, and an avoidance angle in which an interval between adjacent avoidance angles is within the angle range 2θ1 is selected and stored, and the storage is performed according to the coordinates of the measurement point of the sample. The avoidance angle closest to the coordinates of the measurement point is read out from the avoidance angles, the sample is set to the read avoidance angle by controlling the rotating means, and the measurement point of the sample is controlled by controlling the parallel moving means. The primary X-ray irradiation position is set.

  According to the X-ray analyzer of the second configuration of the present invention, it is possible to automatically suppress and avoid scattered rays and impurity lines generated from the vicinity of the edge of the disk-shaped sample having a crystal structure and the device structure in the vicinity of the sample. At the same time, by avoiding the diffracted X-rays generated from the sample, it is possible to easily analyze with high accuracy.

  The X-ray analysis method of the third configuration of the present invention includes a sample stage on which a disk-shaped sample having a crystal structure is placed, an X-ray source that irradiates the sample with primary X-rays, and 2 generated from the sample. A detector for detecting a secondary X-ray, a translation means for translating the sample stage so as to irradiate the primary X-ray at an arbitrary position on the sample measurement surface, and the axis about the axis perpendicular to the sample measurement surface. Rotating means for rotating the sample stage, and measuring an arbitrary measurement site near the edge of the sample so that the primary X-ray is irradiated from the region above the sample and reflected outside the region. X-ray analyzer is used.

Further, in this X-ray analysis method, the sample placed on the sample stage is irradiated with primary X-rays while being rotated 360 ° around a predetermined point of the sample by the rotating means, and is generated from the sample to generate the detector. A diffraction pattern in which the intensity of the secondary X-ray incident on the sample is made to correspond to the rotation angle of the sample is acquired, and based on the radius R of the sample and the radius T of the field of view of the detector on the measurement surface of the sample, ) Is calculated and stored for each diameter of the sample,
sin θ1 = (R−T) / R (1)
Based on the calculated and stored angle range 2θ1 and the diffraction pattern displayed on the display means, a plurality of avoidance angles that can avoid diffracted X-rays, and the adjacent intervals between the avoidance angles are within the angle range 2θ1. storing the avoidance angle is selected and, depending on the coordinates of the measuring points of the sample, read the closest avoidance angle coordinates of the measuring point from the avoidance angle to said storage, and read out the by said rotating means The sample is set at the avoidance angle, and the measurement point of the sample is set to the irradiation position of the primary X-ray by the parallel moving means for analysis.

  According to the X-ray analysis method of the third configuration of the present invention, while suppressing and avoiding scattered rays and impurity lines generated from the vicinity of the edge of the disk-shaped sample having a crystal structure and the device structure in the vicinity of the sample, By avoiding the generated diffracted X-rays, it is possible to easily analyze with high accuracy.

1 is a schematic diagram showing an X-ray analysis apparatus according to a first embodiment of the present invention. It is a figure which shows the initial position of the sample in the sample stand of the apparatus. It is a figure which shows the diffraction pattern of the sample measured with the same apparatus. It is a figure which shows the positional relationship of the measurement point A of the same apparatus, and a virtual line. It is a figure which shows the positional relationship of the measurement point B of the same apparatus, and a virtual line. It is a figure which shows the positional relationship of the measurement point C of the same apparatus, and a virtual line. It is a figure which shows the positional relationship of the measurement point D of the same apparatus, and a virtual line. It is a figure which shows the sample position when acquiring a diffraction pattern with the same apparatus. It is the figure where the measurement point F of the same apparatus was set to the diffraction X-ray avoidance angle. It is the schematic which shows the X-ray analyzer of 3rd Embodiment of this invention. It is an enlarged view of the scattered radiation generation part from the sample in the conventional X-ray analyzer.

  The X-ray analyzer according to the first embodiment of the present invention will be described below. First, the configuration of the X-ray analyzer will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of an X-ray analyzer such as a total reflection fluorescent X-ray analyzer used for carrying out the X-ray analysis method of the present invention. This X-ray analyzer has a crystal structure such as a wafer. X-ray source 1 such as an X-ray tube that emits primary X-rays 2 toward a disk-shaped sample S having a fluorescent X-ray and diffracted X-rays generated from the sample S by the irradiation of primary X-rays 2 The detector 7 for detecting the intensity of the secondary X-ray 4 such as the sample stage 8, the sample stage 8 on which the sample S is placed, and the sample stage 8 are rotated around an axis perpendicular to the measurement surface of the sample S. In the embodiment, the rotating means 11 is rotated around the center O of the sample S, and the measurement is performed so that the primary X-ray 2 is irradiated at an arbitrary position on the measurement surface of the sample S while the rotating means 11 is rotatably supported. And a parallel moving means 12 such as an R-θ stage for moving in the R-θ direction in a plane parallel to the surface. ing. For example, the R-θ stage is a stage disclosed in JP-A-8-161049.

The coordinates of the sample S are indicated by R-θ coordinates. As shown in FIG. 2, the clockwise angle in the R-θ coordinate is represented as -θ, and the counterclockwise angle is represented as + θ. the rotation angle when a total of the direction that will be rotated to display a sign ω by. The sample S is placed on the sample stage 8, and is set to the initial position with reference to the notch N of the wafer, the orientation flat, and the like. At the initial position of the sample S, the center O of the sample S coincides with the center P of the field of view V of the detector 7. Symbols I 1, II, III, and IV shown in FIG. 2 indicate the first quadrant, the second quadrant, the third quadrant, and the fourth quadrant of coordinates.

  As shown in FIG. 1, an arbitrary measurement site near the edge of the sample S can be measured by being positioned so that the primary X-ray 2 is irradiated from the region above the sample S and reflected outside the region. In addition, the primary X-ray 2 is irradiated to the vicinity of the right edge of the sample S from the left side of the drawing. The irradiation direction of the primary X-ray 2 to the sample S is fixed in a predetermined direction. The detector 7 is a semiconductor detector such as an SDD. The detector 7 is fixed to a predetermined part of the apparatus, and the visual field V on the sample S measurement surface has a constant size (a constant area). In the X-ray analyzer of the first embodiment, for example, the field of view V of the detector 7 is circular, and the radius T is 10 mm.

The X-ray analysis apparatus of the first embodiment further includes a control unit 15, a display unit 16, a calculation storage unit 17 and a selection unit 18. Control means 15, the sample S is irradiated with X-ray source 1 from the primary X-ray 2 while 360 ° rotation it clockwise by the rotating means 11 to the center O around the sample S, is generated from the sample S A diffraction pattern in which the intensity of the secondary X-ray 4 incident on the detector 7 is made to correspond to the rotation angle ω of the sample S is displayed on the display means 16, and the diffraction pattern is stored. FIG. 3 shows an example of a diffraction pattern acquired by irradiating the primary X-ray W-Lβ1 with the apparatus of the present embodiment, displayed on the display means 16, and stored. The rotation direction of the sample S can be a counter-clockwise direction.

  The arithmetic storage means 17 is an imaginary line facing the same direction as the horizontal component of the primary X-ray 2 to the sample S, and is two imaginary lines in contact with the outer periphery of the field of view of the detector 7 on the measurement surface of the sample. However, the θ coordinates of the upper and lower limit values of the translation range of the sample S that can be positioned on the measurement surface of the sample S are calculated and / or stored for each diameter R of the sample S. The imaginary line is indicated by the symbols H and M shown in FIG. 4 and faces the same direction as the horizontal component of the primary X-ray 2 and is on the outer periphery of the visual field V of the detector 7 on the measurement surface of the sample S. It is a virtual line that touches. As described with reference to FIG. 1, the irradiation direction of the primary X-ray 2 onto the sample S is fixed in the direction indicated by the arrow in FIG. 4 and the field of view V of the detector 7 is also constant. , M are at fixed positions shown in FIG. The measuring point A is arranged at the center P of the field of view V of the detector 7 and measured by the translation means 12.

  The measurer uses the selection unit 18 to set the adjacent interval to the upper limit of the θ coordinate based on the upper and lower limit values of the θ coordinate calculated or stored by the calculation storage unit 17 and the diffraction pattern displayed on the display unit 16. An avoidance angle that is within the lower limit range and that can avoid diffracted X-rays is selected.

  The control means 15 uses the selection means 18 to store the selected avoidance angle ω, and according to the measurement point coordinates of the sample S, the closest avoidance angle ω among the stored avoidance angles ω. The angle ω is read, the sample S is set to the read avoidance angle ω by controlling the rotating means 11, and the sample S is moved while the set avoidance angle ω is maintained by controlling the parallel moving means 12. The measurement point is made to coincide with the center P of the field of view V of the detector 7.

  The following will describe the θ coordinates of the upper and lower limit values of the parallel movement range of the sample S in which the two virtual lines H and M can be positioned on the measurement surface of the sample S in the R-θ coordinate of the sample S. When the positions of the measurement point B (R, −90) and the visual field V of the detector 7 are in the state shown in FIG. 5, the right virtual line M is outside the measurement surface of the sample S, and the primary X-ray 2 Hits the right edge of the sample S, and scattered rays are generated. Further, the primary X-ray 2 is irradiated on the device structural material existing below the sample S (in the depth direction of the drawing in FIG. 5), and the scattered X rays and impurity lines (fluorescence X generated from the device structural material existing below the sample S). Line) occurs. The first scattered and impure lines generated in this way generate further scattered and impure lines. First scattered rays and impure rays, and further scattered rays and impure rays enter the detector 7.

  On the other hand, when the positions of the measurement point C (R, −θ1) and the visual field V of the detector 7 are in the state shown in FIG. 6, the left virtual line H is on the measurement surface of the sample S, and the right virtual line M is It contacts the right side surface of the sample S. Therefore, even if a part of the primary X-rays 2 is irradiated to the right side edge of the sample S or the apparatus structural material existing below the sample S, scattered rays and impure lines generated from those portions are not detected by the detector 7. The light travels outside the field of view V and does not enter the detector 7.

  As described above, when the sample S is arranged by the parallel moving means 12 so that the two virtual lines of the left virtual line H and the right virtual line M are both located on the measurement surface of the sample S, the scattered rays and the impure lines are detected by the detector. 7 can be prevented from entering.

  For the measurement point D (R, −θ2) shown in FIG. 7, the left imaginary line H and the right imaginary line M are both on the measurement surface of the sample S, and θ1 (FIG. 6) of the measurement point C and the measurement point D The angle relationship of θ2 is θ1> θ2. As can be seen, if the position of the measurement point is in the angle range of 0 to −θ1, scattered rays and impure rays can be prevented from entering the detector 7.

  Although the first quadrant coordinate of the sample S has been described, the same applies to the second quadrant coordinate. If the position of the measurement point is within the angle range of 0 to + θ1, both scattered rays and impure lines are incident on the detector 7. You can avoid it. That is, if the position of the measurement point is within the angle range of −θ1 to + θ1, it is possible to prevent both scattered rays and impure lines from entering the detector 7, where + θ1 is the upper limit angle and −θ1 is the lower limit angle, The angle range of the absolute value is 2θ1.

  As shown in FIG. 6, the following equation (1) is established among the upper limit angle θ1, the radius R of the sample S, and the radius T of the field of view V of the detector 7.

sin θ1 = (R−T) / R (1)

The detector 7 is fixed to a predetermined part of the apparatus, the radius T of the field of view V of the detector 7 is also constant, and the upper limit angle θ1 can be obtained from the radius R of the sample S.

  The calculation storage means 17 stores the above equation (1) and the radius T of the detector field. When the sample radius R is input by the input means 19, the calculation is performed to obtain the upper and lower limit angles ± θ1 and 2θ1. Are displayed on the display means 16 and stored.

  Next, along with the operation of the X-ray analyzer of the first embodiment, the X-ray analysis method of the second embodiment of the present invention will be described. Prior to the total reflection X-ray fluorescence analysis of the sample S having a diameter of 200 mm, a 360 ° diffraction pattern of the sample S is acquired.

That is, the sample S is placed on the sample table 8 shown in FIG. 1 by a sample transport means (not shown). The sample S is moved from the initial position on the sample stage 8 by the parallel moving means 12, and is set to a measurement point E (R1, 0) that is less affected by scattered rays from the sample edge as shown in FIG. . The sample stage 8 and the sample S by the rotating means 11, while 360 ° rotation it clockwise around the center O of the sample S, is irradiated from the X-ray source 1 to the measuring point E 1 primary X-rays 2, the sample S The secondary X-ray 4 including the fluorescent X-ray and the diffracted X-ray generated from is detected by the detector 7. As a result, the diffraction pattern shown in FIG. 3 is displayed on the display means 16 and stored in the control means 15. FIG. 3 shows the measured diffraction pattern of the W-Lβ line (W), where the horizontal axis represents the rotation angle ω of the sample S and the vertical axis represents the X-ray intensity of the W-Lβ line.

  Next, the measurer inputs the radius R of the sample S from the input unit 19 to the calculation storage unit 17. When the radius R of the sample S is inputted, the calculation storage means 17 calculates the upper and lower limit angles ± θ1 and 2θ1 based on the above equation (1), and displays and stores them on the display means 16. In the present embodiment, the detector visual field radius T is 10 mm, the sample radius R is 100 mm, and θ1 is 64 ° and 2θ1 is 128 °.

  In the above example, the radius R of the sample S is input and calculated by the calculation storage means 17 to obtain the upper and lower limit angles ± θ1 and 2θ1, but a silicon wafer, a liquid crystal glass, a hard disk, which is the sample S having a crystal structure, In the semiconductor industry, the diameter of a magnetic disk or the like is standardized to 50 mm (2 inches), 76 mm (3 inches), 100 mm, 125 mm, 150 mm, 200 mm, 300 mm, and the like. It is also possible to store the upper and lower limit angles ± θ1 and 2θ1 corresponding to and read them at the time of measurement.

  Next, the measurer avoids the diffracted X-rays in which the intensity of the diffracted X-rays is low in the diffraction pattern shown in FIG. 3 displayed on the display means 16 and does not show a sharp intensity increase at the adjacent angular position. The angle is selected by the selection means 18. At this time, for example, 25 °, so that the angle width of the adjacent angular position of the selected avoidance angle is less than the angle range 2θ1 calculated by the calculation storage means 17, in this embodiment, less than 128 °. Select 95 °, 180 °, 260 °, 345 °. The avoidance angle selected by the selection means 18 is registered. When registered, the control means 15 stores the avoidance angle as a measurement condition, and each position of the avoidance angles 25 °, 95 °, 180 °, 260 °, and 345 ° on the diffraction pattern displayed on the display means 16. A vertical line avoidance angle mark is displayed on the screen.

  In this way, since the selected avoidance angle mark is displayed on the diffraction pattern, it is easily visible whether the angle width of the adjacent angular position of the selected avoidance angle is an avoidance angle of less than 128 °. can do. Furthermore, when the angle width exceeds 128 °, it cannot be registered. Thus, the angle width can be reliably set to an avoidance angle of less than 128 °.

Next, when the measurement is started, the avoidance angle ω1 closest to the θ coordinate of the measurement point is read from the avoidance angles stored by the control means 15, and the sample S is set to the avoidance angle ω1 by the rotation means 11. When the sample S by the rotation means 11 is set to avoid the angle .omega.1, since the measurement points in the visual field V or et when total direction of the detector 7 angle .omega.1 - [theta] shifted, the control unit 15 controls the translation means 12 The sample S is moved in a state where the set avoidance angle ω1 is maintained, and the measurement point is made to coincide with the center P of the visual field V of the detector 7.

For example, when measurement of the measurement point F (100, −30) is started, the avoidance angle −15 ° (345 °) closest to the angle position of the θ coordinate of the measurement point F from the avoidance angles stored in the control unit 15. ) And the sample S is set by the rotating means 11 at an avoidance angle of −15 °. When the sample S is rotated to -15 ° by the rotating means 11, the measuring point F is shifted 15 ° in view V or et when total direction of the detector 7, as shown in FIG. 9, the control unit 15 is parallel movement The means 12 is controlled to move the sample S while maintaining the set avoidance angle of −15 ° so that the measurement point F coincides with the center P of the field of view V of the detector 7.

  Accordingly, the sample S is set to an avoidance angle of −15 ° (345 °) avoiding the diffracted X-ray, and the measurement point F of the sample S is irradiated with the primary X-ray 2 from the X-ray source 1, The generated secondary X-ray 4 is detected by a detector 7 and analyzed. For other measurement points, the control unit 15 controls the rotation unit 11 according to the coordinates to avoid diffracted X-rays from the sample S. The avoidance angles are set to 25 °, 95 °, 180 °, 260 °, and 345 °. Then, the parallel moving means 12 is controlled to set the measurement point of the sample S to the irradiation position of the primary X-ray and analyze it. The measurement points other than the vicinity of the edge of the sample S are similarly analyzed.

  Although the sample S having a diameter of 200 mm has been described, the samples S having other diameters are similarly analyzed.

  As described above, according to the X-ray analysis apparatus of the first embodiment and the method of the second embodiment, the apparatus structure near the edge of the sample S and the vicinity of the sample S according to the diameter R of the sample S having a crystal structure. By avoiding suppressing scattered rays and impure rays generated from an object, and avoiding diffracted X-rays generated from the sample S, it is possible to easily perform a highly accurate analysis.

  Next, an X-ray analyzer according to a third embodiment of the present invention will be described. As shown in FIG. 10, this apparatus does not include the control means 15 and the selection means 18 of the X-ray analysis apparatus of the first embodiment, but includes a control selection means 20 instead, and the other configurations are the same. Only different configurations will be described.

  The control selection means 20 emits the primary X-ray 2 from the X-ray source 1 while rotating the sample S around the predetermined point of the sample S by 360 ° by the rotation means 11, and is generated from the sample S and incident on the detector 7. A diffraction pattern in which the intensity of the secondary X-ray 4 is made to correspond to the rotation angle of the sample S is displayed on the display means 16 and the diffraction pattern is stored. The stored diffraction pattern (FIG. 3) is scanned with a predetermined X-ray intensity threshold, and if an X-ray intensity below this threshold exists over a predetermined angular range, for example, 3 ° to 5 °, this predetermined The center angle position of the angle range is stored as an avoidance angle. The central angle position is, for example, 25 °, 95 °, 180 °, 260 °, 345 °, or the like.

Based on the upper and lower limit values of the θ coordinate calculated and / or stored by the calculation storage unit 17 and the diffraction pattern displayed on the display unit 16, the control selection unit 20 sets the adjacent interval between the upper and lower limit value ranges of the θ coordinate. And an avoidance angle ω1 that is an X-ray intensity equal to or less than a predetermined threshold in the diffraction pattern and that can avoid the diffraction X-ray is selected and stored, and according to the coordinates of the measurement point of the sample S, The avoidance angle ω1 closest to the coordinates of the measurement point is read from the stored avoidance angle ω1, and the rotating means 11 is controlled so as to set the sample S at the avoidance angle ω1. When the sample S by the rotation means 11 is set to avoid the angle .omega.1, since the measurement points deviate field V or et at total direction angle .omega.1 - [theta] of the detector 7, the control selection means 20 controls the translation means 12 The measurement point is moved to the center P of the visual field V of the detector 7 while maintaining the set avoidance angle ω1.

  Next, the X-ray analysis method of the fourth embodiment will be described together with the operation of the X-ray analysis apparatus of the third embodiment. The apparatus according to the third embodiment does not include the control means 15 and the selection means 18 of the apparatus according to the first embodiment, but includes a control selection means 20 instead. The other configurations are the same, and therefore only different operations are performed. explain.

  In the apparatus of the first embodiment, the measurer avoids the diffracted X-rays in which the intensity of the diffracted X-rays is low from the diffraction patterns displayed on the display means 16 and does not show a sharp increase in intensity at the adjacent angular positions. Although the avoidance angle is selected by the selection means 18, in the apparatus of the third embodiment, the control selection means 20 automatically selects and stores the avoidance angle, and the avoidance angle closest to the coordinates of the measurement point among the stored avoidance angles. And the parallel movement means 12 and the rotation means 11 are controlled to automatically set the sample S at the avoidance angle, and the measurement point is set in the field of view V of the detector 7 while the set avoidance angle is maintained. Move to center P and analyze.

  According to the X-ray analysis apparatus of the third embodiment and the method of the fourth embodiment, automatically from the vicinity of the edge of the sample S and the apparatus structure near the sample S according to the diameter of the sample S having a crystal structure. By avoiding suppressing scattered rays and impure rays that are generated, and avoiding diffracted X-rays generated from the sample S, it is possible to perform analysis more easily and accurately.

  In the X-ray analysis apparatus of the present embodiment, the total reflection X-ray fluorescence analysis apparatus has been described. However, an energy dispersion type X-ray fluorescence analysis apparatus, a wavelength dispersion type X-ray fluorescence analysis apparatus, or the like that is not a total reflection type may be used. The present invention may be any X-ray analyzer that needs to avoid scattering and impurity lines generated from the sample S having a crystal structure and avoid diffracted X-rays. For example, a fluorescent X-ray analyzer, X It may be a composite X-ray analyzer in which a line reflectivity measuring device, an X-ray diffractometer or the like is combined.

DESCRIPTION OF SYMBOLS 1 X-ray source 2 Primary X-ray 4 Secondary X-ray 7 Detector 8 Sample stand 11 Rotating means 12 Parallel moving means 15 Control means 16 Display means 17 Calculation storage means 18 Selection means 20 Control selection means S Sample

Claims (3)

A sample stage on which a disk-shaped sample having a crystal structure is placed;
An X-ray source for irradiating the sample with primary X-rays;
A detector for detecting secondary X-rays generated from the sample;
Translation means for translating the sample stage so as to irradiate the primary X-rays at an arbitrary position on the sample measurement surface;
A rotating means for rotating the sample stage around an axis perpendicular to the sample measurement surface;
With
An X-ray analyzer that measures an arbitrary measurement site in the vicinity of the edge of a sample by being positioned so that primary X-rays are irradiated from the region above the sample and reflected outside the region,
The sample is irradiated with primary X-rays from the X-ray source while rotating the sample around a predetermined point of the sample by 360 ° by the rotating means, and the intensity of the secondary X-rays generated from the sample and incident on the detector is measured. Control means for displaying the diffraction pattern corresponding to the rotation angle on the display means, and storing the diffraction pattern;
Calculation storage means for calculating and / or storing the angular range 2θ1 obtained from the following formula (1) based on the radius R of the sample and the radius T of the field of view of the detector on the measurement surface of the sample for each diameter of the sample. When,
sin θ1 = (R−T) / R (1)
Based on the angle range 2θ1 calculated and / or stored by the calculation storage means by the measurer and the diffraction pattern displayed on the display means , there are a plurality of avoidance angles that can avoid the diffracted X-rays. selection means for spacing adjacent to each other to select the avoidance angle is within the angular range 2.theta.1,
With
The control means stores the avoidance angle selected by the measurer using the selection means, and according to the measurement point coordinates of the sample, the avoidance angle closest to the measurement point coordinates among the stored avoidance angles X-ray analysis apparatus that reads the signal, sets the sample to the read avoidance angle by controlling the rotating means, and sets the measurement point of the sample to the irradiation position of the primary X-ray by controlling the parallel moving means. A sample stage on which a disk-shaped sample having a crystal structure is placed;
An X-ray source for irradiating the sample with primary X-rays;
A detector for detecting secondary X-rays generated from the sample;
Translation means for translating the sample stage so as to irradiate the primary X-rays at an arbitrary position on the sample measurement surface;
A rotating means for rotating the sample stage around an axis perpendicular to the sample measurement surface;
With
An X-ray analyzer that measures an arbitrary measurement site in the vicinity of the edge of a sample by being positioned so that primary X-rays are irradiated from the region above the sample and reflected outside the region,
The sample is irradiated with primary X-rays from the X-ray source while rotating the sample around a predetermined point of the sample by 360 ° by the rotating means, and the intensity of the secondary X-rays generated from the sample and incident on the detector is measured. A control selection means for displaying the diffraction pattern corresponding to the rotation angle on the display means, and storing the diffraction pattern;
Calculation storage means for calculating and / or storing the angular range 2θ1 obtained from the following formula (1) based on the radius R of the sample and the radius T of the field of view of the detector on the measurement surface of the sample for each diameter of the sample. When,
With
sin θ1 = (R−T) / R (1)
Based on the angle range 2θ1 calculated and / or stored by the calculation storage means and the diffraction pattern displayed on the display means, the control selection means has an X-ray intensity below a predetermined threshold in the diffraction pattern. A plurality of avoidance angles that can avoid the diffracted X-rays, and an avoidance angle in which an interval between adjacent avoidance angles is within the angle range 2θ1 is selected and stored, and the storage is performed according to the coordinates of the measurement point of the sample. The avoidance angle closest to the coordinates of the measurement point is read out from the avoidance angles, the sample is set to the read avoidance angle by controlling the rotating means, and the measurement point of the sample is controlled by controlling the parallel moving means. X-ray analyzer set at the primary X-ray irradiation position. A sample stage on which a disk-shaped sample having a crystal structure is placed;
An X-ray source for irradiating the sample with primary X-rays;
A detector for detecting secondary X-rays generated from the sample;
Translation means for translating the sample stage so as to irradiate the primary X-rays at an arbitrary position on the sample measurement surface;
A rotating means for rotating the sample stage around an axis perpendicular to the sample measurement surface;
With
An X-ray analysis method using an X-ray analysis apparatus that measures an arbitrary measurement site in the vicinity of the edge of a sample by positioning it so that primary X-rays are irradiated from the region above the sample and reflected outside the region. There,
The intensity of the secondary X-ray generated from the sample and incident on the detector is irradiated with primary X-rays while the sample placed on the sample stage is rotated 360 ° around a predetermined point of the sample by the rotating means. To obtain a diffraction pattern corresponding to the rotation angle of the sample,
An angle range 2θ1 obtained from the following equation (1) based on the radius R of the sample and the radius T of the field of view of the detector on the measurement surface of the sample is calculated and stored for each sample diameter,
sin θ1 = (R−T) / R (1)
Based on the calculated and stored angle range 2θ1 and the diffraction pattern displayed on the display means, a plurality of avoidance angles that can avoid diffracted X-rays, and the adjacent intervals between the avoidance angles are within the angle range 2θ1. storing the avoidance angle is selected and, depending on the coordinates of the measuring points of the sample, read the closest avoidance angle coordinates of the measuring point from the avoidance angle to said storage, and read out the by said rotating means An X-ray analysis method in which a sample is set at an avoidance angle, and a measurement point of the sample is set as a primary X-ray irradiation position by the parallel moving means.

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