JP2000249667A - Fluorescent x-ray analysis device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent X-ray analysis device for rapidly and accurately analyzing an arbitrary fine site in a sample. SOLUTION: The image of a sample surface la is directly picked up by an image pick-up means 14, and the image is monitored by a display means and at the same time an arbitrary fine site is specified and set by a control means. For weak fluorescent X rays 6 from the set fine site, wavelength distribution characteristics are roughly examined quickly by an energy-distribution-type first detection means 30 with high sensitivity, and then intensity is measured by a wavelength-distribution-type second detection means 7 with high resolution only within a required wavelength range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent X
The present invention relates to a line analyzer.

[0002]

2. Description of the Related Art Conventionally, for example, as shown in FIG.
A sample 1 is irradiated with primary X-rays 4 using a so-called scanning type (wavelength dispersive type) fluorescent X-ray analyzer, and the sample surface 1a in a minute range at an arbitrary position and its vicinity in the depth direction (hereinafter referred to as sample X-rays 6 generated from one micro site)
There is a mapping measurement for measuring the intensity of the light and measuring the intensity distribution.

Here, for example, a disk-shaped sample 1 is stored in a sample holder 2, and the sample holder 2 is mounted on a sample stage 3, and the sample stage 3 is fixed to a so-called θ stage (rotary stage) 42. Have been. A plate-shaped collimator 43 having an aperture 43a for limiting the field of view of the detecting means 37 is provided between the sample table 3 and a diverging solar slit 19 of the detecting means 37 described later. This collimator 4
Reference numeral 3 denotes a driving means such as a pulse motor (not shown) moved by an arbitrary distance within a predetermined range by a control means 46 in a direction perpendicular to the paper surface.

Therefore, the minute portion to be analyzed is, for example, at a distance of r1 from the center of the sample surface 1a (the center axis of rotation of the sample holder 2 and the θ stage 42 passes) and at an angle of θ1 from the direction perpendicular to the paper. At this time, the θ stage 42 is rotated by −θ1 by the control means 46, and the aperture 43a
If the collimator 43 is moved so that the distance from the position where the center of the sample surface 1a is viewed to the position r1 is reached, the aperture 43a will see the minute part to be analyzed. Then, the primary X-ray 4 is irradiated to a wide area of the exposed sample surface 1 a, and the primary X-ray 4 is generated from the sample 1 and the aperture 4 of the collimator 43 is formed.
The fluorescent X-ray 6 passing through 3a, that is, the fluorescent X-ray 6 generated from an arbitrary minute portion of the sample 1, is detected by a divergent solar slit 19, a spectral element 8, a light-receiving solar slit 9, and a detector 10 such as a scintillation counter. Means 3
7, the intensity can be measured, that is, the micro site can be analyzed (see Japanese Patent Application Laid-Open No. 6-308060).

However, an X-ray source 5 such as an X-ray tube or a divergent solar slit 1
9 etc. are installed, and while directly looking at the sample surface 1a,
As described above, it is not possible to set a micro site to be measured. Therefore, conventionally, for example, before mounting the sample holder 2 on the sample stage 3, that is, outside the sample chamber 17 where the primary X-ray 4 is irradiated on the sample 1, a predetermined A transparent graph paper is placed on the sample surface 1a in accordance with the direction and the position, and X- and Y-coordinates (for the coordinate origin are, for example, sample surface 1a
Is read, the grid paper is removed, and the sample holder 2 is placed in such a manner that the predetermined direction and position of the sample holder 2 correspond to the corresponding directions and positions on the sample stage 3 in the initial state. Then, the input means 4 inputs the X coordinate and the Y coordinate.
5, the control means 46 calculates an appropriate rotation angle of the sample 1 by the θ stage 42 and a linear movement amount of the collimator 43 by the driving means based on the two coordinate values,
The setting and the measurement of the micro site to be measured are sequentially performed.

[0006]

However, although it is transparent, it is not easy to specify an arbitrary minute portion of the sample 1 when viewed through a grid paper. Further, it is difficult to read and input the X coordinate and the Y coordinate. It is troublesome and susceptible to typographical errors,
It is not possible to quickly and accurately set minute parts.

Further, for example, a sample surface 1a placed on the sample stage 3 is imaged by a CCD or the like and displayed on a CRT or the like,
Although it is conceivable to specify a micro site to be measured based on the displayed image, as described above, the sample stage 3
Since the X-ray source 5 such as an X-ray tube, the divergent solar slit 19, and the like are installed above the sample 1 placed on the
D may need to image the sample surface 1a from an oblique direction. In this case, the generated image is the same as the image obtained when the image is obtained from just above the sample surface 1a, that is, from the direction perpendicular to the sample surface 1a. Is different, and the image is different in scale (magnification) between vertical and horizontal. Therefore, it is not easy to specify a micro site to be measured based on such an image, and it may not be possible to quickly and accurately set the micro site.

Further, when a part of the sample surface 1a is imaged and enlarged and displayed so that a minute portion can be designated without a complicated mechanism such as zooming, an image of the entire sample surface 1a cannot be displayed. Therefore, it is not easy to specify a micro site to be measured based only on such a partial image of the sample surface 1a, and it may not be possible to quickly and accurately set the micro site.

Furthermore, even if the minute portion to be measured is accurately set, the intensity of the fluorescent X-ray 6 from such a minute portion is low, and the solar slit 1
Since the intensity tends to be very weak after passing through 9, 9 and the spectroscopic element 8, the intensity is measured with a high resolution over a wide wavelength range by interlocking the spectroscopic element 8 with the detector 10 such as a scintillation counter and the solar slit 9 using a goniometer. This may take a long time, and may cause a problem that a rapid analysis of a micro site cannot be performed.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a fluorescent X-ray analyzer capable of quickly and accurately analyzing an arbitrary minute portion in a sample.

[0011]

In order to achieve the above object, an X-ray fluorescence spectrometer according to a first aspect of the present invention comprises a sample stage on which a sample is placed and an X-ray for irradiating the sample with primary X-rays. Source,
Detecting means for measuring the intensity of fluorescent X-rays generated from the sample. Further, there is provided moving means for relatively moving the sample, the X-ray source and the detecting means.

[0012] Further, an image pickup means for picking up an image of the sample surface from an oblique direction to generate an image, and correcting the image of the sample surface generated by the image pickup means to an image picked up from a direction perpendicular to the sample surface. Correction means, display means for displaying an image of the sample surface corrected by the correction means,
Control means for controlling the moving means such that fluorescent X-rays generated from a site of the sample designated based on the image of the sample surface displayed by the display means are incident on the detection means.

According to the first aspect of the present invention, an arbitrary minute portion can be specified while directly imaging the surface of the sample and looking at the corrected image as if it was imaged from directly above. The site can be set quickly and accurately. Therefore, any micro site in the sample can be analyzed quickly and accurately.

An X-ray fluorescence analyzer according to a second aspect of the present invention includes a sample stage, an X-ray source, a detecting unit, and a moving unit, as in the first embodiment. Then, an imaging unit that captures an image of a part of the sample surface to generate an image, and the moving unit is driven to obtain a plurality of partial images of the sample surface generated by the imaging unit. A synthesizing means for synthesizing an image of the entire sample surface from the image, a display means for displaying an image of the entire sample surface synthesized by the synthesizing means, and a designation means based on the image of the entire sample surface displayed by the display means. Control means for controlling the moving means so that the fluorescent X-rays generated from the site of the sample are incident on the detecting means.

According to the second aspect of the present invention, an arbitrary minute portion can be designated while viewing an image of the entire sample surface synthesized by directly imaging a plurality of portions of the sample surface. The site can be set quickly and accurately.
Therefore, any micro site in the sample can be analyzed quickly and accurately.

According to a third aspect of the present invention, in the X-ray fluorescence spectrometer according to the second aspect, an image of the entire surface of the sample synthesized by the synthesizing unit and the imaging unit including the designated sample portion are generated. The displayed enlarged image of a part of the sample surface is displayed on the same screen of the display means, and based on the displayed enlarged image of the part of the sample surface, the fluorescent light X generated from a designated part of the sample is further displayed. Control means is provided for controlling the moving means so that a line is incident on the detecting means.

According to the third aspect of the present invention, an arbitrary minute portion is designated while viewing an image of the entire sample surface synthesized by directly imaging a plurality of portions of the sample surface, and thereby the designated portion of the sample is designated. Can be displayed on the same screen as the image of the entire sample surface, including the image of the entire sample surface. Any micro site to be measured in can be set more accurately.

According to a fourth aspect of the present invention, there is provided an X-ray fluorescence spectrometer which comprises a sample stage on which a sample is placed and an X-ray for irradiating the sample with primary X-rays.
A source, an energy-dispersive first detecting means for measuring the intensity of the fluorescent X-rays generated from the sample in close proximity to the sample, and measuring the intensity by spectrally separating the fluorescent X-rays generated from the sample by a spectroscopic element Second detecting means, the sample stage and first and second
A collimator provided between the first and second detectors, the collimator being provided between the first and second detectors. Further, there is provided moving means for relatively moving the sample and the X-ray source and the first detecting means or the sample and the X-ray source and the second detecting means.

Further, imaging means for imaging the sample surface to generate an image, display means for displaying the image of the sample surface generated by the imaging means, and image processing means for displaying an image of the sample surface displayed by the display means. And control means for controlling the moving means so that the fluorescent X-rays generated from the designated site of the sample are incident on the first detecting means or the second detecting means.

According to the device of the fourth aspect, an arbitrary minute portion can be designated while looking at an image directly picked up from the surface of the sample, so that any minute portion to be measured in the sample can be set quickly and accurately. Furthermore, regarding weak fluorescent X-rays from a minute part whose field of view is limited by a collimator,
First, after examining the wavelength distribution characteristics in a short time by the highly sensitive energy dispersive first detecting means, the intensity can be measured by the high resolution wavelength dispersive second detecting means only in the necessary wavelength range. In addition, it is possible to quickly and accurately analyze a set micro site. Therefore, any micro site in the sample can be analyzed quickly and accurately.

According to a fifth aspect of the present invention, there is provided an X-ray fluorescence analyzer.
In the apparatus described above, the imaging means captures an image of the surface of the sample placed on the sample stage to generate an image. According to the apparatus of the fifth aspect, an arbitrary minute portion can be specified while looking at an image obtained by directly imaging the surface of the sample placed on the sample stage immediately before the measurement, so that any minute portion to be measured in the sample can be more accurately determined. Can be set to

The X-ray fluorescence spectrometer according to claim 6 is the fifth invention.
In the above device, the second detecting means has a divergent solar slit. The divergent solar slit and at least a part of the imaging means are provided between the collimator and the spectral element, and one of them is selectively positioned so as to face a sample mounted on a sample stage. Means. According to the apparatus of claim 6, since the selecting means for moving the imaging means can also serve as a divergent solar slit exchanger, the configuration of the apparatus is easy.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An apparatus according to a first embodiment will be described below with reference to the drawings. First, the configuration of this device will be described. As shown in FIG. 1, the apparatus includes a sample table 3 on which a sample 1 is placed, an X-ray source 5 such as an X-ray tube for irradiating the sample 1 with primary X-rays 4, Generated fluorescent X
An energy dispersive type first detecting means (for example, SSD) 30 for measuring the intensity of the line 6 close to the sample 1 and measuring the intensity of the fluorescent X-ray 6 generated from the sample 1 by dispersing it with the spectroscopic element 8 And second detection means 7 for performing the operation.

The apparatus further comprises a collimator 13 provided between the sample table 3 and the first and second detecting means 30 and 7 for limiting the field of view of the first or second detecting means 30 and 7. I have. That is, in the sample chamber 17 where the primary X-ray 4 is irradiated to the sample 1, the control unit 1 is brought close to the sample 1.
6 is provided with a plate-shaped collimator 13 which is moved in a direction perpendicular to the plane of the drawing by a driving means such as a pulse motor (not shown).
3a, 13b (13b is shown in FIG. 4 which is a view in the direction of arrow D (partial sectional view)), and the first detection means is provided behind the aperture 13b (in the traveling direction of the fluorescent X-ray 6). Barrel SS
D30 is attached.

The second detecting means 7 includes a divergent solar slit 19 through which the fluorescent X-rays 6 generated from the sample 1 pass, a spectroscopic element 8 for dispersing the fluorescent X-rays 6 passing therethrough, and Detector 1 such as a proportional counter or a scintillation counter for measuring the intensity of the received solar slit 9 and the fluorescent X-ray 6 passing therethrough
Consists of zero. The spectroscopic element 8, the light-receiving solar slit 9, and the detector 10 are linked by a so-called goniometer, and perform measurement in a predetermined wavelength range. Further, there is provided a moving unit 12 for relatively moving the sample 1 and the X-ray source 5 and the first detecting unit 30 or the sample 1 and the X-ray source 5 and the second detecting unit 7. The sample 1 is stored in a sample holder 2 and the moving means 12 is a so-called rθ stage 1
2, but may be an XY stage or the like. In any case, the moving direction and the like are set so that there is no obstacle to the movement of the sample holder 2 by the moving means.

It is preferable that a filter plate 40 be provided in front of the X-ray source 5 in order to irradiate the primary X-rays 4 corresponding to the sample 1. The filter plate 40 has filters having various transmission characteristics and a cut-off portion that does not transmit X-rays from the X-ray source 5 in the direction perpendicular to the plane of the paper. Moved to In addition,
The filter plate 40 may be substantially disc-shaped, have various filters and blocking portions in the circumferential direction, and be rotated by the control means 16.

Further, this apparatus captures a part of the surface 1a of the sample 1 placed on the sample table 3 via the sample holder 2 from an oblique direction (for example, from a direction at 40 degrees with respect to the sample surface 1a). And an imaging unit 14 for generating an image. Then, a correction means 60 is provided which corrects an image of a part of the sample surface 1a generated by the imaging means 14 into an image obtained by imaging from a direction perpendicular to the sample surface 1a (from directly above the sample surface 1a). ing. Further, the rθ table 12 is driven to obtain a plurality of partial images of the sample surface 1a generated by the imaging unit 14 and corrected by the correction unit 60, and an image of the entire sample surface 1a is synthesized from the plurality of images. The synthesizing means 61 is provided.

The display means 15 such as a liquid crystal panel for displaying an image of the entire sample surface 1a synthesized by the synthesizing means 61, and a designation is made based on the image of the entire sample surface 1a displayed by the display means 15. The fluorescent X-rays 6 generated from the site of the sample 1 (including the entire sample when the entire sample is minute) are supplied to the first detection unit 30 or the second detection unit 7.
Control means 16 for controlling the rθ stage 12 so as to be incident on the stage. More specifically, this control means 1
A display unit 15 displays an image of the entire sample surface 1a synthesized by the synthesis unit 60 and an enlarged image of a part of the sample surface 1a generated by the imaging unit 14 including the designated portion of the sample 1. Is displayed on the same screen 15b, and based on the displayed enlarged image of a part of the sample surface 1a, the fluorescent X-rays 6 generated from the part of the sample 1 further designated are the first detecting means 30 or the second detecting means. Stage 12 can also be controlled so as to be incident on.

The imaging means 14 is provided inside a spectroscopic chamber 18 in which the fluorescent X-rays 6 generated from the sample 1 are separated. Here, as shown in FIG. 2 in detail, the image pickup means 14 has a cylindrical case 14d, a window 14c made of lead glass or the like provided at the tip thereof, and allows light entering through the window 14c to pass therethrough. A lens 14b, a CCD 14a for generating an image from light passing through the lens 14b, and one end of the case 1
4d is connected to the rear end, covers the connection cord 62, and the other end is connected to the inner wall 18a of the spectroscopic chamber 18 (see FIG. 1). The connection cord 62 extends from the rear end of the case 14 d of the imaging unit 14, penetrates the wall of the spectroscopic chamber 18, and corrects the image signal generated by the CCD 14 a as shown in FIG. Is transmitted to the display means 15 via the.

The space between the front end of the case 14d and the window 14c in FIG. 2, the rear end of the case 14d and one end of the tube 14e, and the other end of the tube 14e in FIG. The reason why the imaging means 14 is configured in this way is that the inside of the spectroscopic chamber 18 is set in a vacuum atmosphere, but the performance of the CCD 14a in FIG. 2 cannot be guaranteed in a vacuum atmosphere.
This is for communicating the inside of the case 14d with the atmospheric pressure atmosphere outside the spectroscopic chamber 18.

It should be noted that only a reflecting mirror is provided in the spectroscopic chamber 18 as a part of the image pickup means 14, and a mirror image thereof is picked up by a CCD 14a outside the spectroscopic chamber 18 through a window provided in the wall of the spectroscopic chamber 18. You may. In addition, only one end of the optical fiber cable is provided in the spectroscopic chamber 18 as a part of the imaging unit 14, and the other end is penetrated through the wall of the spectroscopic chamber 18.
It may be configured to capture an image transmitted in connection with the external CCD 14a. In the case of such a configuration, a portion provided with a window or a portion through which an optical fiber cable penetrates in the wall of the spectroscopic chamber 18 is sealed. In addition, imaging means 1
Reference numeral 4 preferably has a light (not shown) for illuminating the sample surface 1a at the time of imaging at a tip portion thereof, in the vicinity of the window 14c in FIG.

Further, this apparatus is provided with a divergent solar slit 19 and an image pickup means 14 between the collimator 13 and the spectroscopic element 8 (also between the sample table 3 and the spectroscopic element 8) as shown in FIG. And a selecting means 20 for selectively positioning one of them so as to face the sample 1 placed on the sample table 3. 3 is a plan view of a part of FIG.
As shown in FIG.
The case 14d including the two divergent solar slits 19A, 19B, and 19C and the CCD 14a of the imaging means 14 is one
The two driven gears 21 are mounted such that their axes are parallel to the rotation axis 21a of the driven gear 21 and are equidistant from the rotation axis 21a, and the rotation angles are at positions every 90 degrees. . As shown in FIG. 2, the selection means 20 including the driven gear 21 is configured as follows.

The rotating shaft 21a of the driven gear is connected to the spectral chamber 1
The driven gear 21 is rotatably supported by a base 22 fixed to the inner wall of the drive gear 8 and meshes with a drive gear 24. The rotating shaft 2 of the motor 25 is
5a is connected and fixed. Rotary shaft 25a of motor 25
Is parallel to the rotation shaft 21 a of the driven gear 21, and the motor 25 is connected to the base 2 via a support 26 and an arm 27.
It is fixed to 2. Therefore, the selecting means 20, which is the entire mechanism configured as described above, can selectively position any of the divergent solar slits 19A, 19B, 19C and the imaging means 14 so as to face the sample 1. As described above, according to the apparatus of the first embodiment, since the selecting means 20 for moving the imaging means 14 also serves as an exchange for the divergent solar slits 19A, 19B, and 19C, the configuration of the apparatus is easy.

In the apparatus of the first embodiment, the selecting means 20 uses the driving side gear 24 and the driven side gear 21
Both are constituted by spur gears, but as shown in the plan view of FIG. 10, the driving side is a pinion 54, the driven side is a rack 51a which moves in the direction perpendicular to the paper surface, and the divergent solar is mounted on a plate 51 to which the rack 51a is attached. Slit 19 and imaging means 14
May be arranged side by side in a direction perpendicular to the paper surface of FIGS. 1 and 2 to constitute the selection means 50.

Next, the operation of this device will be described.
In FIG. 1, first, a sample holder 2 containing a sample 1 is placed on a sample table 3, and when an instruction to set a micro site to be measured is input to the control unit 16, the control unit 1
6 retreats the collimator 13 in a direction perpendicular to the plane of the drawing by a driving means (not shown) so as not to obstruct the imaging, and sets the imaging means 14 so as to face the sample 1 by the selection means 20 so that a part of the sample surface 1a is inclined. An image is generated by imaging from the direction.

Here, as shown in FIG. 11 (a), assuming that meshes are provided evenly on the sample surface 1a, the imaging means 14 provided at an oblique angle of 40 degrees with respect to the sample surface 1a. As shown in FIG. 11B, the image generated in FIG. 1 is an image compressed by multiplying the vertical direction (the horizontal direction in FIG. 1) by sin 40 °. In such an image, there is no real feeling, and it is not easy to specify a micro site to be measured based on the image. Therefore, in the apparatus of the first embodiment, the correction unit 60 of FIG. 1 converts the image of a part of the sample surface 1a generated by the imaging unit 14 in the vertical direction (FIG. 1).
The image is stretched by 1) multiplied by 1 / sin 40 ° and corrected to an image taken from a direction perpendicular to the sample surface 1a (directly above the sample surface 1a), that is, an image as shown in FIG. I do.

Strictly speaking, the angle of the image pickup means 14 (FIG. 1) with respect to the sample surface 1a differs depending on the vertical position on the sample surface 1a. Strictly speaking, it depends on the vertical position of the image. If the angle is shallow and the image has a wide range in the vertical direction, the effect will be greater.In such a case, consider that as well, for example, by dividing the image in the vertical direction into several parts. Set the correction magnification appropriately. In the horizontal direction (perpendicular to the plane of FIG. 1),
The image is corrected by the lens 14b (FIG. 2) of the image pickup means so that both the near and far objects have the same length when viewed from the image pickup means 14 in FIG.

However, even if the above modifications are made,
The apparatus according to the first embodiment captures and enlarges and displays a part of the sample surface 1a so that a minute part can be designated without using a complicated mechanism such as zooming, so that the rθ table 12 is driven as it is. However, only a part of the sample surface 1a can be displayed, and an image of the entire sample surface 1a cannot be displayed. As described above, it is not easy to specify a minute part to be measured based on only a part of the image of the sample surface 1a in a state where the image of the entire sample surface 1a cannot be fully viewed. Therefore,
In the device of the first embodiment, the instruction of the control unit 16
The synthesizing unit 61 drives the rθ table 12 to obtain a plurality of partial images of the sample surface 1a generated by the imaging unit 14 and corrected by the correcting unit 60 (13 rectangular images shown by solid lines in FIG. 12). Image), and an image of the entire sample surface 1a (one circular image indicated by a two-dot chain line in FIG. 12) is synthesized from the plurality of images. In FIG. 12, although there are overlapping portions in the 13 rectangular images indicated by the solid lines, for example, an image captured earlier may be preferentially used for synthesis.

The control means 16 in FIG. 1 causes the display means 15 to display an image of the entire sample surface 1a synthesized by the synthesizing means 61 (left side in FIG. 13). At the time of imaging, the filter plate 40 is moved, and a blocking unit that does not transmit X-rays from the X-ray source 5 is located in front of the X-ray source 5. The reason for this operation is that even if X-rays are generated from the X-ray source 5, the X-rays do not reach the lens 14b (FIG. 2) of the imaging means 14 and cause a problem such as discoloration. At the same time,
The sample surface 1a is illuminated by the light of the imaging means 14, but the illumination light is reflected by the back surface (lower surface) of the filter plate 40, and the sample surface 1a is illuminated even brighter.

Here, the screen 15b of the display means 15 is an input means such as a so-called touch panel.
If the operator can directly specify a micro site to be measured based on the entire image of the sample surface 1a displayed on the left side of the screen 15b, the operator can directly specify “specify from the entire image” on the lower right side of the screen 15b. The user can press and select an arbitrary position in the image of the entire sample surface 1a displayed on the left side with a pen or the like to designate and input a minute part to be measured. Instead of pressing screen 15b directly, screen 1
The cursor appearing on 5b can be moved by an input means such as a mouse (not shown) so as to coincide with an arbitrary position on the screen 15b and clicked to select, designate, input, or the like.

When the part to be measured is particularly minute,
When it is difficult to directly specify the minute part to be measured based on the entire image of the sample surface 1a, the operator directly presses "designation from a partial image" on the lower right side of the screen 15b with a pen or the like. When the user selects and designates an arbitrary position of the image of the entire sample surface 1a displayed on the left side by directly pressing with a pen or the like, the control unit 16 generates the image by the imaging unit 14 including the specified portion of the sample 1. Of the sample surface 1a (2
The enlarged image of the portion surrounded by the dashed line) is displayed on the same screen 15b of the display means 15, as shown on the right side of FIG. 13, and the operator can view the enlarged image of a part of the displayed sample surface 1a. By pressing an arbitrary position directly with a pen or the like, a minute part to be measured can be designated and input.

In addition to specifying and inputting a minute portion to be measured, it is also possible to specify the both ends of the line segment and the number of divisions in addition to the point by point (see Japanese Patent Application No. 09-232308). . For example, in the case of five divisions, two points at both ends and the division number 5
Just specify the 6 on the line segment determined by the two points at both ends.
Points (points at which the line segment is divided into five and including both ends) are designated and input as minute parts to be measured. Alternatively, two points on the diagonal of the rectangle and the number of divisions in both the vertical and horizontal directions may be designated (see the same issue). For example, in the case of three vertical divisions and four horizontal divisions, simply designating two diagonal points and the number of divisions 3 and 4 divides a rectangle determined by two diagonal points into three vertically and four horizontally. Twenty points on the grid to be divided (including both ends of the grid and the corners of the rectangle) are designated and input as minute parts to be measured.

When the input of the end of the designation is input, the control means 16 of FIG.
An appropriate rotation angle and linear movement amount of the sample 1 by the θ stage 12 are calculated, and the primary X
The X-ray 4 is irradiated, and the fluorescent X-ray 6 generated therefrom is
The rθ stage 12 is controlled to set a minute part to be measured so as to be incident on the detecting means 30. in this way,
According to the apparatus of the first embodiment, an arbitrary minute portion can be designated while looking at an image obtained by directly imaging the sample surface 1a placed on the sample stage 3 immediately before measurement. The site can be set quickly and accurately.

Further, the control means 16 sets such a minute part and moves the collimator 13 in the direction perpendicular to the plane of the drawing, so that the aperture 13b and the first detecting means 30
Is appropriately positioned (switching to use the aperture 13b). Further, the operator selects a filter on the filter plate 40 according to the wavelength of the fluorescent X-rays 6 to be generated. This selection may be performed by the control unit 16 by inputting the wavelength of the fluorescent X-ray 6 to be generated or the like. When an appropriate filter is selected, the control means 16
The sample 1 is irradiated with the primary X-ray 4 from the X-ray source 5 and the intensity of the generated fluorescent X-ray 6 is measured by the first detecting means 30 which is an SSD. Thus, according to the device of the first embodiment,
Regarding the fluorescent X-rays 6 having a weak intensity from a minute portion, first, the wavelength distribution characteristics can be roughly investigated in a short time by the energy-sensitive first detection means 30 having high sensitivity.

Next, the operator examines the wavelength distribution characteristics and inputs the wavelength range to be analyzed in detail to the control means 16. Then, the collimator 13 is moved in the direction perpendicular to the plane of the paper to position the aperture 13a appropriately (the aperture 13a
Switch to use). Further, the operator positions an appropriate divergence slit, for example, a divergence slit 19 </ b> A according to the wavelength of the fluorescent X-ray 6 to be analyzed, by the selection unit 20 so as to face the sample 1. This selection is also made by the control means 1
6 may be performed. Similarly, selection of a filter in the filter plate 40 is performed. Appropriate divergence slit 19
A. When the filter is selected, the control means 16 irradiates the sample 1 with the primary X-rays 4 from the X-ray source 5 and intensifies the fluorescent X-rays 6 generated in a wavelength range to be analyzed in a desired detail. Is measured by the second detection means 7. When a plurality of micro sites to be measured are specified collectively, for example, the setting and measurement of each micro site are performed in the specified order.

As described above, according to the apparatus of the first embodiment, with respect to the fluorescent X-ray 6 having a weak intensity from a minute part,
After the first detection means 30 roughly examines the wavelength distribution characteristics in a short time, the intensity can be measured by the wavelength-dispersion type second detection means 7 having a high resolution only in a necessary wavelength range. The site can be analyzed quickly and accurately. That is, any micro site to be measured in the sample 1 can be set quickly and accurately, and the set micro site can be analyzed quickly and accurately. Therefore, any micro site in the sample 1 can be analyzed quickly and accurately.

Next, an apparatus according to a second embodiment of the present invention will be described with reference to the drawings. First, the configuration of this device will be described. As shown in FIG.
4 is provided outside the sample chamber 17 and the spectroscopic chamber 18,
Since there is no obstacle above the sample 1 to be imaged, an image of the entire sample surface 1a before being mounted on the sample table 3 can be taken from directly above to generate an image ( Therefore, it is different from the device of the first embodiment in that it does not include the correcting means 60 and the synthesizing means 61) and does not include the selecting means 20 and the filter plate 40 as described above.
The other points are the same, and the description is omitted.

Here, the imaging means 3 of the apparatus of the second embodiment
4 is a cylindrical case 3 which is entirely in an atmospheric pressure atmosphere.
4d, a lens 34b provided at the tip thereof, and a CCD 34a for generating an image from light passing through the lens 34b.
And an imaging table 34g on which the sample holder 2 containing the sample 1 is placed, and a support 3 for supporting the case 34d on the imaging table 34g such that the CCD 34a faces the surface 1a of the sample 1.
4f. The code 15a of the display means 15 extends from the rear end of the case 34d of the imaging means 34, and extends from the CCD 34a.
Is transmitted to the display means 15 body.

Next, the operation of this device will be described.
First, the sample holder 2 containing the sample 1 is inserted into the CCD 34a.
For example, the sample holder 2 is oriented in a predetermined direction just below
Is mounted on the imaging table 34g by, for example, aligning the projection 2a provided on the imaging table 34g with the mark provided on the imaging table 34g. And control means 3
When an instruction to store an image of the sample surface 1a (entire sample surface 1a, hereinafter the same in the second embodiment) is input to the control unit 6, the control unit 36 captures the image of the sample surface 1a by the image capturing unit 34 and displays the image. Generate and store the image. further,
When specifying and inputting the measurement conditions, when the control means 36 is instructed to set a part to be measured, the control means 36 displays the stored image of the sample surface 1a on the display means 15. Let it. Here, similarly to the device of the first embodiment, the screen 15b of the display means 15 is an input means such as a so-called touch panel.
An arbitrary position of the image of the sample surface 1a shown in FIG. 2b can be directly pressed with a pen or the like, and designated and input as a site to be measured.

When the designation and input of the measurement conditions are completed, the sample 1
Is placed in the center of the sample table 3. When the setting of the part to be measured and the fact that measurement is to be performed are input, the control means 36 first rotates the sample stage 3 by the rθ stage 12, and the projection 2 a of the sample holder 2 is reflected by the reflection sensor 70. By detecting, the sample 1 is oriented in a predetermined direction (a direction that matches the image of the sample surface 1a).
Toward the initial state. Subsequently, similarly to the device of the first embodiment, the control means 36 calculates an appropriate rotation angle and a linear movement amount of the sample 1 by the rθ stage 12 from the position of the designated point on the screen 15b, and specifies the designated position. The rθ stage 12 is controlled to set a part to be measured so that the primary X-ray 4 is irradiated most strongly on the part which has been irradiated and the fluorescent X-ray 6 generated therefrom is incident on the first detection means 30. In addition, by providing a rotation angle adjuster (θ stage) and the reflection type sensor 70 also in the imaging table 34g, the sample 1 at the time of imaging
May be determined by the control means 36.

As described above, according to the apparatus of the second embodiment, an arbitrary minute portion can be designated while looking at the image directly taken of the sample surface 1a. Can be set accurately. Thereafter, measurement can be performed in the same manner as in the apparatus of the first embodiment, and the first detecting unit 30 detects the weak fluorescent X-rays 6 from the minute part.
After roughly examining the wavelength distribution characteristics in a short time,
Only in a necessary wavelength range, the intensity can be measured by the wavelength-dispersion type second detection means 37 having a high resolution, so that a set minute portion can be analyzed quickly and accurately. That is, any micro site to be measured in the sample 1 can be set quickly and accurately, and the set micro site can be analyzed quickly and accurately. Therefore, any micro site in the sample 1 can be analyzed quickly and accurately.

In the apparatus of the second embodiment, since the imaging means 34 is provided outside the narrow sample chamber 17 and the spectroscopic chamber 18 instead of inside, the configuration of the apparatus is easy. That is, without exposing the CCD 34a to a vacuum atmosphere,
There is no need to devise at least a part of 4 in the sample chamber 17 or the spectroscopic chamber 18.

According to the apparatus of the first or second embodiment, the measurement results can be displayed on the screen 15b of the display means 15 at the same time as the image of the sampled surface 1a. It's easy to do. For example, in FIG. 6, the positions A, B, and C of the designated portions are superimposed and displayed on the image of the sampled surface 1a on the left side of the screen 15b, and the composition of each portion is displayed as a table on the right side. In FIG. 7, similarly, the composition at each site is displayed as a bar graph at the corresponding position on the perspective view of the sample 1 on the right side.
In FIG. 8, similarly, on the right side, the content of each element for each element is represented by the color density (shown as hatching density in FIG. 8) at the corresponding position on the plan view of Sample 1. Displayed). In FIG. 8, 0 to 2 and the like mean 0% or more and less than 2%.

The apparatus according to the first and second embodiments includes:
For example, the collimator 13 shown in FIG. 4 is provided with a large-diameter aperture to provide a normal, non-micro site (the entire sample when the entire sample is not particularly micro). Also included). In such a case, if the intensity of the fluorescent X-rays 6 generated from the portion of the sample 1 to be measured is sufficient, the first detecting means 30 is not used, and the second detecting means 7 is initially provided in a wide wavelength range. , 37, the intensity can also be measured.

[0055]

As described above in detail, according to the present invention, an arbitrary minute portion can be specified while looking at an image directly taken of the sample surface. Can be set accurately. Therefore,
For any micro site in a sample, it can be analyzed quickly and accurately.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a fluorescent X-ray analyzer according to a first embodiment of the present invention.

FIG. 2 is a diagram illustrating a selection unit, an imaging unit, and the like of the apparatus.

FIG. 3 is a plan view of a part of FIG. 2;

FIG. 4 is a view (partial sectional view) taken in the direction of arrow D in FIG. 1;

FIG. 5 is a schematic diagram showing a fluorescent X-ray analyzer according to a second embodiment of the present invention.

FIG. 6 is a diagram illustrating a display example of a measurement result obtained by the X-ray fluorescence spectrometer according to the first or second embodiment of the present invention.

FIG. 7 is a diagram showing another display example of a measurement result by the same device.

FIG. 8 is a diagram showing still another display example of a measurement result by the same device.

FIG. 9 is a schematic view showing an example of a conventional X-ray fluorescence analyzer.

FIG. 10 is a plan view showing another selection means and the like of the X-ray fluorescence spectrometer according to the first embodiment of the present invention.

FIG. 11 is a diagram showing the operation of the correcting means of the X-ray fluorescence analyzer according to the first embodiment of the present invention.

FIG. 12 is a view showing the operation of the synthesizing means of the apparatus.

FIG. 13 is a diagram showing a display example when a minute part to be measured is designated by the same device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... sample, 3 ... sample stage, 4 ... primary X-ray, 5 ... X-ray source, 6
... X-ray fluorescence, 7 ... Second detection means, 8 ... Spectroscopy element, 12 ...
Moving means (rθ stage), 13 ... collimator, 14 ...
Imaging means, 15 display means, 16 control means, 19 divergent solar slit, 20, 50 selection means, 30 first
Detecting means (SSD), 60 ... correcting means, 61 ... combining means.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoki Kawahara 14-8 Akaoji-cho, Takatsuki-shi, Osaka Prefecture Inside Rigaku Denki Kogyo Co., Ltd. (72) Inventor Koichi Aoyagi 14-8 Akaoji-cho, Takatsuki-shi, Osaka Science Inside Electric Machinery Co., Ltd. (72) Inventor Etsuhisa Yamamoto 14-8 Akaoji-cho, Takatsuki-shi, Osaka Rigaku Electric Industry Co., Ltd.

Claims (6)

[Claims] 1. A sample table on which a sample is placed, an X-ray source for irradiating the sample with primary X-rays, detection means for measuring the intensity of fluorescent X-rays generated from the sample, a sample and the X-ray A moving means for relatively moving the source and the detecting means, an imaging means for imaging the sample surface from an oblique direction to generate an image, and an image of the sample surface generated by the imaging means being perpendicular to the sample surface. Correction means for correcting the image taken when viewed from the direction, display means for displaying the image of the sample surface corrected by the correction means, and a sample designated based on the image of the sample surface displayed by the display means X-ray fluorescence analyzer comprising: control means for controlling said moving means so that fluorescent X-rays generated from said part are incident on said detection means. 2. A sample table on which a sample is placed, an X-ray source for irradiating the sample with primary X-rays, a detecting means for measuring the intensity of fluorescent X-rays generated from the sample, a sample and the X-ray A moving unit that relatively moves the source and the detecting unit; an imaging unit that captures a part of the sample surface to generate an image; and a driving unit that drives the moving unit to move the sample surface generated by the imaging unit. Combining means for obtaining a plurality of partial images and synthesizing an image of the entire sample surface from the plurality of images; display means for displaying an image of the entire sample surface synthesized by the synthesizing means; X-ray fluorescence analyzer comprising: control means for controlling the moving means so that fluorescent X-rays generated from a site of the sample designated based on the displayed image of the entire sample surface are incident on the detecting means. . 3. The image of the entire sample surface synthesized by the synthesizing means according to claim 2,
An enlarged image of a part of the sample surface generated by the imaging unit including the specified sample part is displayed on the same screen of the display unit, and the displayed enlarged image of a part of the sample surface is displayed. An X-ray fluorescence analyzer further comprising control means for controlling the moving means so that X-rays generated from a site of the sample further designated based on the detection means are incident on the detection means. 4. A sample stage on which a sample is placed, an X-ray source for irradiating the sample with primary X-rays, and an energy dispersive type for measuring the intensity of fluorescent X-rays generated from the sample in close proximity to the sample. A first detection unit, a second detection unit that disperses fluorescent X-rays generated from the sample by a spectroscopic element and measures the intensity thereof, and is provided between the sample stage and the first and second detection units, A collimator for limiting the field of view of the first or second detection means, and a movement means for relatively moving the sample and the X-ray source and the first detection means, or a sample and the X-ray source and the second detection means. An imaging unit that captures an image of the sample surface to generate an image; a display unit that displays an image of the sample surface generated by the imaging unit; and a display unit that is designated based on the image of the sample surface displayed by the display unit. X-ray fluorescence emitted from the site of the sample Said to be incident to the first detecting means or the second detecting means, the fluorescent X-ray analyzer and a control means for controlling said moving means. 5. The X-ray fluorescence spectrometer according to claim 4, wherein the imaging unit captures an image of a surface of the sample placed on the sample stage to generate an image. 6. The divergence solar slit according to claim 5, wherein the second detection means has a divergence solar slit, and the divergence solar slit and at least a part of the imaging means are provided between the collimator and the spectral element. X-ray fluorescence spectrometer provided with a selection means for selectively positioning one of them so as to face a sample placed on a sample stage.