JPS63169544A - X-ray inspection device for crystalline substance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to material investigation using diffraction radiation, and more specifically to an X-ray inspection device for crystalline materials, mainly for the purpose of elucidating and refining the structure of the material. To determine the overall intensity of X-ray reflection by a single crystal, to examine the electron concentration distribution within a single crystal, and to investigate the structure, phase composition, texture, and macro- and micro-distortion of polycrystalline materials. To find out,
Used to study the intensity of reflections diffracted by polycrystals.

Elucidating problems such as phase changes in the composition of ferroelectric, piezoelectric, and thermoelectric materials, and the interaction of electromagnetic radiation, magnetic fields, and electric fields with materials is originally related to the elucidation and analysis of crystal structures. There is. The investigation of the processes that occur in crystals during their use and manufacture in industry involves the experimental study of changes in structure and electron distribution caused by both the normal environment and the effects of temperature, pressure, electromagnetic, magnetic and electric fields on the sample. requires analysis of the data obtained. The most powerful equipment available for elucidating crystal and molecular structures is a single-crystal X-ray structure analyzer. However, structural investigation under external influence is complicated by the effects on the sample that depend on the direction of application, and this direction must be kept constant within the crystal during the manual interpretation of the X-ray structural data. Furthermore, during X-ray examination of the electron distribution in a crystal, the collection of reflections from the crystal should be as perfect as possible, minimizing losses in the blurred areas created by the individual components of the X-ray examination equipment, and All reflexes, however weak, should be recorded.

[Conventional technology]

A device with an equatorial ceremonial scanning array, commonly referred to as a four-circle diffraction device, is known, consisting of an X-ray source fixed to a horizontal base, a movable X-ray detector, rotatable about an axis, and two The sample holder is fastened to a movable ring made of a coaxial ring, and the outer part of the coaxial ring is pivotally mounted in alignment with the rotational axis of the X-ray radiation detector. The rotation axis of the detector is perpendicular to the direction of the chief ray of the X-rays and the axis of the circle formed by the two coaxial rings.

Their intersections belong to the axes of the sample holder, so the sample is held at all intersections of the above-mentioned axes (L., A. Aslanov, "Instrumental technology of X-ray structural analysis", Moscow State University Press of the USSR, 1983, 185 (See pages 187-187).

However, with the above-mentioned four-circle diffractometer, it is not possible to investigate the crystal structure when acting on the test crystal in a given crystallographic direction, such as for example with a direct laser beam or a strong magnetic flux. Probably. This is because the optimal direction for crystal assessment, which coincides with the axis of rotation of the specimen holder, can take any spatial position, from horizontal to vertical, depending on the reflection position of the test crystal, resulting in maintaining the action along a given direction. ,
Simultaneously with actuation of the sample holder, it would be necessary to move the source relative to the sample, which is clearly impractical if the source is a laser or the like. Moreover, this design is prone to forming "blind" or blurred areas in cryogenic testing, for example at liquid helium temperatures.

In another conventional device, the cooperative action of a circle of two coaxial rings is replaced by rotation of the sample holder about an additional axis at an angle of 50 degrees to the axis of rotation of the detector (see above).
193).

However, this device also lacks the conditions to investigate the structure of crystals affected by electromagnetic, magnetic, or physical forces.

The conventional technology closest to the present invention is an X-ray inspection device for crystalline substances (USSR Inventor's Certificate, No. 1,040,390, International Patent Classification GOIN 23/227, issued on March 16, 1983); a horizontally extending base supporting a movable base operatively coupled to a mechanism for rotation about an axis perpendicular to the base, carrying an X-ray radiation source and a detector of diffracted X-ray radiation; and both of them are operably connected to a mechanism for rotating each other individually and in conjunction with each other about an axis parallel to the base, and further a mechanism for rotating about an axis parallel to the base. An operably connected crystalline material sample holder is supported on the base by a bracket.

In the above-mentioned X-ray inspection apparatus for crystalline substances, the bracket that supports the mechanism for rotating the sample holder on the base has an arc-shaped cantilevered arm, and the attachment point between the bracket and the base and the mechanism for rotating the sample holder are connected to each other. is placed on the opposite side of the table from the rotation axis. Although this arrangement interferes with the proximity of the X-ray source and detector to the test specimen, it is essential in the investigation of weakly reflective crystals. Furthermore, this arrangement creates a substantial "blind zone" in the space on the sample holder side, reducing the number of reflections useful for investigation. Also, arcuate cantilevered arms create blurred areas.

This arrangement makes it impossible to record the diffraction pattern produced by a flat polycrystalline sample rotated perpendicular to the surface.
This is a process commonly associated with powder crystal diffractometers. Moreover, in setting the focal array in the investigation of polycrystalline materials, this arrangement limits the amount of movement of the test sample from the intersection of the platform's array axis and the rotation mechanism of the X-ray source and detector.

Additionally, conventional instrument arrangements severely limit the maximum dimensions of the source of action on the test specimen, such as helium cryostats, high-power ultra-thick electromagnets, etc., thereby limiting their adoption for investigations into which they are introduced.

[Problem that the invention seeks to solve]

A holder for a specimen or sample of test crystal material, a rotation mechanism thereof, and a bracket supporting the mechanism on a base measure the diffraction pattern of a polycrystalline sample with a flat surface, and To provide an X-ray inspection device for crystalline substances, which is arranged to provide conditions for rotating a sample around a line perpendicular to the object, and has a receptive power to inspect a single crystal in the entire surrounding space of the sample. is the object of the present invention.

[Means for solving problems]

a horizontally extending base supporting a movable base operably connected to a rotation mechanism about an axis perpendicular to the base; mounted thereon, both of which are operably connected to a mechanism for rotating independently and in conjunction with each other about an axis parallel to the base, the rotation mechanism about an axis parallel to the base; The above object is achieved in a crystalline material X-ray examination apparatus in which a crystalline material sample holder operably connected to a crystalline material sample holder is supported on a base by a bracket, in which the crystalline material sample holder , a rotation mechanism centered on an axis parallel to the base, and the bracket are arranged on the same side of the rotation axis of the rigging.

Conveniently, the present X-ray examination device also includes an extension connecting the rotation mechanism about an axis parallel to the base and the crystalline material sample holder.

It is also convenient for the X-ray examination device to include at least one source of action on the crystalline material sample to elucidate the structure and determine the electron concentration distribution during its action.

The X-ray inspection device for crystalline materials constructed according to the present invention is capable of investigating the electron concentration distribution in a single crystal, and examining the structure of polycrystals.
It provides resolution of phase structure, texture, macro- and micro-distortion, while enabling any focal alignment needed for polycrystalline investigation.

〔Example〕

The present invention will be described in detail with reference to the accompanying drawings with regard to embodiments of an X-ray inspection apparatus for crystalline materials.

The X-ray examination apparatus for crystalline substances constructed according to the present invention consists of a horizontally extending base 1 (FIG. 1), which comprises:
It supports a movable platform 2 which is operably and firmly connected to a rotation mechanism 3 about a Z-axis perpendicular to the base 1. In the embodiment currently being described, the mechanism 3 for rotating the platform 2 comprises an electric motor associated with a rotation angle transmission (not shown).

In this embodiment, the platform 2 is installed on the base 1 so as to move on three spherical rolling contact bearings 4 regularly spaced along the circumference (only one bearing 4 is shown in the figure). show). The stand 2 is equipped with an X-ray radiation source 5 and a detector 6 for diffracted X-ray radiation, both of which have respective mechanisms for rotating independently and in conjunction with each other around the glaze parallel to the base 1. 7 and 8. The mechanisms 7, 8 are drives including rotation angle transmissions (not shown).

The apparatus further comprises a holder 9 for a sample of crystalline material to be investigated under normal conditions and under the influence of electromagnetic, magnetic or electric fields, physical forces, temperature, etc. The holder 9 is operably connected to a rotation mechanism 10 centered on an axis (Y axis) parallel to the base 1, and supported on the base 1 by a bracket 11.The sample holder 9, the rotation mechanism 10, and the bracket 11
are arranged on the same side of the rotation axis Z of the table 2.

The X-ray inspection apparatus further includes an extension means 1 connected to a mechanism 10 for rotating the sample holder 9 and to the sample holder 9 itself.
Contains 2. In the embodiment just described, the extension means is a simple rod, but in other embodiments the extension means may be of a telescoping design.

Regarding the investigation of the sample S - single crystal - when acting in an electromagnetic field, the source of action on the crystalline material sample S for determining its structure and electron concentration distribution is a laser 13 mounted on the base 1, whose beam is a removable extension bracket 15
is guided along the rotation axis of the sample holder 9 (Y axis) by a mirror 14 supported by a bracket 11.

Regarding the investigation of single crystals in a magnetic field, the design of the corresponding form of the device is essentially the same as that described above. The difference, however, is that the source of the crystalline material sample for determining the structure and electron concentration distribution during magnetic action takes the form of an electromagnet with the investigation sample accommodated between its poles (FIG. 2). In this embodiment, the extension holder 9 passes through the coil of one of the poles of the electromagnet 16 and is supported on the bracket 11 by an extension bracket 15 which is removable as in the previous example.

For investigation of single crystals in an electric field, the electromagnet 16 is replaced by a capacitor (not shown). In order to investigate the physical effects, the sample S is placed in a high-pressure cell with a diamond anvil attached to the holder 9 in the same way, but in order to investigate the temperature conditions, a helium cryostat or a helium cryostat is attached to the bracket 15. If not, support the furnace to heat the sample S (both not shown).

This X-ray inspection device can investigate any combination of effects on the sample.

The embodiment shown in FIG. 3 of a polycrystal inspection apparatus with a Bragou-Brentano focal arrangement is essentially equivalent to that schematically shown in FIG. The difference in this example is that the sample S is perpendicular to the X axis. In this embodiment, the X-ray radiation from the radiation source 5 is preferably calibrated by a Solar slit (not shown), and the extension means 12 are variable in length, for example in a telescoping manner.

[For production]

The operation of the X-ray inspection apparatus for crystalline materials in the embodiment for investigating single crystals is as follows.

0, 3 when investigating a single crystal in the absence of external effects
A sample S (FIG. 1) having a size of n++n or less is glued to a glass or crystal holder 9 mounted on a standard angle measurement head (not shown). Due to the three vertical linear arrangements of the angle measurement heads, the center of the sample S coincides with the intersection of the geometrical axis of rotation of the stage 2 and the geometrical axes of the detector 6 and the X-ray radiation source 5. . Emergent angular measurements are taken from the axes of a Cartesian coordinate system whose centers coincide with the intersection points of the above-mentioned geometrical axes.

The Z-axis of such a coordinate system extends upwardly from the base 1 in alignment with the geometric rotation axis of the platform 2, and the Y-axis extends upwardly from the base 1
extends from the mechanism 10 in line with the geometrical axis of rotation of the sample S according to 0, and the X axis extends perpendicular to the plane of YZ,
X, Y, Z define a three-way pair of right vectors. The coordinate system associated with the rotational axis system in the present crystal material X-ray examination apparatus is shown in detail in the accompanying drawing, Figure 4, in which the indicated rotational angles of a four-circle diffractometer with an equatorial ceremonial arrangement are shown in detail. The symbols adopted are: phi (φ) - the rotation angle of the sample S around the axis parallel to the base 1, omega (
ω) - the rotation angle of the X-ray radiation source about the axis parallel to the base 1; theta (θ) - the rotation angle of the detector of the diffracted X-rays about the axis parallel to the base 1; and chi (χ)
- the angle of rotation of the platform 2 about an axis perpendicular to the platform 1; The zero values of the omega, chi, and phi angles are selected appropriately.

Currently, in the described embodiment, the zero value of omega corresponds to the position where the X-ray source 5 is aligned with the (+) branch of the Z-axis. Then, the zero value of the plug angle theta corresponds to the position where the receiving slit of the X-ray radiation detector 6 is aligned with the (-) branch of the Z axis, and the zero value of chi corresponds to the position where the receiving slit of the X-ray radiation detector 6 aligns with the (-) branch of the Z-axis. Mechanisms 7 and 8 (FIG. 1) that move the Y-axis (fourth
Figure) Corresponds to the position that matches the branch. The zero value of phi is chosen arbitrarily but must be kept constant during at least the entire process of examining a single specimen or sample. To measure the reflection by the AAA crystal under examination,
1 unit 2, the X-ray radiation source 5, and the
．． 1, 3, 7.8 (FIG. 1) and monitoring the readings of the corresponding rotational angle transmission (not shown). To determine the overall intensity of the measured reflections, the sample S is kept stationary and the X-ray radiation source 5 (FIG. 4) and the detector 6 are rotated and scanned. The rotation of the radiation source 5 and detector 6 in the same direction and with the same angular velocity corresponds to an omega scan in a conventional equatorial ceremonial array four-circle diffractometer. That is, ω/
2θ scanning is effected by rotating the detector 6 of the radiation source 5 in opposite directions at the same angular velocity. and detector 6
If the radiation source 5 is rotated while keeping it stationary, the omega/theta condition is completed. Any other scanning scheme is achievable.

From the result of recording the total internal reflection of the measurable test sample, the electron concentration distribution of the crystal is calculated.

In the apparatus disclosed here, by arranging the X-ray radiation source 5 and the detector 6 at a short distance from the test sample S, it is possible to test the weakly reflected electron concentration distribution of the sample.

When a single crystal is to be examined with respect to an external action applied to it under certain conditions, by way of example laser action 13 (FIG. 1), the single crystal to be investigated is selected so that its selected direction is aligned with the Y axis. A mirror 14 with a diameter of 1 to 2+ nm is mounted on the bracket 15, and the beam of the laser 13 is projected onto the sample S, oriented as shown in FIG. The rest of the investigation procedure is basically the same as the operation described above.

When investigating a single crystal using a magnetic field, an electromagnet with an axial bore in the center (Fig. 2) is attached to the bracket 15 so that the east axis of its magnetic force is aligned with the Y axis, and the sample holder 9 is Mount the sample S through the directional bore so that the selected direction of the crystal is aligned with the Y axis.

The rest of the procedure is the same as the operation described above.

The ice crystal material X-ray examination device examines polycrystals in the Bragou-Brentano arrangement and therefore practically does not require readjustment.

When investigating a cylindrical sample, it is set in the embodiment apparatus shown in FIG. 1 so that its axis is aligned with the alignment axis of the rotation mechanism 10. The diffraction pattern is recorded by setting chi to zero and rotating the X-ray radiation source 5 and detector 6 in the positive branch direction of the X-axis at the same angular velocity.

To sub-inspect a sample with a flat surface, the sample S is fixed to the tip of an extension means 12 (FIG. 3) perpendicular to the Y-axis, and its surface is aligned with the Z-axis. The diffraction pattern of the polycrystalline sample S is recorded by rotating the table 2 to set chi to 90 degrees and rotating the radiation source 5 and detector 6 in the positive branch direction of the Y-axis at the same angular velocity. Diffraction patterns can be used to investigate phase configurations, spatial lattice periods, microscopic distortions, and more. In order to investigate the macroscopic distortion of a sample, a slope diagram of the diffraction reflection can be obtained by varying the value of chi and measuring selected diffraction lines each time, for example using the slope diagram method. In the case of tissue examination, the opposite polarity values and records are the individual changes in chi (due to the rotation of the table 2), the records of selected diffraction lines with the radiation source 5 and detector 6 stationary, and the 360 degrees from 0 degrees.
This is achieved through phi that changes to the degree. Other tests on flat polycrystalline samples can be performed without readjusting the equipment. The only condition is to make sure that the spacing between the sample S and the Xl-ray radiation source, on the one hand, and between the sample S and the detector 6 of the diffracted radiation, on the other hand, comply with the focus requirements of the Bragou-Brentano method.

〔Effect of the invention〕

The X-ray examination apparatus for crystalline materials disclosed herein allows the measurement of the overall intensity of diffraction reflections in the periphery of a single crystal without blurring due to equipment equipment, and thus allows for the measurement of the overall intensity of diffraction reflections in the circumference of a single crystal, thus bypassing the blurred regions. Allows you to save time. By coordinating the mechanism arrangement of the present device with the extension means, realizing a mechanism for rotating the sample holder away from the sample can substantially reduce the "blind zone" caused by the rotation mechanism of the sample holder, thereby reducing the electron concentration. Minimum spacing between source and detector for determination accuracy allows investigation of weakly reflecting crystals, without readjusting polycrystalline structure, phase configuration, macro- and micro-distortions. can be investigated.

[Brief explanation of the drawing]

Fig. 1 is a schematic perspective view of an embodiment of an X-ray inspection device for crystalline materials in conjunction with a laser unit, and Fig. 2 is a modified example of the embodiment of Fig. 1 in which a magnetic force source is provided without a laser unit. 3 is a perspective view of a modified example of a device for investigating polycrystalline materials with a Bragou-Brentano focal array without a laser unit; FIG. 4 is a geometrical representation of the embodiment of the device shown in FIG. Figure 3 schematically shows the orientation of the axes and the rotation angles of the radiation source, detector, sample holder and stage in a four-circular scanning arrangement according to the invention; DESCRIPTION OF SYMBOLS 1... Base, 2... Stand, 3... Mechanism for rotating the stand 2 around an axis parallel to the base 1, 4...
Spherical rolling contact bearing, 5... X-ray radiation source, 6...
7. Detector of diffracted X-ray radiation; A mechanism for rotating the radiation source 5 and the detector 6 relatively individually and in conjunction with each other about an axis parallel to the base 1, 9...Crystalline material sample holder, 10. ... Mechanism for rotating the holder 9 around an axis parallel to the base 1, 11... Bracket, 12... Extension means, 13... Laser,
14... Mirror, 15... Removable bracket, 16... Electromagnet, 17... Sample holder, S.
...Crystalline material sample, X, Y, Z... Vertical axis of coordinate system, phi (φ)... Rotation angle of sample S around axis parallel to base 1, seek (θ)...・60 rotation angles of the diffraction X-ray detector centered on the axis parallel to the base 1, omega (ω
)...X-ray radiation source 50 centered on an axis parallel to the base 1
Rotation angle, chi (χ)...The rotation angle of the platform 2 around the axis perpendicular to the base 1. t/b:4 EJ

Claims (3)

[Claims] (1) Rotation mechanism (3) centered around an axis perpendicular to the base (1)
) includes a horizontally extending base (1) supporting a movable platform (2) operably connected thereto, the platform (2) having an X-ray radiation source (5) and a diffracted X-ray radiation source (5); detector (6), both of which are operably connected to a mechanism (7, 8) for rotation independently and in conjunction with each other about an axis parallel to the base (1). , a crystal material sample or specimen holder (9) operably connected to a rotation mechanism (10) about an axis parallel to the base (1) is supported on the base by a bracket (11). A substance testing device that includes a holder for a crystalline substance sample or sample (9) and a base (1).
An X-ray inspection apparatus for crystalline substances, characterized in that a rotation mechanism (10) centered on an axis parallel to the rotation axis and a bracket (11) are arranged on the same side of the rotation axis of the table (2). (2) comprising extension means (12) for connecting the crystalline material sample holder (9) to a rotation mechanism (10) about an axis parallel to the base (1); The X-ray inspection device for crystalline substances according to item 1. (3) It comprises at least one source of action on a crystalline material sample or sample in order to elucidate the structure of the crystalline material and determine its electron concentration distribution during action. An X-ray inspection device for crystalline substances according to item 1 or 2.