Pressure / strain device, x-ray diffraction device using the same, microscopic raman scattering measurement device, and optical microscope

Abstract

To provide a pressure / strain device capable of performing pressurization in one direction, and automatically measuring physical property evaluation of a sample from the one direction and a direction perpendicular to the one direction, an X-ray diffraction device using the pressure / strain device, a microscopic Raman scattering measurement device and an optical microscope.SOLUTION: A pressure / strain device of the present invention comprises first and second diamond anvils for holding a sample. The pressure / strain device comprises: a sample holding part in which the first diamond anvil rotates; a rotation mechanism that rotates the first diamond anvil; a pressing mechanism that mechanically applies pressure from the first diamond anvil side; an actuator that applies pressure by an electric signal to the second diamond anvil, and is hollow; a pressure sensor that detects a pressure applied to the sample held between the first and second diamond anvils; and a control mechanism that controls, and detects these operations.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a pressure / strain apparatus, and an X-ray diffraction apparatus, a microscopic Raman scattering measurement apparatus, and an optical microscope that use the same, and more particularly to an ultra-high pressure pressure / strain apparatus that uses a diamond anvil, and an X-ray diffraction apparatus, a microscopic Raman scattering measurement apparatus, and an optical microscope that use the same. [Background technology]

[0002] Diamond anvil cells (DACs) are known to generate extremely high pressures exceeding 1 million atmospheres, but since all materials become solid under pressures of 12 GPa or more, experiments are not conducted under isotropic pressure but under differential stress. Therefore, it is also necessary to know the state of materials under strain and differential stress. Numerous physical property evaluations of samples pressurized under high pressure have been conducted (for example, see Non-Patent Documents 1 to 7).

[0003] Non-Patent Document 1 shows an apparatus that applies a rotational strain to a sample in a pressurized DAC by driving a motor, and performs X-ray diffraction in the direction of the pressure axis, but since it does not support X-ray diffraction in the radial direction, information on the strain state cannot be obtained. Non-Patent Documents 2 and 3 show that the apparatus has a DAC rotation mechanism, but does not support X-ray diffraction in the radial direction.

[0004] Non-Patent Documents 4 and 5 disclose a pressure device using tungsten carbide anvils, but tungsten carbide has low X-ray transmittance and is not suitable for X-ray diffraction measurement under pressure.

[0005] According to Non-Patent Document 6, remote pressurization is realized using a piezoelectric actuator, but the dynamic range of pressure is small using only a piezoelectric actuator. Furthermore, Non-Patent Document 6 cannot apply strain to the sample in the DAC. Non-Patent Document 7 achieves automatic pressurization using a pressure mechanism using a gas pressure membrane and a piezoelectric actuator independent of this, but also does not have a rotation mechanism for applying strain. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] N. Novikov et al., Journal of Superhard Materials, 2015, Vol. 37, pp. 1-7 [Non-Patent Document 2] R. Nomura et al.,Review of Scientific Instruments,2017,Vol.88,Issue 4,pp.044501 [Non-Patent Document 3] V. Blank et al., Physics Letters A, 1994, Vol. 188, Issue 3, pp. 281-286 [Non-Patent Document 4] H. Razavi-Khosroshahi et al., Journal of Materials Chemistry A, 2017, Vol. 5, Issue 38, pp. 20298-20303 [Non-Patent Document 5] RZValiev et al., JOM, 2006, Vol. 58, Issue 4, pp. 33-39 [Non-Patent Document 6] William J. Evans et al.,Review of Scientific Instruments,2007,78,073904 [Non-Patent Document 7] Stanislav V. Sinogeikin et al.,Review of Scientific Instruments,2015,86,072209 Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the above, an object of the present invention is to provide a pressure / strain device that can automatically measure and evaluate the physical properties of a sample in one axial direction and in a direction perpendicular to the axial direction while applying pressure in one axial direction and rotating the sample in a direction perpendicular to the axial direction, and an X-ray diffraction device, a microscopic Raman scattering measurement device, and an optical microscope that use the same. [Means for solving the problem]

[0008] The pressure / strain device according to the present invention comprises first and second diamond anvils for holding a sample, a sample holder on which the first diamond anvil rotates, a rotation mechanism for rotating the first diamond anvil, a hollow actuator for applying pressure by an electric signal from the first diamond anvil side, a pressing mechanism for mechanically applying pressure from the second diamond anvil side, a pressure sensor for detecting the pressure applied to the sample held between the first and second diamond anvils, and a control mechanism for controlling the operation of the rotation mechanism, the actuator, and the pressing mechanism and detecting the operation of the pressure sensor, the rotation mechanism comprising a drive unit and a hollow rotating shaft rotated by the drive unit, the sample holder comprises a hollow first receiving stand that is joined to the first diamond anvil and fixes the first diamond anvil, and a center support for the first receiving stand. The present invention relates to a method for manufacturing a diamond anvil having a pressure transmitting section that receives pressure from the actuator and transmits the pressure to the first diamond anvil, a rotating section that is joined to the first support stand and engages with the rotating shaft to rotate, and a bearing that rotates the rotating section against the load received from the pressure transmitting section; a hollow second support stand that is joined to the second diamond anvil and fixes the second diamond anvil; a hollow second support stand that supports the second support stand, receives pressure from the pressing mechanism and transmits the pressure to the second diamond anvil; and a cylinder that holds the first support stand, the first support stand, the second support stand, and the second support stand while exposing the first and second diamond anvils, wherein the rotating shaft is located within the actuator, engages with the rotating section of the first support stand, and rotates the first diamond anvil, thereby achieving the above-mentioned object. There may be a step between the pressure transmitting portion and the rotating portion, and the pressure transmitting portion may be convex with respect to the rotating portion. The pressing mechanism may be selected from the group consisting of a stepper motor, a hydraulic piston, and a gas pressure membrane. The actuator may be a stacked piezoelectric actuator. The stroke of the actuator may be in the range of 50 μm to 200 μm. The pressure sensor may be a piezoelectric quartz sensor. The drive unit may include a stepping motor that generates torque, and an arm unit that transmits the torque to the rotation shaft via a gear, and the arm unit may rotate about the rotation shaft. The control mechanism may control the operations of the rotation mechanism, the pressing mechanism, and the actuator and detect the operation of the pressure sensor so that: (A) the pressing mechanism applies pressure to the sample from the second diamond anvil side; (B) while pressure is being applied to the sample, the pressure sensor measures the pressure value by the actuator and adjusts the actuator so that it becomes the pressure starting point of the actuator; (C) while pressure is being applied to the sample, the actuator adjusted to the pressure starting point applies pressure continuously from the first diamond anvil side; and (D) while pressure is being applied to the sample, the rotation mechanism rotates the first diamond anvil. The apparatus may further include a positioning mechanism for determining the position of the sample, the positioning mechanism including a lower stage, a support leg connected to the first support table for adjusting the position of the sample, and a contact plate for contacting the second support table. The apparatus may further include a deflection mechanism connected to the lower stage for changing the horizontal direction of the compression / strain device. The orientation mechanism may adjust the horizontal and vertical position of the sample. The control mechanism may further control operation of the deflection mechanism. The control mechanism may include an actuator drive circuit that applies an electrical signal to the actuator, a conversion measurement unit that converts and measures the pressure of the pressure sensor, a pressure drive circuit that sends a drive signal to the pressure mechanism, a rotation drive circuit that sends a drive signal to the rotation mechanism, and a central processing unit that controls the actuator drive circuit, the conversion measurement unit, the pressure drive circuit, and the rotation drive circuit. The rotary actuator may further include a pulse generator connected to the rotary drive circuit. The X-ray diffraction apparatus according to the present invention includes the above-mentioned pressure / strain device, thereby solving the above-mentioned problems. The microscopic Raman scattering measurement apparatus according to the present invention includes the above-mentioned pressure / strain device, thereby solving the above-mentioned problems. The optical microscope apparatus according to the present invention includes the above-mentioned pressure / strain device, thereby solving the above-mentioned problems. Effect of the Invention

[0009] The pressure / strain device of the present invention is equipped with a pressing mechanism that applies pressure mechanically and an actuator that applies pressure by an electric signal, so that continuous pressure by the actuator and stepwise large pressure by the pressing mechanism are used in combination, and pressure with a wide dynamic range can be continuously applied to the sample in one axial direction (i.e., the pressure direction). With such pressure applied, the first diamond anvil is rotated by the rotation mechanism, so that the sample is rotated in a direction perpendicular to the one axial direction (radial direction), and strain can be applied to the sample. The operation of the rotation mechanism, actuator, and pressing mechanism is controlled by the control mechanism along with detection by the pressure sensor, so that pressure application and strain can be automatically performed on the sample.

[0010] In addition, in the pressure / strain device of the present invention, the first and second pedestals of the sample holder, the actuator, and the rotating shaft engaged with the first pedestal are all hollow, so that, for example, X-rays can be incident in one axial direction to perform X-ray diffraction measurement of the sample. Also, since the first and second diamond anvils are exposed in the sample holder, X-rays can be incident from a direction perpendicular to the one axial direction to perform X-ray diffraction measurement in the radial direction of the sample.

[0011] An X-ray diffraction device and a microscope Raman scattering measurement device can be provided by combining the pressure / strain device of the present invention with an X-ray source or light source, a light receiving unit for receiving scattered light or diffracted light, a detector, etc. Also, an optical microscope device can be provided by combining the pressure / strain device of the present invention with a microscope. [Brief description of the drawings]

[0012] [Figure 1] Schematic diagram showing the compression and strain device of the present invention. [Diagram 2] Schematic diagram showing a rotation mechanism of the present invention. [Diagram 3] Schematic diagram showing the positioning mechanism [Figure 4] FIG. 1 is a block diagram showing a control mechanism applied to the compression and strain device of the present invention. [Diagram 5] FIG. 13 is a diagram showing the relationship between the load and the generated pressure monitored by the pressure sensor in Reference Example 1. [Figure 6] FIG. 6 is an enlarged view of region A in FIG. 5. [Figure 7] FIG. 6 is an enlarged view of region B in FIG. 5. [Figure 8] FIG. 1 shows an X-ray diffraction pattern in one axis direction in Reference Example 1. [Figure 9] FIG. 1 shows an X-ray diffraction pattern in the radial direction in Reference Example 1. [Figure 10] FIG. 1 is a diagram showing the relationship between the load and the generated pressure monitored by the pressure sensor in the first embodiment. [Figure 11] FIG. 11 is an enlarged view of region C in FIG. 10. [Figure 12] FIG. 1 shows an X-ray diffraction pattern in one axis direction in Example 1. [Figure 13] FIG. 1 shows an X-ray diffraction pattern in the radial direction in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Note that like elements are given like reference numerals and their description will be omitted.

[0014] The compression and strain device of the present invention will now be described. FIG. 1 is a schematic diagram showing a compression and strain apparatus of the present invention.

[0015] The pressure / strain apparatus 100 of the present invention includes first and second diamond anvils 111, 112 for clamping a sample 11X, a sample holder 110 in which the first diamond anvil 111 rotates, a rotation mechanism 120 for rotating the first diamond anvil 111, a hollow actuator 130 for applying pressure by an electrical signal from the first diamond anvil 111 side, a pressing mechanism 140 for mechanically applying pressure from the second diamond anvil 112 side, a pressure sensor 150 for detecting the pressure applied to the sample 11X clamped between the first and second diamond anvils 111, 112, and a control mechanism 160 for controlling the operation of at least the rotation mechanism 120, the actuator 130, and the pressing mechanism 140, and further for detecting the operation of the pressure sensor 150.

[0016] The pressure-strain apparatus 100 of the present invention can continuously apply pressure with a wide dynamic range to the sample 11X in one axial direction (the horizontal direction in FIG. 1 ) by combining continuous pressure based on an electrical signal from the actuator 130 and stepwise large mechanical pressure from the pressing mechanism 140.

[0017] With such pressure applied, the first diamond anvil 111 is rotated by the rotation mechanism 120, so that the sample 11X is rotated in a direction perpendicular to one axial direction (radial direction), and strain can be applied to the sample 11X. The operations of the rotation mechanism 120, the actuator 130, and the pressing mechanism 140 are controlled by the control mechanism 160 along with detection by the pressure sensor 150, so that pressure application and strain application to the sample 11X can be performed automatically. In this specification, an apparatus that can apply not only pressure but also strain to a sample is called a pressure / strain apparatus, but the apparatus of the present invention may also be called a strain-applying pressure apparatus or a high-pressure strain application apparatus.

[0018] Each component will be described in detail below. The first and second diamond anvils 111 and 112 are adapted to clamp the sample 11X via a gasket 11Y. The ends of the first and second diamond anvils 111 and 112 that clamp the sample 11X are flat, and the smaller the area of ​​the flat ends, the greater the load applied to the sample 11X. The end of the first diamond anvil 111 that clamps the sample 11X is preferably circular, and the end of the second diamond anvil 112 that clamps the sample 11X is preferably polygonal, such as a square, hexagon, or octagon. This allows only the first diamond anvil 111 to be easily rotated by the rotation mechanism 120, so that radial rotation can be applied to the sample 11X. The sample 11X may be held together with a pressure medium substance such as sodium chloride (NaCl) and a standard sample such as gold.

[0019] The sample holder 110 comprises a first receiving stand 113 that is joined to the first diamond anvil 111 and fixes the first diamond anvil 111, a first support stand 114 that supports the first receiving stand 113, a second receiving stand 118 that is joined to the second diamond anvil 112 and fixes the second diamond anvil 112, a second support stand 119 that supports the second receiving stand 118, receives pressure from the pressing mechanism 140, and transmits this to the second diamond anvil 112, and a cylinder 11 that holds the first receiving stand 113, the first support stand 114, the second receiving stand 118, and the second support stand 119.

[0020] Since the first receiving stand 113, the first support stand 114, the second receiving stand 118, and the second support stand 119 are all hollow, for example, it is possible to perform X-ray diffraction measurement of the sample 11X when irradiated with X-rays from the horizontal direction in FIG. 1, or to perform in-situ observation in combination with a microscope.

[0021] In addition, the first and second diamond anvils 111, 112 held by the sample holder 110 transmit light in a very wide wavelength band, from 220 nm to terahertz, millimeter waves, and even microwaves. Therefore, for example, an infrared laser can be irradiated from the second diamond anvil 112 side to heat the sample 11X under high pressure, or monochromatic light can be incident on the sample 11X to measure the Raman scattering spectrum of the sample 11X under high pressure.

[0022] The cylinder 11 holds the first and second diamond anvils 111, 112 in an exposed state, and thus allows X-ray diffraction measurement by irradiating X-rays from a direction perpendicular to the uniaxial direction (radial direction) to the sample 11X in a high-pressure state held between the first and second diamond anvils 111, 112. For ease of viewing, the radial direction is shown in Fig. 1 as an arrow pointing upward from the bottom of the page, but in reality, it is intended to be a direction perpendicular to the page.

[0023] The cylinder 11 may be configured to hold the first and second receiving stages 113 and 118 by means of a set screw 11Z, thereby enabling fine adjustment of the position of the sample 11X in the horizontal direction.

[0024] The first support base 114 includes a pressure transmission unit 115 that receives pressure from the actuator 130 and transmits the pressure to the first diamond anvil 111, a rotating unit 117 that is joined to the first receiving base 113 and engages with a rotating shaft 122 described below to rotate, and a bearing 116 that rotates the rotating unit 117 against the load received from the pressure transmission unit 115. There is a step between the pressure transmission unit 115 and the rotating unit 117, and the pressure transmission unit 115 may be convex with respect to the rotating unit 117. As a result, the actuator 130 does not come into surface contact with the rotating unit 117 via the bearing 116, so that the rotating unit 117 is not hindered by the pressure from the actuator 130 and can effectively rotate.

[0025] The first and second receiving stages 113, 118 are preferably made of a hard material such as tungsten carbide, which allows the first and second diamond anvils 111, 112 to be fixed. The first and second receiving stages 113, 118 are preferably fixed and positioned to the rotating section 117 and the second support stage 119 by means of set screws 11Z such as hexagon socket set screws.

[0026] The actuator 130 is not particularly limited as long as it can convert an external electric signal into a physical expansion and contraction motion, but typically it is a piezoelectric element that converts a voltage as an electric signal into a force. Among them, a laminated type piezoelectric actuator may be used. If it is a laminated type, it can expand and contract in the range of several nm to several hundred μm depending on the number of layers of the piezoelectric element by applying a voltage. Such expansion and contraction on the order of nanometers enables continuous pressure application different from that of the pressing mechanism 140. Such a piezoelectric element is made of a laminated structure such as lead zirconate titanate (PZT, Pb(Zr,Ti)O3), potassium niobate (KNN, (K,Na)NbO3), etc.

[0027] There is a limit to the stroke of the actuator 130 (i.e., the maximum extension and contraction range). However, if the stroke is short, it is sufficient to control the interlocking with the pressing mechanism 140 more, and if the stroke is long, it is sufficient to control the interlocking with the pressing mechanism 140 less. The stroke of the actuator 130 is preferably in the range of 50 μm to 200 μm. If it is in this range, it is possible to provide a pressure-strain device capable of continuous pressure application up to ultra-high pressure (up to 350 GPa) without using a special actuator. In particular, actuators with a stroke in the range of 60 μm to 100 μm are easy to obtain.

[0028] The actuator 130 may be loaded into the cylinder tube 131 with the rotating shaft 122 provided therein, and the position of the actuator 130 may be adjusted within the cylinder tube 131 according to the expansion and contraction of the actuator 130. One end of the cylinder tube 131 is coupled to the pressure transmission part 115 of the first support stand 114, and the pressure of the actuator 130 is efficiently applied to the first diamond anvil 111. A cylindrical connecting part 132 may be attached to the other end of the cylinder tube 131. The cylindrical connecting part 132 may cover the pressure sensor 150 provided on the actuator 130.

[0029] There are no particular limitations on the pressing mechanism 140 as long as it mechanically applies pressure to the second diamond anvil 112. In this specification, mechanically applying pressure means applying pressure to the second diamond anvil 112 by the principle of leverage, spring force, screw force, gas pressure, hydraulic pressure, or the like, and intends dynamic, step-by-step pressure application.

[0030] In the following explanation, the pressing mechanism 140 in FIG. 1 is a hollow gas pressure membrane, and is connected to an external gas (not shown) and, if necessary, a pressure booster. However, other than the gas pressure membrane, a stepping motor and a hydraulic piston can also be used.

[0031] By using the actuator 130 and the pressing mechanism 140 in combination, it is possible to fill in 0.1% steps between the minimum pressure steps applied by the pressing mechanism 140. For example, a large dynamic range of 2 GPa to 350 GPa can be achieved by the pressing mechanism 140, and the pressure between them can be filled in 0.1% steps by the actuator 130, enabling continuous pressurization.

[0032] The pressure sensor 150 is not particularly limited as long as it detects the pressure applied to the sample 11X between the first and second diamond anvils 111, 112 by the actuator 130 and / or the pressing mechanism 140, and examples thereof include a quartz pressure sensor, a strain gauge pressure sensor, a semiconductor pressure sensor, etc. Among them, a quartz piezoelectric sensor that utilizes the piezoelectric effect is preferable because it can measure high loads and can be used repeatedly.

[0033] By using the pressure sensor 150, it is possible to set the pressurization start point of the actuator 130. In detail, the pressure value by the actuator 130 is 0, and the applied voltage and position of the actuator 130 are adjusted in accordance with changes in the pressure value detected by the pressure sensor 150 so that the point at which the pressure value starts to be detected becomes the pressurization start point of the actuator 130. Continuous pressurization is always possible by the stroke of the actuator 130 from the set pressurization start point.

[0034] Naturally, the end point of pressurization can be set by detecting the maximum value of the stroke of the actuator 130 using the pressure sensor 150. Continuous depressurization by the stroke of the actuator 130 from the set end point of pressurization is also possible.

[0035] FIG. 2 is a schematic diagram showing the rotation mechanism of the present invention.

[0036] The rotation mechanism 120 includes a driving unit 121 and a rotating shaft 122 rotated by the driving unit 121. The rotating shaft 122 is hollow and is positioned so as to be loaded into the actuator 130, which is also hollow, and is engaged with the rotating unit 117 of the first support table 114 so as to be fitted therein. The rotating shaft 122 is rotated by the torque generated by the driving unit 121. Next, as the rotating shaft 122 rotates, the rotating unit 117, the first receiving table 113 joined thereto, and the first diamond anvil 111 rotate, and the sample 11X rotates in the radial direction. As a result, a radial strain is applied to the sample 11X.

[0037] The driving unit 121 preferably includes a stepping motor 210 that generates torque, a spur gear 220 that transmits the torque to the rotating shaft 122, and a rotatable arm unit 230. The arm unit 230 is rotatably fixed to the stepping motor 210 by a bolt 240, and is configured to rotate with respect to the rotating shaft 122. The rotation of the arm unit 230 facilitates loading of the rotating shaft 122 into the actuator 130. The spur gear 220 may be covered and protected by a spur gear cover 250.

[0038] FIG. 3 is a schematic diagram showing the positioning mechanism.

[0039] The compression / strain apparatus 100 of the present invention may further include a positioning mechanism 300 for determining the position of the sample 11X. This allows fine adjustment of the position of the sample 11X in the horizontal and vertical directions (here, the up and down directions on the paper surface of FIG. 1). As a result, various measurements such as X-ray diffraction measurements can be accurately performed on the same position of the sample 11X in both the horizontal and radial directions.

[0040] 3, the positioning mechanism 300 includes a lower stage 310, a support leg 320 (hereinafter simply referred to as a support leg with fine adjustment screw) connected to the first support base 114 and equipped with a fine adjustment screw 32X for adjusting the position of the sample 11X, and a backing plate 330 that abuts against the second support base 119. The support leg with fine adjustment screw 320 and the backing plate 330 are fixed to the lower stage 310.

[0041] The support leg 320 with fine adjustment screw is connected to the first support base 114 by a push-pull screw. This allows fine movement in the horizontal direction. The support leg 320 with fine adjustment screw may be connected to the cylinder tube 131 in addition to the first support base 114. This allows stable fine movement in the vertical direction.

[0042] The compression / strain apparatus 100 of the present invention may further include a deflection mechanism 340 connected to the lower stage 310. The deflection mechanism 340 is rotatable and can change the horizontal orientation of the compression / strain apparatus 100. This enables various measurements, such as X-ray diffraction measurements, to be performed automatically in the horizontal and radial directions. The deflection mechanism 340 may be capable of controlling the horizontal and vertical positions of the sample 11X. Such a deflection mechanism 340 may be configured to include one or more stages and an encoder.

[0043] 1 again, as described above, the control mechanism 160 controls the operations of the rotation mechanism 120, the actuator 130, and the pressing mechanism 140, and detects the operation of the pressure sensor 150, so that the pressurization / strain device 100 can automatically apply pressure and strain to the sample 11X.

[0044] In detail, the control mechanism 160 controls the operation as follows. Operation (A): First, the pressing mechanism 140 applies a mechanical pressure to the sample 11X from the side of the second diamond anvil 112. If the pressing mechanism 140 is a gas pressure membrane, gas may be introduced from an external gas source (not shown).

[0045] Operation (B): With mechanical pressure applied to sample 11X by pressing mechanism 140, pressure sensor 150 measures the pressure value by actuator 130, and adjusts actuator 130 so that this is the pressure start point of actuator 130. At this time, preferably, the stroke of actuator 130 is 0, and the actuator is not extended at all. In this manner, the pressure start point of actuator 130 is set.

[0046] For example, when the actuator 130 is applying pressure, the applied voltage is adjusted to make the stroke of the actuator 130 zero, just before pressure is applied. For example, when the actuator 130 is not applying pressure, the position of the actuator 130 inside the cylinder tube 131 is adjusted to be just before pressure is applied. In this case, the stroke of the actuator 130 is also zero.

[0047] Operation (C): Next, while the pressing mechanism 140 applies pressure to the sample 11X, the actuator 130, adjusted to the pressure application start point, continuously applies pressure to the first diamond anvil 111. For example, if the actuator 130 is a laminated piezoelectric actuator, pressure can be applied to the first diamond anvil 111 by the stroke of the actuator 130 simply by gradually applying a voltage, but by controlling the amount of expansion and contraction of the actuator 130, pressure can be applied finely within the stroke.

[0048] Operation (D): In a state where a mechanical pressure and a pressure due to an electric signal are applied to the sample 11X, the rotation mechanism 120 rotates the first diamond anvil 111. This applies a radial strain to the sample 11X.

[0049] Prior to operation (D), the control mechanism 160 can continuously apply pressure to the sample 11X up to ultra-high pressure (e.g., 350 GPa) by repeating mechanical pressure application by the pressing mechanism 140 and pressure application by the actuator 130 using an electrical signal following the above-mentioned operations (A) to (C) of the pressing mechanism 140, the actuator 130, and the pressure sensor 150.

[0050] Operation (E): In the control mechanism 160, while the actuator 130 is applying pressure to the first diamond anvil 111 side, the pressing mechanism 140 applies further pressure to the second diamond anvil 112 side. For example, if the actuator 130 is a laminated piezoelectric actuator and the pressing mechanism 140 is a gas pressure membrane, gas may be further introduced while maintaining the voltage applied to the laminated piezoelectric actuator. As a result, the actuator 130 and the first diamond anvil 111 are physically close to each other, so that the pressure from the actuator 130 is further applied to the first diamond anvil 111 side.

[0051] Prior to operation (E), the voltage to the actuator 130 may be removed to reduce the pressure applied to the first diamond anvil 111. This reduction in pressure may be performed continuously for the stroke of the actuator 130.

[0052] Operation (F): Next, while the pressing mechanism 140 applies further pressure to the second diamond anvil 112 side, the pressure sensor 150 detects the pressure that the actuator 130 applies to the first diamond anvil 111 side, and adjusts the actuator 130 so that the pressure sensor 150 starts to detect the pressure value. This operation (F) is the same as the above-mentioned operation (B).

[0053] Operation (G): Next, while the pressing mechanism 140 applies further pressure to the sample 11X, the actuator 130, adjusted to the pressure starting point again, applies pressure continuously to the first diamond anvil 111 side. Operation (G) is similar to operation (C), but the pressure applied by the pressing mechanism 140 is different. Therefore, by controlling the amount of expansion and contraction of the actuator 130 within the new pressure range, pressure can be applied finely.

[0054] In this way, by repeating operations (E) to (G), pressure can be continuously applied up to ultra-high pressure (for example, 350 GPa). By using the compression / strain device 100 of the present invention, it is possible to apply pressure until the first and second diamond anvils 111, 112 break, and furthermore, it is possible to identify the end point of the breakage. Here, the operation of pressurizing up to ultra-high pressure has been described, but it will be easily understood by those skilled in the art that it is also possible to continuously reduce pressure from ultra-high pressure by using the maximum value of the stroke as the reduction start point instead of the pressurization start point where the stroke of the actuator 130 is 0, and performing the reverse operation.

[0055] Furthermore, by carrying out operation (D) at the desired pressure of operations (E) to (G), it is possible to obtain information regarding the strain state of the sample under any pressure.

[0056] The control mechanism 160 may further control the operation of the deflection mechanism 340. By combining the compression / distortion apparatus 100 of the present invention with, for example, an X-ray source and an X-ray detector, it is possible to automatically obtain information regarding the distortion state of the sample 11X not only in the horizontal direction but also in the radial direction.

[0057] FIG. 4 is a block diagram showing a control mechanism applied to the compression and strain device of the present invention.

[0058] The control mechanism 160 includes at least an actuator drive circuit 410 that applies an electric signal such as a voltage to the actuator 130, a conversion measurement unit 420 that converts and measures the pressure of the pressure sensor 150, a pressing drive circuit 430 that sends a drive signal such as a drive current to the pressing mechanism 140, a rotation drive circuit 460 that sends a drive signal such as a drive current to the rotation mechanism 120, and a central processing unit 440 that controls the actuator drive circuit 410, the conversion measurement unit 420, the pressing drive circuit 430, and the rotation drive circuit 460. This makes it possible to apply pressure up to ultra-high pressure by the above-mentioned operations (A) to (G), or conversely, to reduce pressure from ultra-high pressure, and to apply radial strain to the sample.

[0059] A function generator 450 may be further connected to the actuator driving circuit 410. This allows the actuator driving circuit 410 to amplify a pulse voltage having a waveform (pulse signal) of an electric signal output from the function generator 450 and apply it to the actuator 130. That is, a voltage can be continuously applied to the actuator 130 according to the pulse width, enabling continuous pressure increase or decrease. For example, if a pulse voltage of 1 Hz is used, a voltage can be applied in a 1 second cycle, enabling periodic pressure increase or decrease. The function generator may be a pulse generator. The actuator driving circuit 410 may also have a voltage amplification function for amplifying and outputting the pulse voltage.

[0060] There are no particular limitations on the conversion and measurement unit 420 as long as it converts the pressure of the pressure sensor 150 into an electrical signal such as an amount of charge and measures it. For example, a charge amplifier can be used as the conversion and measurement unit 420.

[0061] The pressing drive circuit 430 sends a drive signal (e.g., a drive current) to the pressing mechanism 140 to operate the pressing mechanism 140. For example, if the pressing mechanism 140 is a gas pressure membrane, the pressing drive circuit 430 may preferably be a pressure controller, and the gas pressure supplied to the gas pressure membrane is increased or decreased by an electric signal from the pressure controller, thereby controlling the mechanical pressure applied to the second diamond anvil 112 side.

[0062] The rotation drive circuit 460 sends a drive signal (e.g., a drive current) to the rotation mechanism 120 to operate the rotation mechanism 120, and preferably is further connected to a pulse generator 470. The pulse generator 470 provides a pulse signal to the rotation drive circuit 460, and adjusts the torque of the stepping motor 210 (FIG. 2) provided in the rotation mechanism 120 by adjusting the frequency of the pulse signal. The generated torque is transmitted to the rotation shaft 122 via the spur gear 220 (FIG. 2), and applies a radial strain to the sample 11X together with the first diamond anvil 111.

[0063] The central processing unit 440 may include a memory (not shown) in which a program for repeatedly applying mechanical stepwise pressure by the pressing mechanism 140 and applying continuous fine electrical pressure by the actuator 130, and a program for rotating the first diamond anvil 111 by the rotating mechanism 120 at a predetermined pressure are recorded. This allows automatic pressurization up to ultra-high pressure (e.g., 350 GPa) / decompression from ultra-high pressure, and radial distortion to be applied to the sample 11X at a desired pressure. In addition, a driving signal (driving current) for the pressing mechanism 140 and a pulse signal for the actuator 130 and / or the rotating mechanism 120 may be set via an input device (not shown) such as a keyboard or a touch panel, and these set values ​​may be recorded in the memory.

[0064] Such a central processing unit 440 may be configured by hardware logic, or may be realized by software using a personal computer equipped with a CPU (Central Processing Unit).

[0065] In addition, if the compression / distortion apparatus 100 further includes a direction-changing mechanism 340, the control mechanism 160 may further include a direction-changing drive circuit (not shown) that sends a drive signal such as a drive current to the direction-changing mechanism 340, and a program for changing the direction of the compression / distortion apparatus 100 may be stored in the memory of the central processing unit 440.

[0066] As described above, by equipping the pressure / strain device 100 of the present invention with various light sources or X-ray sources, a light receiving unit for receiving scattered light or diffracted light, a detector, etc., it is possible to construct an X-ray diffraction device or a microscopic Raman scattering measurement device capable of measuring the physical properties of a sample to which high pressure and strain have been applied. Furthermore, by mounting the pressure / strain device 100 of the present invention on a microscope, it is possible to provide an optical microscope device capable of observing a sample to which high pressure and strain have been applied. Naturally, a plurality of these various measurement devices may be combined.

[0067] The present invention will now be described in detail with reference to specific examples, but it should be noted that the present invention is not limited to these examples. EXAMPLES

[0068] [Pressure and strain device] The compression and strain apparatus 100 shown in FIG. 1 was constructed as follows. Diamond anvils with a tip diameter of 0.3 mm were used as the first and second diamond anvils 111 and 112. The tips of the first and second diamond anvils 111 and 112 were both flat, but the tip of the first diamond anvil 111 was machined to a circular shape, and the tip of the second diamond anvil 112 was machined to an octagonal shape. The first and second diamond anvils 111 and 112 were joined to hollow first and second receiving stands 113 and 118, respectively, made of tungsten carbide. The first and second receiving stands 113 and 118 were fixed to the rotating part 117 and the second support stand 119, respectively, by hexagonal socket set screws 11Z.

[0069] Here, the first receiving stage 113 was held by a first support stage 114 including a pressure transmission section 115 receiving pressure from an actuator described below, a bearing 116, and a rotating section 117 engaging with a rotating shaft to rotate. The rotating section 117 rotates to rotate the first diamond anvil 111 together with the first receiving stage 113. Meanwhile, the second receiving stage 118 was connected to a second support stage 119 receiving pressure from a pressing mechanism 140 described below. The first and second receiving stages 113, 118 and the first and second support stages 114, 119 were held by a stainless steel cylinder 11 with the first and second diamond anvils 111, 112 exposed, constituting a sample holder 110.

[0070] A gas pressure membrane (manufactured by DIAX) was installed on the second receiving stand 118 side as the pressing mechanism 140. The gas pressure membrane was connected to argon gas (not shown), and the gas pressure was adjusted by a pressure controller (PACE5000 manufactured by GE) as the pressing drive circuit 430. This was connected to a personal computer equipped with a CPU as the central processing unit 440.

[0071] The actuator 130 is a hollow laminated piezoelectric actuator (Piezosys The piezoelectric actuator was a piezoelectric actuator (HPSt 1000 / 25-15 / 80 VS35, lead zirconate titanate, stroke length: 80 μm, manufactured by tem Jena GmbH), which was placed in a cylinder tube 131, and a part of which was housed in a sample holder 110. The piezoelectric actuator was connected to a piezoelectric actuator amplifier (Piezosystem, SVR 1000, manufactured by Jena GmbH) 410 and a function generator 450 (WF1973, manufactured by NF Corporation) as an actuator drive circuit 410, which was then connected to a computer.

[0072] A quartz piezoelectric sensor (manufactured by HBK, CLP / 62KN) was installed in the cylinder tube as the pressure sensor 150, and the load due to the gas pressure membrane and the piezoelectric actuator was measured. A piezoelectric sensor amplifier (manufactured by HBK, CMD600) was connected as the conversion measurement unit 420, and connected to a computer via an Ethernet hub. The pressure change (change in load) was determined from the lattice constant of gold by X-ray diffraction (for example, Taku Tsuchiya, JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 108, NO. B10, 2462, 2003).

[0073] The rotation mechanism 120 was equipped with a geared stepping motor (PK564BW-H1005, manufactured by Oriental Motor Co., Ltd.) as a drive unit 121, and a hollow rotating shaft 122 that rotates by the torque of the motor. The rotation drive circuit 460 was a stepping motor driver connected to a pulse generator (PM16C-04XDL, manufactured by Tsuji Electronics Co., Ltd.). The rotating shaft 122 was mounted in a hollow actuator 130 and engaged with the rotating unit 117. The rotation drive circuit 460 of the stepping motor was connected to a computer.

[0074] The control mechanism 160 includes a piezoelectric actuator amplifier, a function generator, a piezoelectric sensor amplifier, a pressure drive circuit (circuit for the gas pressure membrane), a rotation drive circuit (circuit for the rotation mechanism), and a CPU, thereby controlling the operation of the rotation mechanism 120, the pressure mechanism 140, and the actuator 130, and detecting the operation of the pressure sensor 150.

[0075] The pressure-strain apparatus 100 further included a positioning mechanism including a lower stage 310, a support leg 320 with a fine adjustment screw, and a contact plate 330, for positioning the sample.

[0076] [Reference example 1] In Reference Example 1, in the constructed pressure / strain apparatus, a mixture of gold and BaF2 (barium fluoride) was set as sample 11X in the hole at the center of gasket 11Y, and the physical properties of the sample were investigated when pressure was applied to the sample without rotating the first diamond anvil.

[0077] The first and second diamond anvils 111 and 112 were mechanically pressurized to about 2 GPa by the gas pressure membrane. Next, the pressure starting point of the piezo actuator was adjusted by the quartz piezoelectric sensor. After that, a pulse signal (piezo voltage) generated by a function generator was input to the piezo actuator amplifier, and a voltage 120 times that of the signal was supplied to the piezo actuator, which extended the actuator and pressurized the first diamond anvil 111 side. The piezo voltage was pressurized and fixed to 1175 V, and mechanical pressure was applied again by the gas pressure membrane. The pressure change on the sample obtained in this way is shown in Figures 5 to 7. X-ray diffraction measurements were performed in one axial direction (horizontal direction in Figure 1) and radial direction (perpendicular to the paper surface of Figure 1) when each pressure was applied. These results are shown in Figures 8 and 9.

[0078] [Example 1] In Example 1, the constructed pressure-strain device was further equipped with a direction-changing mechanism 340, and a rotatable pressure-strain device was used. In detail, the lower stage 310 of the pressure-strain device was connected to the direction-changing mechanism 340, which combines various stages for adjusting the position in the X-, Y-, and Z-axis directions with a rotary encoder and a ring-type precision encoder.

[0079] In the rotatable pressure / strain apparatus, a mixture of gold and BaF2 (barium fluoride) was set as sample 11X in the hole in the center of gasket 11Y, pressure was applied to the sample, and the physical properties of the sample were investigated when the first diamond anvil was rotated. With pressure applied to the sample, a rotational strain of 180° was applied, and then a further rotational strain of 180° (total 360°) was applied. These operations were performed automatically. The pressure change at this time and the results of X-ray diffraction measurements from uniaxial and radial directions (perpendicular to the paper surface of Fig. 1) are shown in Figs. 10 to 13.

[0080] These results will be summarized. FIG. 5 is a diagram showing the relationship between the load monitored by the pressure sensor and the generated pressure in Reference Example 1. In FIG. FIG. 6 is an enlarged view of region A in FIG. FIG. 7 is an enlarged view of region B in FIG.

[0081] According to Fig. 5, it can be seen that the pressure-strain device of the present invention can be used to continuously apply pressure to a sample in one axial direction (horizontal direction in Fig. 1). In detail, the region A in Fig. 5 shows electrical pressure applied by an actuator, and the region B in Fig. 5 shows mechanical pressure applied by a gas pressure membrane, with a large dynamic range of pressure from 2 GPa to 10 GPa. Fig. 6 shows the change in pressure when the piezoelectric voltage is changed, with the sample numbers BaF3-1 to BaF3-11 at each piezoelectric voltage. Fig. 7 shows the change in pressure when the piezoelectric voltage is fixed at 1175 V and the gas pressure is changed, with the sample numbers BaF3-12 to BaF3-18 at each gas pressure.

[0082] FIG. 8 is a diagram showing an X-ray diffraction pattern in one axial direction in Reference Example 1. As shown in FIG. FIG. 9 is a diagram showing an X-ray diffraction pattern in the radial direction in Reference Example 1.

[0083] According to Fig. 8, BaF2 retains the fluorite-type structure at pressures below 3.6 GPa, but changes completely to the cotunite-type structure at pressures above 3.6 GPa. This shows that, when no rotational distortion is applied to the sample, the application of a pressure of 3.6 GPa or more is necessary for the phase transition from the fluorite-type structure to the cotunite-type structure.

[0084] Figure 9 shows the Debye diffraction pattern expanded for each direction, with the "waviness" in the diffraction lines indicating the degree of strain. The waviness of BaF3-12 subjected to 3.87 GPa (Figure 9A) was larger than that of BaF3-8 subjected to 3.03 GPa (Figure 9B). This indicates that the phase transition from the fluorite type structure to the cotunnite type structure progresses as the strain in BaF2 increases.

[0085] FIG. 10 is a diagram showing the relationship between the load and the generated pressure monitored by the pressure sensor in the first embodiment. FIG. 11 is an enlarged view of region C in FIG.

[0086] Figures 10 and 11 show the pressure change when the piezoelectric voltage is fixed at 980V, the gas pressure is fixed at 30 Bar, the first diamond anvil is rotated 180° at 2.60 GPa, and then rotated another 180° (total 360°). According to Figures 10 and 11, the pressure change with the rotation is small (2.60 GPa → 2.67 GPa → 2.64 GPa). The sample numbers before rotation, after 180° rotation, and after 360° rotation are BaF2-5 to BaF2-7.

[0087] FIG. 12 is a diagram showing an X-ray diffraction pattern in one axial direction in Example 1. As shown in FIG.

[0088] According to Fig. 12, BaF2 before rotation (BaF2-5) had a fluorite type structure, while BaF2 after 180° rotation (BaF2-6) had a completely cotunnite type structure. Furthermore, in BaF3 rotated by 180° (BaF2-7), the cotunnite type structure was stabilized.

[0089] Comparing FIG. 8 of Reference Example 1 in which no rotational strain was applied to the sample with FIG. 12 of Example 1 in which rotational strain was applied to the sample, it was found that by applying rotational strain, a phase transition from the fluorite structure to the cotunnite structure can be induced at a lower pressure (here, only about 2.6 GPa).

[0090] FIG. 13 is a diagram showing an X-ray diffraction pattern in the radial direction in Example 1.

[0091] According to Fig. 13, the waviness of BaF2-7 after 360° rotation (Fig. 13A) was larger than that of BaF2-5 before rotation (Fig. 13B). This indicates that the phase transition from the fluorite type structure to the cotunnite type structure proceeds due to the increase in strain in BaF2, which is consistent with the results in Fig. 9.

[0092] As explained above, it has been shown that by using the pressure-straining device of the present invention, it is possible to apply rotational strain to a sample in a direction perpendicular to the uniaxial direction while applying ultra-high pressure in the uniaxial direction. In addition, it has been shown that by combining the pressure-straining device of the present invention with an X-ray diffraction device, it is possible to investigate the effect of strain under high pressure on the physical properties in the uniaxial direction and the radial direction. Since the pressure-straining device of the present invention is equipped with a control mechanism, it can automatically perform the process from applying pressure to applying rotational strain. It goes without saying that the pressure-straining device of the present invention can be combined with an optical microscope or a microscopic Raman scattering measurement device other than an X-ray diffraction device to observe the sample and investigate various physical properties such as molecular structure, chemical bond, and crystal state. [Industrial Applicability]

[0093] By using the pressure / strain device of the present invention, it is possible to apply strain in the rotational direction, forcibly apply differential stress to a high-pressure sample at an arbitrary pressure, irradiate the sample with X-rays from both vertical and horizontal directions under this condition, and observe the structure and stress state by diffracted X-rays including the radial direction. Since it is constructed so that these operations can be performed remotely, measurements can be safely performed while irradiating powerful X-rays inside a hatch at a synchrotron radiation facility, etc. [Explanation of symbols]

[0094] 11 Cylinders 11X sample 11Y Gasket 11Z Push screw 11Z Hexagon socket set screw 100 Pressure and strain device 110 Sample holder 111 First Diamond Anvil 112 Second Diamond Anvil 113 First Cradle 114 First Support 115 Pressure transmission section 116 Bearing 117 Rotating Part 118 Second Cradle 119 Second Support 120 Rotation Mechanism 121 Drive unit 122 Rotational Axis 130 Actuator 131 Cylinder tube 132 Cylindrical joint 140 Pressing mechanism 150 Pressure Sensor 160 Control Mechanism 210 Stepping motor 220 Spur Gear 230 Arm section 240 Volts 250 Spur Gear Cover 300 Positioning mechanism 310 Lower Stage 320 Support legs with fine adjustment screw 32X Fine Adjustment Screw 330 Backing Plate 340 Directional Mechanism 410 Actuator drive circuit 420 Conversion Measurement Unit 430 Pressing drive circuit 440 Central Processing Unit 450 Function Generator 460 Rotational Drive Circuit 470 Pulse Generator

Claims

1. a sample holder including first and second diamond anvils for clamping a sample, the first diamond anvil rotating; a rotation mechanism that rotates the first diamond anvil; an actuator that applies pressure by an electric signal from the first diamond anvil side and is hollow; a pressing mechanism that mechanically applies pressure from the second diamond anvil side; a pressure sensor that detects a pressure applied to the sample held between the first and second diamond anvils; and a control mechanism that controls the operations of the rotation mechanism, the actuator, and the pressing mechanism and detects the operation of the pressure sensor; Equipped with the rotation mechanism includes a drive unit and a hollow rotation shaft that is rotated by the drive unit; The sample holder comprises: a hollow first pedestal that is joined to the first diamond anvil and fixes the first diamond anvil; a hollow first support base for supporting the first support base, the first support base comprising: a pressure transmission part that receives pressure from the actuator and transmits the pressure to the first diamond anvil; a rotating part that is joined to the first support base and engages with the rotation shaft to rotate; and a bearing that rotates the rotating part against the load received from the pressure transmission part; a hollow second pedestal that is joined to the second diamond anvil and fixes the second diamond anvil; a hollow second support base that supports the second support base, receives pressure from the pressing mechanism, and transmits the pressure to the second diamond anvil; a cylinder that holds the first pedestal, the first support base, the second pedestal, and the second support base while exposing the first and second diamond anvils; Equipped with The rotary shaft is located within the actuator and engages with the rotary portion of the first support base to rotate the first diamond anvil.

2. The pressurizing and straining device according to claim 1 , wherein a step is provided between the pressure transmitting portion and the rotating portion, and the pressure transmitting portion is convex relative to the rotating portion.

3. The pressure and strain device of claim 1 , wherein the pressing mechanism is selected from the group consisting of a stepping motor, a hydraulic piston, and a gas pressure membrane.

4. 2. The pressure-strain device according to claim 1, wherein the actuator is a stacked piezoelectric actuator.

5. 2. The pressure-strain device according to claim 1, wherein the stroke of the actuator is in the range of 50 [mu]m to 200 [mu]m.

6. 2. The pressure and strain device according to claim 1, wherein the pressure sensor is a quartz piezoelectric sensor.

7. the drive unit includes a stepping motor that generates torque and an arm unit that transmits the torque to the rotation shaft via a gear; The pressure-strain device according to claim 1 , wherein the arm portion rotates about the rotation axis.

8. The control mechanism (A) the pressing mechanism applies pressure to the sample from the second diamond anvil side; (B) while pressure is being applied to the sample, the pressure sensor measures the pressure value applied by the actuator, and adjusts the actuator so that the pressure value is the pressure starting point of the actuator; (C) while pressure is being applied to the sample, the actuator adjusted to the pressure starting point continuously applies pressure from the first diamond anvil side; (D) rotating the first diamond anvil with the rotation mechanism while applying pressure to the sample; 2. The pressure and strain device according to claim 1, wherein the operations of the rotation mechanism, the pressing mechanism, and the actuator are controlled in such a manner as to detect the operation of the pressure sensor.

9. a positioning mechanism for determining the position of the sample; The positioning mechanism includes: The lower stage and a support leg connected to the first support table and configured to adjust the position of the sample; a backing plate that abuts against the second support base; The pressure and strain device of claim 1 , comprising:

10. The pressure-strain apparatus of claim 9 , further comprising a deflection mechanism connected to the lower stage for changing the horizontal orientation of the pressure-strain apparatus.

11. 11. The pressure and strain apparatus of claim 10, wherein the deflection mechanism adjusts the horizontal and vertical position of the sample.

12. The pressure-strain device of claim 11 , wherein the control mechanism further controls operation of the deflection mechanism.

13. The control mechanism an actuator drive circuit that applies an electric signal to the actuator; a conversion / measurement unit that converts and measures the pressure of the pressure sensor; a pressing drive circuit that sends a drive signal to the pressing mechanism; a rotation drive circuit that sends a drive signal to the rotation mechanism; a central processing unit that controls the actuator drive circuit, the conversion measurement unit, the pressure drive circuit, and the rotation drive circuit; The pressure and strain device of claim 1 , comprising:

14. The pressure-strain device of claim 13 further comprising a pulse generator connected to the rotary drive circuit.

15. An X-ray diffraction apparatus comprising the pressure and strain device according to any one of claims 1 to 14.

16. A microscopic Raman scattering measurement device comprising the pressure and strain device according to any one of claims 1 to 14.

17. An optical microscope apparatus comprising the pressure and strain device according to any one of claims 1 to 14.

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