Small-angle scattering and wide-angle scattering integrated data collaborative acquisition method and device based on single-crystal diffractometer and readable storage medium thereof

Abstract

The invention relates to a small-angle scattering and wide-angle scattering integrated data collaborative acquisition method and device based on a single-crystal diffractometer and a readable storage medium thereof, and the method comprises the steps: designing two improved sample racks (the first sample rack is used for a grazing incidence mode, and the second sample rack is used for a transmission mode), replacing a magnetic head structure of an original single-crystal diffractometer, and improving the measurement accuracy of the small-angle scattering and wide-angle scattering integrated data collaborative acquisition method. And vertical fixation of the sample and high-precision incident angle control are realized. The first sample rack adopts a structure of a fixing plate, a vertical backrest and a groove, and a sample is fixed through a rigid connecting piece; and the second sample holder adopts a backup plate with a detection hole to support the fixation of the substrate-free film. The method breaks through the limitation of the traditional test range, eliminates the signal splicing error, realizes the full-dimensional characterization of the material structure, and is suitable for the depth gradient analysis of thin films, free films and blocky samples.

Description

Technical Field

[0001] The present invention relates to, in particular to, a method and device for collaboratively collecting integrated data of small-angle scattering and wide-angle scattering based on a single crystal diffractometer and a readable storage medium thereof. Background Art

[0002] The existing wide-angle scattering test method based on single crystal diffractometer (such as CN113049617B) has the following limitations: 1. Imprecise control of the incident angle: It is difficult to fix sheet samples vertically using the traditional magnetic head (or crystal ring) fixation method, and the reliance on flexible plasticine fixation leads to angle deviation and sample collapse.

[0003] 2. Limited test range: The 2θ starting angle is limited to 3° in the grazing incidence mode, and the scattered signal in the small angle area of ​​0-3° cannot be detected.

[0004] 3. Incomplete signal acquisition: The beamstop support rod blocks the scattered signal in the qz direction (vertical to the sample surface), and only the information in the qx direction (horizontal direction) can be obtained.

[0005] 4. Signal stitching error: Traditional small-angle and wide-angle scattering need to be collected by separate devices. The intensity difference leads to the introduction of human control during stitching, which affects the objectivity of the data.

[0006] Therefore, a method for collaboratively collecting small-angle scattering and wide-angle scattering data based on a single crystal diffractometer is urgently needed to solve the problems that the existing technology cannot simultaneously realize the accurate collection of small-angle and wide-angle scattering signals on a single crystal diffractometer, and there are problems such as low incident angle control accuracy, signal shielding in the qz direction, limited test range and signal splicing errors. Summary of the invention

[0007] The purpose of the present invention is to address the above-mentioned problems existing in the prior art and to provide a method, device and readable storage medium for collaborative collection of integrated small-angle scattering and wide-angle scattering data based on a single crystal diffractometer.

[0008] The core technology of the present invention is mainly to design a rigid sample holder to achieve vertical sample fixation and high-precision incident angle control, combine specific parameter settings and quaternion diffractometer degree of freedom control, break through the beamstop (beam blocker, mainly its two brackets, the first beam blocker bracket and the second beam blocker bracket) blocking limitation, and synchronously collect small-angle and wide-angle scattering signals starting from 0.5° to achieve full-dimensional characterization of the material structure.

[0009] In order to achieve the above application objectives, in the first aspect, the present invention adopts the following technical solutions: The present invention relates to a method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer, comprising the following steps: S00, select and improve the sample holder according to the requirements of grazing incidence mode and transmission mode; The improved sample holder is used to replace the magnetic head on the original sample stage of the single crystal diffractometer, and the improved sample holder includes a first sample holder for a grazing incidence mode and a second sample holder for a transmission mode; The first sample holder includes a fixing plate with a fixing hole and a vertical backrest with a height higher than the fixing plate, the fixing hole is provided with a connecting piece for fixing the sample, a groove for placing the sample is formed between the vertical backrest and the fixing plate, and a stud for mounting on the original sample stage of the single crystal diffractometer is provided at the bottom of the groove; The second sample holder includes a support plate with a detection hole, and the bottom of the support plate is also provided with a stud for mounting on the original sample stage of the single crystal diffractometer; S10, preparing the sample and placing it on the improved sample holder, along the direction of X-ray travel; S20, selecting an X-ray light source so that the X-ray light source is aimed at the sample, wherein the X-ray light source is a gallium target; S30, setting the sample rotation angle of the original sample stage of the single crystal diffractometer, and moving the sample forward and backward in the y direction until the sample cuts half of the light blocker to find the zero point position of the sample; S40, rotating the sample along the incident angle direction on the improved sample holder to scan, and starting the test; S50, setting the distance between the sample and the surface detector of the single crystal diffractometer, setting the incident angle by setting the sample rotation angle of the original sample stage of the single crystal diffractometer, and setting the exposure time to collect the scattered signal; S60, collecting scattered X-ray signals through a two-dimensional surface detector and integrating them through software to obtain a one-dimensional diffraction angle 2theta diagram or a one-dimensional scattering diagram of the X-rays.

[0010] Furthermore, in step S30, if the sample is tilted in the vertical direction, the vertical tilt angle of the original sample stage of the single crystal diffractometer is changed to adjust the collimation of the sample in the vertical direction.

[0011] Furthermore, in step S50, the distance between the sample and the detection surface of the single crystal diffractometer is set to 100-240 mm, the incident angle is set to 0.1-1°, and the exposure time is set to 1-60 s.

[0012] Furthermore, in step S00, the depth of the groove is 2 mm.

[0013] Furthermore, in step S00, the diameter of the detection hole is 5-8 mm.

[0014] Furthermore, in step S30, the sample rotation angle of the original sample stage of the single crystal diffractometer is set to a value between 85° and 95°.

[0015] Furthermore, in step S00, the sample is fixed on the support plate by double-sided tape or glue.

[0016] In a second aspect, the present invention provides an electronic device comprising a memory and a processor, wherein the memory stores a computer program, and the processor is configured to run the computer program to execute the above-mentioned method for collaborative data collection of integrated small-angle scattering and wide-angle scattering based on a single crystal diffractometer.

[0017] In a third aspect, the present invention provides a readable storage medium, in which a computer program is stored. The computer program includes a program code for controlling a process to execute the process. The process includes the above-mentioned method for collaborative data collection of integrated small-angle scattering and wide-angle scattering based on a single crystal diffractometer.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. Full-angle coverage and low-angle breakthrough: By optimizing the sample holder design and detector distance (≥200mm), the test starting angle is expanded from 3° (Cu target) of traditional technology to 0.5°, realizing the integrated collection of small-angle scattering (SAXS) and wide-angle scattering (WAXS) signals, covering the full angle range starting from 0.5°.

[0019] 2. Improved signal integrity: The vertical fixation of the sample and the adjustment of the incident angle (0.1-1°) bypass the beamstop (beam blocker) to completely capture the scattered signal in the qz direction (perpendicular to the sample surface), solving the signal loss problem in traditional technologies and supporting in-depth analysis of the ordered stacking structure of the material.

[0020] 3. Data objectivity and accuracy: Synchronously collect small-angle and wide-angle signals to eliminate subjective errors introduced by artificial stitching intensity differences. Through the rigid sample stage and four-element diffractometer degree of freedom control (Chi, Phi, 2Theta, Omega), the incident angle accuracy (±0.01°) and data reproducibility are ensured.

[0021] 4. Application expansion and operational flexibility: It supports switching between grazing incidence and transmission modes, and is suitable for superficial to bulk structural gradient analysis of thin film materials (such as organic photovoltaics and data storage chips). The improved sample stage is compatible with the original diffractometer base, which is easy to operate and highly safe. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a method flow chart of an embodiment of the present invention; Figure 2 is a schematic structural diagram of a first sample rack according to an embodiment of the present invention; Figure 3 is a schematic structural diagram of a second sample rack according to an embodiment of the present invention; Figure 4 It is a structural schematic diagram of the prior art; Figure 5 is a scattering pattern that can be detected by existing technology; Figure 6 This is a schematic diagram of the debugging process of the method of the embodiment of the present invention. Figure 1 ; Figure 7 This is a schematic diagram of the debugging process of the method of the embodiment of the present invention. Figure 2 ; Figure 8 This is a schematic diagram of the debugging process of the method of the embodiment of the present invention. Figure 3 ; Fig. 9 is a scattering diagram of an organic small molecule film deposited on a silicon substrate according to an embodiment of the present invention; Fig.10 It is a diffraction angle 2theta diagram of an organic small molecule film deposited on a silicon substrate according to an embodiment of the present invention.

[0023] In the figure, 1, first sample holder; 2, second sample holder; 3, magnetic head; 4, first beam blocker bracket; 5, second beam blocker bracket; 6, sample stage; 11, fixing plate; 12, vertical backrest; 13, fixing hole; 14, connecting piece; 15, groove; 21, back plate; 22, detection hole. DETAILED DESCRIPTION

[0024] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0025] Those skilled in the art should understand that, in the disclosure of the present invention, the orientation or position relationship indicated by terms such as "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inside" and "outside" are based on the orientation or position relationship shown in the accompanying drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the above terms should not be understood as limiting the present invention.

[0026] Currently available technologies such as Figure 4 As shown in FIG. 1 , since the original magnetic head 3 cannot support the sheet sample standing upright on the magnetic head 3, if the vertically standing sample is fixed on the magnetic head 3 with plasticine, the incident angle cannot be precisely controlled due to the flexibility of the plasticine, and the standing sample tends to collapse to one side as time goes by. Therefore, the final scattering diagram is as follows Figure 5 As shown, the qz direction (i.e., perpendicular to the sample surface) is blocked by the fixing rod of the beamstop (beam blocker, mainly its two brackets, the first beam blocker bracket 4 and the second beam blocker bracket 5), and only the qx direction (i.e., the horizontal direction of the sample surface) can be extracted. Among them, the single crystal diffractometer is consistent with the disclosure of CN113049617B, with four rotational degrees of freedom of Chi (vertical tilt), Phi (horizontal rotation), 2Theta (detector rotation) and Omega (sample rotation), and with the height adjustment, left and right and front and back position adjustment on the goniometer head, the sample can be accurately positioned and centered, with higher operational controllability and improved collection of scattered signals, wherein the goniometer head is a part of the goniometer. In addition, the single crystal diffractometer has a temperature control system and an imaging system.

[0027] In order to solve the problems existing in the prior art, the present invention proposes the following technical solutions to solve the problems existing in the prior art: like Figure 1 As shown, the integrated data collaborative collection method of small-angle scattering and wide-angle scattering based on a single crystal diffractometer includes the following steps: S00, select and improve the sample holder according to the requirements of grazing incidence mode and transmission mode; The improved sample holder is used to replace the magnetic head 3 on the original sample stage 6 of the single crystal diffractometer (the magnetic head 3 is directly mounted on the mounting hole of the sample stage 6 through a stud and then fixed with a screw), and the improved sample holder includes a first sample holder 1 for a grazing incidence mode and a second sample holder 2 for a transmission mode; like Figure 2 As shown, the first sample holder 1 comprises a fixing plate 11 provided with a fixing hole 13 and a vertical backrest 12 whose height is higher than the fixing plate 11. A connecting piece 14 for fixing the sample is provided on the fixing hole 13. A groove 15 for placing the sample is formed between the vertical backrest 12 and the fixing plate 11. A stud for mounting on the original sample stage 6 of the single crystal diffractometer is provided at the bottom of the groove 15. The mounting method of the stud is consistent with the original magnetic head 3. When installing, the magnetic head 3 can be removed and replaced with the first sample holder 1. Since the fixture (first sample holder 1) is rigid, the incident angle has high precision and high reproducibility. The upright backrest (high flat plate) can align the sample in the vertical direction, so that the sample stands upright in the vertical direction, and the sample is fixed horizontally with the screws (connector 14) provided in the first sample holder 1. The groove 15 is 2 mm deep and can accommodate almost all bulk samples or sheet-like film samples.

[0028] like Figure 3As shown, the second sample holder 2 includes a support plate 21 with a 5-8mm detection hole 22. The bottom of the support plate 21 is also provided with a stud for mounting on the original sample stage 6 of the single crystal diffractometer. The installation method of this stud is consistent with the original magnetic head 3. When installing, the magnetic head 3 can be removed and replaced with the second sample holder 2; wherein, the sample is fixed to the support plate 21 by double-sided tape or glue.

[0029] Since the mold (second sample holder 2) is rigid, the incident angle has high precision and high reproducibility. The sample on this mold is vertically upright using double-sided tape and can be adjusted to the center of the goniometer, that is, the area irradiated by the X-ray. The detection hole 22 has a diameter of 5-8 mm and can carry all (substrate-free) sheet-like film samples.

[0030] S10, preparing the sample and placing it on the improved sample holder, along the direction of X-ray travel; S20, selecting an X-ray light source so that the X-ray light source is aimed at the sample, wherein the X-ray light source is a gallium target; S30, setting the sample rotation angle of the original sample stage 6 of the single crystal diffractometer to a value between 85 and 95 degrees, and moving the sample forward and backward in the y direction until the sample cuts half of the beam stop (beam blocker) to find the zero point position of the sample; Figure 6 It is the zero point position when the sample stage 6 moves back and forth, that is, the substrate should cut half of the beamstop in the vertical direction. At this time, the substrate is tilted in the vertical direction. The chi needs to be adjusted here so that the sample is also a straight line in the vertical direction instead of a diagonal line, and cuts half of the beamstop.

[0031] Among them, Figure 7 As shown, if the sample is tilted in the vertical direction, the vertical tilt angle of the original sample stage 6 of the single crystal diffractometer is changed to adjust the collimation of the sample in the vertical direction.

[0032] like Figure 8 It is the zero point position when the sample stage 6 moves back and forth, that is, the substrate should cut the beamstop in half in the vertical direction. At this time, the substrate not only cuts the beamstop in half, but also is perpendicular to the horizontal frame in the vertical direction.

[0033] S40, rotating the sample along the incident angle direction on the improved sample holder for scanning (i.e. changing the omega angle (incident angle)), and starting the test; S50, setting the distance between the sample and the surface detector of the single crystal diffractometer to 100-240 mm, setting the incident angle to 0.1-1° (omega angle value) by setting the sample rotation angle of the original sample stage 6 of the single crystal diffractometer, and setting the exposure time to 1-60 s to collect the scattered signal; like Fig. 9 For organic small molecule films deposited on silicon substrates, the distance from the detector to the sample is 100-240 mm, the incident angle is 0.1-1°, and the exposure time is 30-60 seconds.

[0034] S60, collecting scattered X-ray signals through a two-dimensional surface detector and integrating them through software to obtain a one-dimensional diffraction angle 2theta diagram or a one-dimensional scattering diagram of the X-rays.

[0035] In this step, the software that comes with the device is used to integrate the X-ray one-dimensional diffraction angle 2theta diagram or phase angle gamma diagram, such as Fig.10 The 2theta diffraction angle diagram is shown in Figure 1. The ordinate represents the signal intensity counts and the abscissa represents the 2theta diffraction angle. The specific method of obtaining the one-dimensional diffraction angle 2theta diagram or one-dimensional scattering diagram of X-rays is consistent with the prior art and will not be repeated here.

[0036] Embodiment 2 An electronic device includes a memory and a processor, wherein a computer program is stored in the memory, and the processor is configured to run the computer program to execute the small-angle scattering and wide-angle scattering integrated data collaborative collection method based on a single crystal diffractometer in embodiment 1.

[0037] Embodiment 3 This embodiment also provides a readable storage medium, in which a computer program is stored, the computer program includes a program code for controlling a process to execute a process, the process includes the small-angle scattering and wide-angle scattering integrated data collaborative acquisition method based on a single crystal diffractometer according to the first embodiment. [1] It should be noted that the specific examples in this embodiment can refer to the examples described in the above embodiments and optional implementation modes, and this embodiment will not be described in detail here.

[0038] In general, various embodiments may be implemented in hardware or dedicated circuits, software, logic, or any combination thereof. Some aspects of the invention may be implemented in hardware, while other aspects may be implemented in firmware or software executed by a controller, microprocessor, or other computing device, but the invention is not limited thereto. Although various aspects of the invention may be shown and described as block diagrams, flow charts, or using some other graphical representation, it should be understood that, as non-limiting examples, the boxes, devices, systems, techniques, or methods described herein may be implemented in hardware, software, firmware, dedicated circuits or logic, general-purpose hardware or controllers or other computing devices, or some combination thereof.

[0039] Embodiments of the present invention may be implemented by computer software that is executable by a data processor of a mobile device, such as in a processor entity, or by hardware, or by a combination of software and hardware. Computer software or programs (also referred to as program products) including software routines, applets and / or macros may be stored in any device-readable data storage medium, and they include program instructions for performing specific tasks. A computer program product may include one or more computer executable components configured to perform an embodiment when the program is run. One or more computer executable components may be at least one software code or a portion thereof. In addition, at this point, it should be noted that, for example, Figure 1 Any block of the logic flow in the program may represent program steps, or interconnected logic circuits, blocks and functions, or a combination of program steps and logic circuits, blocks and functions. The software may be stored on physical media such as memory chips or storage blocks implemented within a processor, magnetic media such as hard disks or floppy disks, and optical media such as, for example, DVDs and their data variants, CDs, etc. Physical media are non-transitory media.

[0040] The parts not described in detail in the present invention are prior art, so the present invention does not describe them in detail.

[0041] It is to be understood that the term "one" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple, and the term "one" should not be understood as a limitation on the quantity.

[0042] Although the terms such as first sample holder 1, second sample holder 2, magnetic head 3, first beam blocker support 4, second beam blocker support 5, sample stage 6, fixing plate 11, vertical backrest 12, fixing hole 13, connecting member 14, groove 15, back plate 21, detection hole 22 are used more frequently in this article, the possibility of using other terms is not excluded. The use of these terms is only for more convenient description and explanation of the essence of the present invention; interpreting them as any additional limitation is contrary to the spirit of the present invention.

[0043] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that are the same or similar to the present invention fall within the protection scope of the present invention.

Claims

1. A method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer, characterized in that: The following steps are involved: S00, select and improve the sample holder according to the requirements of grazing incidence mode and transmission mode; Wherein, the improved sample holder is used to replace the magnetic head on the original sample stage of the single crystal diffractometer, and the improved sample holder includes a first sample holder for the grazing incidence mode and a second sample holder for the transmission mode; The first sample holder comprises a fixing plate with a fixing hole and a vertical backrest with a height higher than the fixing plate, the fixing hole is provided with a connecting piece for fixing the sample, a groove for placing the sample is formed between the vertical backrest and the fixing plate, and a stud for mounting on the original sample stage of the single crystal diffractometer is provided at the bottom of the groove; The second sample holder comprises a support plate provided with a detection hole, and the bottom of the support plate is also provided with a stud for mounting on the original sample stage of the single crystal diffractometer; S10, preparing the sample and placing it on the improved sample holder, along the direction of X-ray travel; S20, selecting an X-ray light source so that the X-ray light source is aimed at the sample, wherein the X-ray light source is a gallium target; S30, setting the sample rotation angle of the original sample stage of the single crystal diffractometer, and moving the sample forward and backward in the y direction until the sample cuts half of the light blocker to find the zero point position of the sample; S40, rotating the sample along the incident angle direction on the improved sample holder to scan, and starting the test; S50, setting the distance between the sample and the surface detector of the single crystal diffractometer, setting the incident angle by setting the sample rotation angle of the original sample stage of the single crystal diffractometer, and setting the exposure time to collect the scattered signal; S60, collecting scattered X-ray signals through a two-dimensional surface detector and integrating them through software to obtain a one-dimensional diffraction angle 2theta diagram or a one-dimensional scattering diagram of the X-rays.

2. The method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer according to claim 1, characterized in that: In step S30, if the sample is tilted in the vertical direction, the vertical tilt angle of the original sample stage of the single crystal diffractometer is changed to adjust the collimation of the sample in the vertical direction.

3. The method for collaboratively collecting integrated small-angle scattering and wide-angle scattering data based on a single crystal diffractometer according to claim 1, characterized in that: In step S50, the distance between the sample and the detection surface of the single crystal diffractometer is set to 100-240 mm, the incident angle is set to 0.1-1°, and the exposure time is set to 1-60 s.

4. The method for collaboratively collecting integrated small-angle scattering and wide-angle scattering data based on a single crystal diffractometer according to claim 3, characterized in that: In step S00, the depth of the groove is 2 mm.

5. The method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer according to claim 1, characterized in that: In step S00, the diameter of the detection hole is 5-8 mm.

6. The method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer according to claim 1, characterized in that: In step S30, the sample rotation angle of the original sample stage of the single crystal diffractometer is set to a value between 85° and 95°.

7. The method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer according to claim 1, characterized in that: In step S00, the sample is fixed on the support plate by double-sided tape or glue.

8. An electronic device comprising a memory and a processor, characterized in that: The memory stores a computer program, and the processor is configured to run the computer program to execute the method for collaboratively collecting small-angle scattering and wide-angle scattering integrated data based on a single crystal diffractometer as described in any one of claims 1 to 7.

9. A readable storage medium, characterized in that: The readable storage medium stores a computer program, which includes a program code for controlling a process to execute a process, and the process includes the method for collaborative data collection of integrated small-angle scattering and wide-angle scattering based on a single crystal diffractometer according to any one of claims 1 to 7.

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