High-resolution in-situ X-ray diffraction testing system and method based on multi-field coupling

Abstract

This invention discloses a high-resolution in-situ X-ray diffraction system and its testing method based on multi-field coupling, belonging to the field of X-ray diffraction testing technology. It aims to solve the problem that existing technologies cannot simultaneously monitor the macroscopic electrical properties and microscopic atomic-level structural changes of thin film materials under a heating and electric coupling environment. The system of this invention includes a high-resolution thin film XRD device, an in-situ cavity, an electric heating strip, a temperature sensor, an external electrochemical workstation, a four-electrode system, and a flat conductive layer disposed on the back of the sample. The method of this invention maintains the flatness of the sample through the flat conductive layer, performs thermal drift calibration based on the characteristic diffraction peaks of the substrate, and uses a dual-mode detector to switch collaboratively under pulsed electric field excitation, achieving simultaneous in-situ monitoring of macroscopic electrical properties and microscopic atomic-level structural changes. This invention is mainly used for in-situ structural characterization and electrical property analysis of thin film materials under multi-field coupling environments.

Description

Technical Field

[0001] This invention relates to the field of X-ray diffraction testing and characterization technology, specifically to a high-resolution in-situ X-ray diffraction system and testing method based on multi-field coupling, which is particularly suitable for simultaneously acquiring information on macroscopic electrical properties and microscopic atomic-level structural changes of thin film materials under heating and electric multi-field coupling environments. Background Technology

[0002] In-situ X-ray diffraction (XRD) characterization technology can track the dynamic evolution of the crystal structure of materials in real time under specific external excitation environments, and is an important means to reveal the phase transformation and structural response mechanisms of functional materials. Currently, common in-situ environments include thermal fields (high / low temperature), electric fields (charge and discharge, electrochemical), magnetic fields, optical fields, and acoustic fields. However, the construction of multi-field coupled in-situ environments is extremely challenging due to the coordinated control and mutual interference of multiple physical fields.

[0003] In the prior art, there are already heating and electric dual-field coupled in-situ testing systems based on high-resolution thin-film XRD equipment (such as the scheme disclosed in CN114235869 B). This system realizes in-situ X-ray diffraction testing of semiconductor samples under heating and electric conditions by setting electric heating strips and positive and negative electrode plates in the in-situ cavity and cooperating with an external electrochemical workstation.

[0004] However, this solution still has the following limitations in practical applications:

[0005] Firstly, using only a positive and negative electrode structure only allows voltage to be applied to the sample, making it impossible to simultaneously and accurately measure the macroscopic electrical performance parameters (such as resistance and conductivity) of the sample during the test, resulting in a lack of information on the correlation between microstructure evolution and macroscopic electrical performance. Secondly, directly extending electrode leads from the back of the sample will disrupt the horizontal flatness of the sample surface, severely affecting the acquisition quality of X-ray diffraction signals. Third, during the heating process, the sample fixture and insulating components deform due to thermal expansion, causing the sample surface height to shift, which in turn causes the diffraction peak position to drift, affecting the accuracy and reproducibility of the test data.

[0006] Therefore, there is an urgent need for a high-resolution in-situ X-ray diffraction system and its testing method based on multi-field coupling to solve the problems existing in the current technology. Summary of the Invention

[0007] The purpose of this invention is to address the aforementioned problems in the prior art by providing a high-resolution in-situ X-ray diffraction testing method based on multi-field coupling. By constructing a flat conductive layer on the back of the sample and using edge leads to eliminate physical interference, combined with a high-temperature thermal drift self-calibration mechanism based on substrate characteristic diffraction peaks, and a detection mode that switches between dynamic and steady-state dual detectors under a pulsed electric field, high-precision, high-throughput, and high-resolution real-time monitoring of the microstructure of materials under a high-temperature electric field environment is achieved.

[0008] To achieve the above-mentioned application objectives, the present invention adopts the following technical solution: a high-resolution in-situ X-ray diffraction testing system based on multi-field coupling, based on a high-resolution thin film XRD device, and further including an in-situ cavity disposed on the high-resolution thin film XRD, a sample holder disposed in the in-situ cavity, an electric heating strip and a temperature sensor disposed on the sample holder. An external electrochemical workstation located outside the in-situ cavity; The four-electrode system electrically connected to the external electrochemical workstation includes two working electrodes, one reference electrode, and one counter electrode. Each electrode is insulated from the electric heating bar and the in-situ cavity through an insulating structure. A flat conductive layer is provided on the back of the sample to be tested. The flat conductive layer is electrically connected to the counter electrode and is used to maintain the horizontal flatness of the back of the sample to be tested while maintaining conductivity and thermal conductivity. The in-situ cavity is also connected to a cooling channel that communicates with the in-situ cavity.

[0009] A high-resolution in-situ X-ray diffraction testing method based on multi-field coupling, using the above-mentioned system, includes the following steps: Sample flattening assembly steps: A flat conductive layer is arranged on the back of the sample to form a counter electrode. Conductive wire bundles are led out from the edge area of ​​the flat conductive layer to maintain the overall flatness of the sample. A front electrode assembly containing a reference electrode and a working electrode is arranged on the front of the sample. Optical path alignment and reference locking steps: Adjust the surface of the sample to be tested to the center of the optical path of the X-ray diffraction equipment, and scan to obtain the characteristic diffraction peaks of the sample substrate; Multi-field coupled dual-mode in-situ detection steps: Temperature field and pulsed electric field excitation are applied simultaneously to the sample under test. When the temperature field causes thermal expansion of the test environment, thermal drift calibration is performed using the characteristic diffraction peak of the substrate as an invariant reference to reposition the optical path center. During the modulation stage of pulsed electric field excitation, the first mode detector of the X-ray diffraction equipment is used to continuously scan to obtain dynamic structural evolution information. After the electrical response of the sample under test reaches a steady state, the second mode detector is switched to scan to obtain steady-state high-resolution structural information.

[0010] Furthermore, the front electrode assembly includes two working electrodes and one reference electrode, which together with the counter electrode located on the back side constitute a four-electrode system for in-situ electrical performance measurement. The flat conductive layer is constructed by using conductive paste or ceramic adhesive to bond a rigid conductive sheet with the same area as the back of the sample to the back of the sample; one end of the conductive wire bundle is connected to the lateral edge of the rigid conductive sheet, and the other end is led out and electrically connected to the external test equipment to avoid physical interference caused by the conductive wire bundle directly under the sample.

[0011] Furthermore, thermal drift calibration is performed using the characteristic diffraction peaks of the substrate as an invariant reference, specifically including: After the temperature field is heated and kept constant at a preset high temperature, the substrate peak that does not undergo structural phase change at the preset high temperature is selected as the absolute reference scale. Height scanning and horizontal tilt scanning are performed on the substrate peak. By tracking the peak position offset of the substrate peak, the error of sample surface height change caused by thermal expansion of the insulating fixture is compensated.

[0012] Furthermore, the first-mode detector is an array detector that supports short-exposure rapid imaging, and the second-mode detector is a point detector that supports wide-angle high-resolution data collection; a pulse voltage in the low-frequency range is applied to the front electrode assembly and the counter electrode to trigger the first-mode detector to rapidly track the lattice transient response of the thin film layer of the sample at the moment of electric field stimulation.

[0013] Furthermore, when scanning with the first mode detector, the scanning step size is 0.01° / step and the scanning speed is 1s / step; when switching to the second mode detector for scanning, the scanning step size is 0.01° / step and the scanning speed is 0.1s / step; the frequency of the pulse voltage is 0.125Hz, the duty cycle is 50%, and the voltage amplitude range is ±2V.

[0014] Furthermore, the method also includes a micro-region high-throughput mapping step: The X-ray diffraction equipment uses a point-focus mode X-ray source. By controlling the XY two-dimensional translation stage to move the sample to be tested sequentially, in-situ X-ray diffraction patterns of different microelectrode regions on the surface of the sample are obtained, and a spatial distribution mapping map of structural feature parameters is constructed.

[0015] Furthermore, the X-ray diffraction equipment is equipped with a rotating target point copper target light source to match the differentiated in-situ testing requirements of the thin film interface and depth direction.

[0016] Furthermore, the insulation structure includes an insulating sheet disposed between the electric heating strip and the sample to be tested, and an alumina tube respectively sleeved outside each electrode lead; the electrode leads are isolated from each other by the alumina tubes to prevent short circuits.

[0017] Furthermore, the high-resolution thin-film XRD equipment has at least a rotating target focal Cu light source, a LynxEye detector, and a scintillation counter; the in-situ cavity is equipped with a detachably connected hemispherical beryllium window, which allows X-rays to penetrate and form a closed cavity; the spot size of the rotating target focal Cu light source is adjustable, and in conjunction with the digital XY movement of the sample stage, it enables in-situ high-throughput testing of micro-area multi-field coupling.

[0018] Beneficial effects of the present invention 1. By forming a counter electrode on the back side of the sample and leading conductive wires from its edge region, this invention effectively eliminates the disruption to the sample's horizontal flatness caused by traditional direct back-side wiring. Combined with the reference electrode and working electrode arranged on the front side to form a four-electrode system, it ensures excellent electrical and thermal conductivity while avoiding the loss of X-ray diffraction signals caused by sample surface tilt or height anomalies, significantly improving the accuracy and structural stability of in-situ test data.

[0019] 2. To address the issue of thermal expansion of components such as insulating fixtures in in-situ cavities under high-temperature conditions, this invention introduces a reference locking and calibration mechanism based on substrate characteristic diffraction peaks. By selecting substrate characteristic peaks that do not undergo structural phase transitions at a preset high temperature as an absolute reference scale for height and horizontal tilt scanning, the invention can accurately compensate for height variation errors on the sample surface, solve the problem of optical path deviation caused by high-temperature thermal expansion, and ensure the standardization and reproducibility of diffraction signals during long-term temperature-varying tests.

[0020] 3. To address the complex structural responses under pulsed electric field excitation, this invention employs a dual-mode detector collaborative switching logic. During the modulation phase of pulsed voltage stimulation, a first-mode detector performs short-exposure rapid continuous scanning to accurately capture the dynamic transient response of the thin-film lattice. After the electrical properties reach a steady state, the system switches to a second-mode detector to acquire steady-state evolution information such as cell parameters and crystallinity. This mechanism overcomes the limitations of traditional single-mode detection, achieving multi-dimensional collaborative characterization of macroscopic electrical properties and microscopic transient / steady-state structures.

[0021] 4. By combining a point-focus X-ray source and a two-dimensional XY translation stage with a predetermined Z-height, this invention can obtain spatially resolved in-situ X-ray diffraction patterns for different microelectrode regions on the surface by limiting the size of the X-ray irradiation spot and sequentially moving the test sample without disrupting the in-situ multi-field coupling test environment. This method successfully constructs a spatial distribution mapping map of structural characteristic parameters, expands the test throughput and analysis dimensions for evaluating the phase and lattice evolution of material micro-regions, realizes non-destructive map-based dynamic microstructure characterization of device patterns, and establishes a mapping correlation between the microstructure and macroscopic performance of the device topography. Attached Figure Description

[0022] Figure 1This is a schematic diagram of the overall structure of the system of the present invention; Figure 2 This is a flowchart of the testing method of the present invention; Figure 3 This is a top view of the sample to be tested in this invention. Figure 4 This is a side view of the sample to be tested in this invention; Figure 5 This is a graph showing pulse voltage changes; Figure 6 This is a graph showing the pulse resistance variation. Figure 7 Fine-scan XRD patterns of the resistor under different voltage polarization states when the resistor is stable. Figure 8 This is a graph showing the pulsed conductivity variation. Figure 9 This is a diagram showing the changes in the peak positions of the thin film in instantaneous in-situ XRD.

[0023] In the figure: 1. Electric heating strip; 2. Insulating sheet; 3. Sample to be tested; 4. Temperature sensor; 5. Pt wire; 6. External electrochemical workstation; 7. Gas inlet and outlet; 8. Liquid nitrogen delivery pipe; 9. In-situ cavity; 10. Substrate; 11. Thin film to be tested; 13. Rigid conductive sheet; 14. Counter electrode; 61. Reference electrode; 62. Working electrode. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention are within the scope of protection of the present invention.

[0025] Those skilled in the art should understand that, in the disclosure of this invention, the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. These terms are merely for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, the above terms should not be construed as limitations on the invention. Furthermore, the term "front" refers to the side of the sample 3 on which the thin film 11 is deposited, and "back" refers to the other side of the substrate 10.

[0026] Example 1 like Figure 1 As shown, this embodiment provides a high-resolution in-situ X-ray diffraction system based on multi-field coupling, which is built on the basis of a high-resolution thin-film XRD device.

[0027] The high-resolution thin-film XRD equipment includes at least a rotating target-focused Cu light source (CuKα radiation), a LynxEye detector, and a scintillation counter. The LynxEye detector has zero-dimensional and one-dimensional modes, suitable for rapid reciprocal space imaging data collection of polycrystalline thin films and single-crystal epitaxial films; the scintillation counter is suitable for high-resolution data collection of single-crystal epitaxial films. The equipment is also equipped with a high-low temperature system TC-DOME, which can cover thin-film sample testing from -150℃ to 450℃ and from room temperature to 1100℃. In focusing mode, the spot size of the rotating target-focused Cu light source can be adjusted from 0.1mm to 2mm to match the testing requirements of different micro-area locations.

[0028] The original sample stage of the high-resolution thin film XRD equipment is disassembled, while the multi-axis drive structure (e.g., a seven-axis drive structure) under the sample stage is retained. The in-situ cavity 9 is installed on the multi-axis drive structure, and the spatial position of the in-situ cavity 9 in the X-ray optical path can be easily adjusted through the multi-axis drive structure.

[0029] The in-situ cavity 9 contains a sample holder, on which are mounted an electric heating strip 1 and a temperature sensor 4. The electric heating strip 1 is a Pt heating strip, and an insulating sheet 2 is placed between the Pt heating strip 1 and the sample 3 to be tested. The insulating sheet 2 is made of alumina (Al2O3), which has a melting point of 2054℃ and a boiling point of 2980℃, meeting the testing requirements of high-resolution thin-film XRD equipment up to 1100℃. Ordinary materials such as rubber are not suitable within this temperature range. The temperature sensor 4 is a thermocouple used to monitor the temperature inside the in-situ cavity 9 in real time.

[0030] An external electrochemical workstation 6 is provided outside the in-situ cavity 9. The external electrochemical workstation 6 is electrically connected to the electrode system located inside the in-situ cavity 9 via a wire harness (i.e., Pt wire 5).

[0031] The electrode system includes two working electrodes 62, one reference electrode 61, and one counter electrode 14. All four electrodes use Pt wire 5 as the lead material.

[0032] like Figure 3 As shown, two working electrodes 62 and one reference electrode 61 are mounted on the front side of the sample 3 under test. One of the working electrodes 62 is used to apply an external field voltage, and the other is used to test the resistance. The reference electrode 61 is used to provide a potential reference. Figure 4 As shown, the counter electrode 14 is mounted on the back side of the sample 3 to be tested.

[0033] In high-resolution X-ray diffraction testing, if electrode leads are directly soldered to the back of the sample 3, the protruding parts of the leads will disrupt the horizontal flatness of the sample surface, resulting in the inability to obtain effective substrate peak and thin film peak diffraction signals. To solve this problem, this embodiment provides a flat conductive layer on the back of the sample 3. Specifically, as shown... Figure 4 As shown, La is pre-deposited on the back side of the substrate 10 of the sample to be tested 3. 0.6 Sr 0.4 CoO 3-δ A conductive layer serves as the bottom layer for the counter electrode. Then, Pt paste is coated across the entire back side and baked dry to form a conductive whole, giving the back side both good conductivity and excellent flatness. Based on this, a Pt sheet (rigid conductive sheet 13) with an area equivalent to the back side of the substrate 10 is bonded to the back side of the substrate 10 using silver paste. The silver paste is heat-resistant, withstanding at least 1000°C, and will not melt or fail when heated to 300°C or 500°C, nor will it contaminate the in-situ cavity 9. Pt wires 5 extend from the lateral edges of the Pt sheet (rigid conductive sheet 13) as connecting lines for the counter electrode 14. The wires extend from the side rather than directly below, avoiding physical interference caused by the wires directly below the sample 3, thus eliminating the problem of unevenness on the sample back side caused by wire welding. This flat conductive layer design maintains good conductivity and thermal conductivity while preserving the horizontal flatness of the back side of the sample 3.

[0034] The electrode leads are isolated from each other by an insulating structure to prevent short circuits. The insulating structure includes an alumina insulating sheet 2 disposed between the Pt heating strip 1 and the sample 3, and an alumina tube sleeved over each electrode lead. Specifically, each Pt wire 5 is insulated by a single-hole alumina tube, and the Pt wires 5 are isolated from each other by the alumina tubes. The leads of the two working electrodes 62 and the reference electrode 61 on the front are separated by single-hole alumina tubes. A Pt wire 5 extends from the lateral edge of the Pt sheet (rigid conductive sheet 13) as the connecting wire of the counter electrode 14, and this Pt wire 5 is insulated by a single-hole alumina tube.

[0035] The in-situ cavity 9 is also connected to a cooling channel. The cooling channel includes a cooling water channel and a liquid nitrogen delivery pipe 8. When the Pt heating strip 1 heats the cavity, cooling water needs to be introduced for heat dissipation. Combined with the temperature sensor 4, the temperature inside the in-situ cavity 9 is precisely controlled at a set position. The liquid nitrogen delivery pipe 8 is used for cooling during low-temperature testing. The in-situ cavity 9 is also equipped with a gas inlet and outlet 7, reserved for experiments involving in-situ gas transmission.

[0036] The in-situ cavity 9 is equipped with a detachable hemispherical beryllium window. Made of beryllium metal, the beryllium window allows X-rays to pass through while simultaneously forming a closed cavity, creating an arched, sealed environment for locally uniform heating and cooling. The interior of the in-situ cavity 9 can be operated upon by opening the beryllium window, allowing for sample placement, etc.

[0037] In this embodiment, the spot size of the rotating target-focused Cu light source can be adjusted to a range of 0.1 mm to 2 mm. Combined with the digital XY precision movement of the multi-axis drive structure, in-situ X-ray diffraction tests and electrical performance measurements can be performed on different micro-regions on the surface of the same sample 3, achieving high-throughput in-situ analysis of micro-batteries or micro-electrodes. Furthermore, the system can also be configured with a rotating target-focused copper target light source to match the differentiated in-situ testing requirements of thin film interfaces and depth directions.

[0038] Example 2 like Figure 1 and Figure 2 As shown, this embodiment provides a high-resolution in-situ X-ray diffraction testing method based on multi-field coupling, using the system described in Embodiment 1, and includes the following steps: S100, Sample flattening and assembly steps First, the Cu light source at the target point of the high-resolution thin-film XRD equipment is increased to full power (50kV, 50mA).

[0039] Preparation of test sample 3: The test film 11 is deposited on the front side of substrate 10 to form an epitaxial film structure. La is pre-deposited on the back side of substrate 10. 0.6 Sr 0.4 CoO 3-δ The conductive layer serves as the bottom layer of the counter electrode, and the entire back side is coated with Pt paste and sintered at 700°C. Subsequently, a Pt sheet (rigid conductive sheet 13) with an area equivalent to the back side of the substrate 10 is bonded to the back side using silver paste and dried. Pt wires 5 are led out from the lateral edges of the Pt sheet (rigid conductive sheet 13) as connecting lines for the counter electrode 14.

[0040] The prepared sample 3 is placed on the sample holder in the in-situ cavity 9. An alumina insulating sheet 2 is placed between the Pt heating strip 1 and the sample 3 for electrical insulation. A temperature sensor 4 (thermocouple) is placed on the sample 3 to monitor the temperature.

[0041] A front electrode assembly is installed on the front side of the sample 3 under test: two working electrodes 62 and one reference electrode 61, all led out by Pt wires 5, with each Pt wire 5 insulated by a single-hole alumina tube. One working electrode 62 is used to apply an external field voltage, and the other working electrode 62 is used to test the resistance. The reference electrode 61 is used to provide a potential reference. The lead of the counter electrode 14 on the back side is led out from the Pt sheet (rigid conductive sheet 13) to the edge, and the Pt wire 5 is insulated by a single-hole alumina tube to prevent short circuits.

[0042] Connect the in-situ cavity 9 to electricity, cooling water and liquid nitrogen delivery pipes 8, and install a hemispherical beryllium window to form a sealed environment.

[0043] S200, Optical Path Alignment and Reference Locking Procedure Using the multi-axis drive structure beneath the high-resolution thin-film XRD equipment, a height scan (Z-scan) is performed on the sample 3. Specifically, the Z-axis is scanned from the lowest to the highest, and the curve of X-ray light intensity change from the highest intensity to the lowest intensity is recorded. The Z-height position corresponding to half of the full intensity is taken, and the upper surface of the sample 3 is raised to the center position parallel to the X-ray light path, ensuring that the sample is pushed to the center of the X-ray light path.

[0044] Subsequently, the sample 3 under test is horizontally tilted and scanned along the optical path, from the minimum luminous flux to the maximum luminous flux and then to the minimum luminous flux. The Theta angle at the point of maximum luminous flux is taken as the zero point of the optical path direction to complete the fine adjustment of the horizontal flatness. The sample 3 under test is then rocked to make its surface parallel to the X-ray beam.

[0045] The diffraction intensity of the sample 3 was optimized using a high-resolution thin-film XRD instrument. In the initial state without heating and without power, the substrate peak and the thin film peak were scanned sequentially and used as a reference for subsequent tests.

[0046] S300, Heating and Thermal Drift Calibration Procedure Cover the beryllium window, turn on the cooling water, and heat the sample 3 to the set temperature (e.g., 300℃ or 500℃) through the Pt heating strip (electric heating strip 1). After 5 minutes of constant temperature, the temperature inside the in-situ cavity 9 will stabilize.

[0047] After heating, the thermal expansion of the insulating fixtures (especially the alumina tubes fixing the sample) in the in-situ cavity 9 will cause a shift in the surface height of the sample 3, resulting in diffraction peak position drift or the inability to detect the target diffraction peak. In this case, a Z-scan height scan and horizontal tilt scan need to be performed again using a multi-axis drive structure to finely adjust the height and horizontal flatness. Specifically, after heating to 300℃, the two alumina tubes fixing the sample will expand due to heat and press down the sample surface. At this point, a new Z-scan needs to be performed to determine the new height, and then a rocking curve of the substrate peak needs to be plotted to calibrate the peak shift caused by thermal drift.

[0048] Peak position calibration was performed using the diffraction peaks of substrate 10 as a locked reference. A substrate peak that does not undergo a structural phase transition at this temperature was selected as the absolute reference scale. Since the substrate itself is structurally stable at this temperature and does not undergo a phase transition, the peak position of the substrate peak can serve as a reliable and invariant reference. By tracking the peak position shift of the substrate peaks, the error in sample surface height variation caused by thermal expansion of the insulating fixture was compensated, ensuring that the diffraction spectra of all samples did not drift, and guaranteeing the standardization and reproducibility of the test peak positions.

[0049] After repositioning the optical path center, the expected diffraction peak position and diffraction intensity of the sample 3 were located again using a high-resolution thin-film XRD device.

[0050] S400, Multi-field Coupled Dual-mode In-situ Probe Steps An external electrochemical workstation 6 applies a pulsed voltage to the sample 3, simultaneously acquiring its electrical performance parameters (resistance / conductivity). The pulsed voltage parameters are: pulse frequency 0.125Hz, duty cycle 50%, voltage amplitude range ±2V. The pulsed voltage period is 8s, the duration is 4s, and the circuit is disconnected after the pulsed voltage is turned off. When the pulsed voltage is applied, an external field voltage is applied through one working electrode 62 of the front electrode assembly, the other working electrode 62 measures the resistance, the reference electrode 61 provides a potential reference, and the counter electrode 14 on the back side forms a circuit. Voltages in different directions are controlled by the external electrochemical workstation 6 to reverse the direction of current flow to the positive and negative electrodes.

[0051] During the application of the pulsed voltage (i.e., the modulation phase of the pulsed electric field excitation), a first-mode detector (LynxEye detector) was used to perform rapid in-situ X-ray diffraction data acquisition on the sample 3 in PSD fixed scanning mode. The scanning parameters were set as follows: 2θ range 31° to 33°, step size 0.01° / step, and scan speed 1 s / step. Simultaneously, an external electrochemical workstation 6 performed real-time measurements of conductivity and resistance, collaboratively achieving macroscopic kinetic monitoring. Figure 6 The image shows the measurement results of pulsed resistance changes, reflecting the conductance state of the device after each pulse. For example... Figure 8 The image shows the results of pulsed conductivity changes. Using the above method, time-resolved structural gradient response and transient lattice changes were successfully captured, enabling dynamic monitoring and research. Figure 9 As shown, the instantaneous displacement of the thin film peak reflects the change in the lattice constant of the thin film, and thus reflects the change in the oxygen vacancy concentration in the thin film.

[0052] After the electrical response of sample 3 reaches a new equilibrium state, the standard for judging voltage stability is that the resistance no longer fluctuates (or switching after a fixed time, such as 5 minutes). The system then switches to the second-mode detector (scintillation counter) in continuous scanning mode for high-resolution X-ray diffraction data acquisition. The scanning parameters are set as follows: 2θ range 31° to 43°, step size 0.01° / step, and scan speed 0.1 s / step. This method allows for the acquisition of detailed information about the atomic-level structure under the new equilibrium state, including phase, cell parameters, crystallinity, and grain size, thus enabling phase transition monitoring of the structure. Figure 7 The image shows the fine-scan XRD patterns of the resistor under different voltage polarization states when the resistor is stable.

[0053] The dual-mode detection strategy described above can track the pulse resistance changes and instantaneous structural responses caused by pulsed electrical stimulation during voltage changes, using a LynxEye detector and short exposure time to achieve dynamic monitoring and research. Alternatively, after the voltage stabilizes and the oxygen vacancy concentration reaches a relative equilibrium, the crystal structure expands / contracts and reaches a relative equilibrium state, using a scintillation counter to monitor the average atomic-level structure of this new equilibrium state, thus comprehensively revealing the dynamic evolution mechanism of material structure under electric field stimulation.

[0054] S500, Micro-area High-Throughput Mapping Steps When different micro-regions of the sample 3 need to be analyzed, the rotating target-focused Cu light source is switched to focus mode, and the spot size is adjusted to 0.1 mm to 2 mm. After determining the sample height z by Z scan, the sample surface is moved sequentially to different microelectrode regions or micro-battery regions by controlling the XY two-dimensional digital translation stage of the sample holder. The test process of steps S200 to S400 is repeated for each region to obtain the in-situ X-ray diffraction pattern and electrical performance parameters of each micro-region, and to construct a spatial distribution mapping of structural characteristic parameters, thereby realizing high-throughput micro-region analysis.

[0055] Furthermore, the high-resolution thin film XRD equipment is equipped with a rotating target point cobalt target light source to match the differentiated in-situ testing requirements of the thin film interface and depth direction.

[0056] Example 3 Deposited on YSZ ((ZrO2)) 0.89 (Y2O3) 0.11 LSFO (La) on yttrium-stabilized zirconium oxide (YTO, 001 orientation) substrate 10 0.6 Sr 0.4 FeO 3-δ Taking lanthanum-strontium-iron oxide (110-oriented) thin film material as an example, the specific operation process of the above test method is explained in detail.

[0057] Sample preparation and mounting: An LSFO epitaxial film was deposited on a YSZ substrate 10 using pulsed laser deposition as the test film 11. La was pre-deposited on the back side of the substrate 10. 0.6 Sr 0.4 CoO 3-δ The conductive layer serves as the counter electrode layer. The entire back side is coated with Pt paste and dried at an appropriate temperature to form a conductive whole. A Pt sheet (rigid conductive sheet 13) with an area equivalent to the back side of the substrate 10 is bonded to the back side using silver paste. Pt wires 5 are led out from the lateral edges of the Pt sheet (rigid conductive sheet 13) as connecting lines for the counter electrode 14.

[0058] The CuKα X-ray source of the high-resolution thin-film XRD equipment is powered up to full power (50kV, 50mA). The sample to be tested (3) is placed on the sample holder inside the in-situ cavity (9). The alumina insulating sheet (2), sample 3, and thermocouple (temperature sensor 4) are installed sequentially. Finally, two working electrodes (62) and a reference electrode (61), both Pt wires, are installed on the front side of the sample 3. Each Pt wire (5) is covered with a single-hole alumina tube. The Pt wires (5) on the back side are also covered with single-hole alumina tubes for insulation. The in-situ cavity (9) is connected to electricity and cooling water, and a beryllium window is installed.

[0059] Optical path alignment: The sample to be tested (3) is aligned with the center of the goniometer using a multi-axis drive structure. Using the Z-scan height scanning function of the high-resolution thin-film XRD equipment, the height corresponding to half the intensity at full strength is measured, and the sample is pushed to the center of the X-ray optical path. By rocking the sample to be tested (3), its surface is aligned parallel to the X-ray beam, completing the fine adjustment of height and horizontal flatness.

[0060] Initial setup: Precisely locate the substrate peak and the thin film peak sequentially. Set appropriate scanning parameters on a high-resolution thin film XRD device: 2θ range 20° to 80°, step size 0.01° / step, scan speed 0.1s / step, and acquire X-ray diffraction patterns using a scintillation counter.

[0061] Heating Test: A beryllium window was placed over the entire in-situ cavity 9, and cooling water was circulated. Heating was initiated to 500°C and maintained for 5 minutes. After heating, the height and horizontal flatness of the sample 3 within the in-situ cavity 9 were finely adjusted. Peak position calibration was performed using the LSFO substrate peak as the locking reference standard to eliminate diffraction peak drift caused by thermal expansion. Repeated scanning was conducted to locate the expected diffraction peak positions (sequentially finding the substrate peak and the thin film peak) and optimize the diffraction intensity.

[0062] Power-on test: A pulsed voltage was applied through an external electrochemical workstation 6 with a pulse frequency of 0.125Hz, a duty cycle of 50%, and a voltage amplitude of ±2V.

[0063] During the application of the pulsed voltage, a LynxEye detector was used for rapid scanning in PSD fixed scan mode with the following parameters: 2θ range of 31° to 33°, step size of 0.01° / step, and scan speed of 1 s / step. Simultaneously, an external electrochemical workstation 6 was used to measure conductivity and resistance, thus achieving macroscopic kinetic monitoring.

[0064] After the voltage stabilizes (the resistance stops fluctuating, or it is fixed for 5 minutes before switching), switch to the scintillation counter to scan in continuous scanning mode. The scanning parameters are: 2θ range 31° to 43°, step size 0.01° / step, scanning speed 0.1s / step. Acquire XRD diffraction patterns to monitor the phase transition of the structure.

[0065] like Figure 7 As shown, under different voltage polarization states, the substrate peak of sample 3 remained stable (because the substrate did not undergo a phase transition within this temperature and voltage range), while the peak position of the thin film peak shifted significantly, reflecting the change in the lattice parameters of the LSFO thin film under the influence of the electric field. Figure 9 As shown, during the modulation of thin film conductivity under constant polarization voltage, the peak shift of the thin film can reflect the change in the lattice constant, and thus the change in the oxygen vacancy concentration in the thin film. That is, during oxidation, the thin film conductivity increases, while the peak shifts to the right, the lattice constant decreases, reflecting a decrease in oxygen vacancy concentration.

[0066] Through the above tests, the following information about the LSFO thin film under thermoelectric coupling in-situ environment can be obtained: (1) Microscopic atomic-level structural information of the material in equilibrium state, such as phase composition, cell parameters, crystallinity, and grain size; (2) The changing trend of the corresponding structure during temperature and voltage changes; (3) The correspondence between the instantaneous change of conductivity / resistance under pulse voltage stimulation and the transient response of thin film lattice is established to establish a dynamic mapping between macroscopic electrical properties and atomic-level microstructure. Specifically, it includes the stress response of the material structure to the applied electric field bias voltage and the intermediate state evolution of the material structure after reaching steady state, realizing the multidimensional synergistic characterization of macroscopic electrical properties and microscopic transient / steady-state structure.

[0067] (4) Gradient information of oxygen vacancy concentration change with electric field stimulation. The above method can be extended to the in-situ characterization of systems such as solar cell materials, organic photovoltaic materials, data storage and transmission chips.

[0068] The parts of this invention not described in detail are prior art, therefore they are not described in detail here.

[0069] It is understood that the term "a" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element can be one, while in another embodiment, the number of the element can be multiple, and the term "a" should not be understood as a limitation on the number.

[0070] Although this document uses a considerable amount of technical terminology, the possibility of using other terms is not excluded. These terms are used merely for the convenience of describing and explaining the essence of the invention; interpreting them as any additional limitation would contradict the spirit of the invention.

[0071] This invention is not limited to the preferred embodiments described above. Anyone can derive other products in various forms under the guidance of this invention. However, regardless of any changes made to their shape or structure, any technical solution that is the same as or similar to this invention falls within the protection scope of this invention.

Claims

1. A high-resolution in-situ X-ray diffraction system based on multi-field coupling, using a high-resolution thin-film XRD device, characterized in that, It also includes an in-situ cavity (9) disposed on the high-resolution thin film XRD, a sample holder disposed in the in-situ cavity (9), an electric heating strip (1) and a temperature sensor (4) disposed on the sample holder. An external electrochemical workstation (6) is located outside the in-situ cavity (9); The four-electrode system electrically connected to the external electrochemical workstation (6) includes two working electrodes (62), a reference electrode (61), and a counter electrode (14). Each electrode is insulated from the electric heating strip (1) and the in-situ cavity (9) by an insulating structure. A flat conductive layer is provided on the back of the sample to be tested (3), and the flat conductive layer is electrically connected to the counter electrode (14) to maintain the horizontal flatness of the back of the sample to be tested (3) while maintaining conductivity and heat conduction. The in-situ cavity (9) is also connected to a cooling channel that communicates with the in-situ cavity (9).

2. A high-resolution in-situ X-ray diffraction testing method based on multi-field coupling, using the system described in claim 1, characterized in that, Includes the following steps: Sample flattening assembly steps: A flat conductive layer is arranged on the back of the sample to be tested (3) to form a counter electrode (14), and a conductive wire bundle is led out from the edge area of ​​the flat conductive layer to maintain the overall flatness of the sample to be tested (3). A front electrode assembly containing a reference electrode (61) and a working electrode (62) is arranged on the front of the sample to be tested (3). Optical path alignment and reference locking steps: Adjust the surface of the sample to be tested (3) to the center of the optical path of the X-ray diffraction equipment, and scan to obtain the characteristic diffraction peaks of the substrate of the sample to be tested (3); Multi-field coupled dual-mode in-situ detection steps: A temperature field and a pulsed electric field excitation are simultaneously applied to the test sample (3). When the temperature field causes thermal expansion of the test environment, thermal drift calibration is performed with the characteristic diffraction peak of the substrate as an invariant reference to reposition the optical path center. During the modulation stage of the pulsed electric field excitation, the first mode detector of the X-ray diffraction equipment is used to continuously scan to obtain dynamic structural evolution information. After the electrical response of the test sample (3) reaches a steady state, the second mode detector is switched to scan to obtain steady-state high-resolution structural information.

3. The high-resolution in-situ X-ray diffraction testing method based on multi-field coupling according to claim 2, characterized in that, The front electrode assembly includes two working electrodes (62) and a reference electrode (61), which together with the counter electrode (14) located on the back side constitute a four-electrode system for in-situ electrical performance measurement. The flat conductive layer is constructed by using conductive paste or ceramic adhesive to bond a rigid conductive sheet (13) with the same back area as the test sample (3) to the back of the test sample (3); one end of the conductive wire bundle is connected to the side edge of the rigid conductive sheet (13), and the other end is led out and electrically connected to an external testing device to avoid physical interference caused by the conductive wire bundle directly below the test sample (3).

4. The high-resolution in-situ X-ray diffraction testing method according to claim 2, characterized in that, Thermal drift calibration is performed using the characteristic diffraction peaks of the substrate as a constant reference, specifically including: After the temperature field is heated and kept constant at a preset high temperature, the substrate peak that does not undergo a structural phase transition at the preset high temperature is selected as an absolute reference scale. Height scanning and horizontal tilt scanning are performed on the substrate peak. By tracking the peak position offset of the substrate peak, the error of sample surface height change caused by thermal expansion of the insulating fixture is compensated.

5. The high-resolution in-situ X-ray diffraction testing method according to claim 2, characterized in that, The first mode detector is an array detector that supports short-exposure fast imaging, and the second mode detector is a point detector that supports wide-angle high-resolution data collection; a pulse voltage in the low-frequency range is applied to the front electrode assembly and the counter electrode (14) to trigger the first mode detector to quickly track the lattice transient response of the thin film layer of the sample under test (3) at the moment of electric field stimulation.

6. The high-resolution in-situ X-ray diffraction testing method based on multi-field coupling according to claim 5, characterized in that, When scanning with the first mode detector, the scanning step size is 0.01° / step and the scanning speed is 1s / step; when switching to the second mode detector for scanning, the scanning step size is 0.01° / step and the scanning speed is 0.1s / step; the frequency of the pulse voltage is 0.125Hz, the duty cycle is 50%, and the voltage amplitude range is ±2V.

7. The high-resolution in-situ X-ray diffraction testing method based on multi-field coupling according to claim 2, characterized in that, The method further includes a micro-region high-throughput mapping step: The X-ray diffraction equipment uses a point-focus mode X-ray source. By controlling the XY two-dimensional translation stage to move the sample to be tested (3) in sequence, the in-situ X-ray diffraction patterns of different microelectrode regions on the surface of the sample to be tested (3) are obtained, and a spatial distribution mapping map of structural feature parameters is constructed.

8. The high-resolution in-situ X-ray diffraction testing method based on multi-field coupling according to claim 7, characterized in that, The X-ray diffraction equipment is equipped with a rotating target point copper target light source to match the differentiated in-situ testing requirements of thin film interfaces and depth directions.

9. The high-resolution in-situ X-ray diffraction system based on multi-field coupling according to claim 1, characterized in that, The insulation structure includes an insulating sheet (2) disposed between the electric heating strip (1) and the sample to be tested (3), and an alumina tube respectively sleeved outside each electrode lead; the electrode leads are isolated from each other by the alumina tube to prevent short circuit.

10. The high-resolution in-situ X-ray diffraction system based on multi-field coupling according to claim 1, characterized in that, The high-resolution thin-film XRD equipment has at least a rotating target focal Cu light source, a LynxEye detector and a scintillation counter; the in-situ cavity (9) is provided with a detachably connected hemispherical beryllium window, which allows X-rays to penetrate and form a closed cavity; the spot size of the rotating target focal Cu light source is adjustable, and in conjunction with the digital XYZ movement of the sample stage, it realizes in-situ high-throughput testing of multi-field coupling in micro-area.

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