Sample stages, thin film growth equipment and in-situ measurement systems

Abstract

The present invention discloses a sample stage, a thin film growth device and an in-situ measurement system. The in-situ sample stage comprises a heat-conducting sample holder, a first annular insulating pressing plate, a second annular insulating pressing plate and a fastener used to fix a substrate, and two sets of probe assemblies. In the probe assembly, a probe arm channel is provided at the upper part of a probe arm bracket and an elastic member is provided at the middle part. The probe arm passes through the probe arm channel and can move up and down and / or rotate horizontally; one end of the elastic member is connected to the probe arm bracket, and the other end of the elastic member is detachably connected to the probe arm; a metal wire passes through the probe arm and one end of the wire is connected to a metal probe and the other end is suitable for being connected to an electrochemical testing device; the elastic member is in a stretched state when connected to the probe arm, and the probe arm can make the metal probe contact with the collector under the action of the resilience of the elastic member. The sample stage can realize the coupling of the thin film growth device and the electrochemical testing device, and accurately, conveniently and efficiently test the high-temperature electrochemical properties of the thin film sample in situ.

Description

Technical Field

[0001] The invention belongs to the technical field of thin film preparation and characterization, and in particular relates to a sample stage, a thin film growth device and an in-situ measurement system. Background Art

[0002] Electrochemical impedance spectroscopy is an important method for studying electrode materials of solid oxide fuel cells. By applying different frequencies to the battery during the test, the impedance of the electrode and electrolyte can be obtained and the mechanism of the electrochemical reaction can be analyzed. However, after the thin film electrode sample is prepared and transferred to the test chamber for electrochemical testing, the sample will inevitably be exposed to H in the ambient atmosphere. 2 O、SO 2 and CO 2 Impurities such as Si and other impurities in the electrochemical test chamber will cause measurement errors and electrode degradation and polarization, seriously affecting the accuracy of electrochemical testing. In addition, before testing, the sample undergoes a temperature change process of cooling in the film growth chamber, and different cooling conditions may cause different changes in the electrode film structure, which in turn leads to unstable test results of different film samples, thus affecting the accuracy and reliability of the test analysis. Therefore, avoiding possible contamination during sample preparation and testing and ensuring the cleanliness of the sample during the test can ensure accurate research on the relationship between electrode material structure and performance. Summary of the invention

[0003] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, one object of the present invention is to provide a sample stage, a thin film growth device and an in-situ measurement system. The sample stage can be used to couple the thin film growth device and the electrochemical testing device. The sample stage is placed in the thin film growth device for preparing thin film electrode materials. After the preparation is completed, the electrochemical performance test of the sample can be achieved without taking out the sample, and the high-temperature electrochemical performance of the thin film sample can be accurately, conveniently and efficiently tested in-situ.

[0004] In one aspect of the present invention, the present invention provides an in-situ sample stage for thin film growth and electrochemical testing. According to an embodiment of the present invention, the in-situ sample stage comprises:

[0005] A thermally conductive sample holder, wherein a fixing hole is provided on the thermally conductive sample holder;

[0006] a first annular insulating pressing sheet, wherein the first annular insulating pressing sheet is provided with a first through hole corresponding to the fixing hole, the first annular insulating pressing sheet is suitable for being attached to the thermally conductive sample holder and supporting a substrate, and two collecting electrodes are provided on a side of the substrate away from the first annular insulating pressing sheet;

[0007] a second annular insulating pressing sheet, wherein the second annular insulating pressing sheet is provided with a second through hole corresponding to the first through hole, and the second annular insulating pressing sheet is suitable for covering the circumferential edge of the substrate and exposing the collector;

[0008] A fastener, the fastener is adapted to pass through the second through hole and the first through hole and be detachably connected to the fixing hole;

[0009] Two groups of probe assemblies, each group of the probe assemblies independently comprises a metal probe, a metal wire, a probe arm and a probe arm bracket: the probe arm bracket is arranged adjacent to the end of the thermally conductive sample stage, the probe arm bracket is provided with a probe arm channel at the top and an elastic member in the middle, the probe arm passes through the probe arm channel and can move up and down and / or rotate horizontally; one end of the elastic member is connected to the probe arm bracket, and the other end of the elastic member is detachably connected to the probe arm; the metal wire passes through the probe arm, and one end of the metal wire is connected to the metal probe, and the other end of the metal wire is suitable for being connected to an electrochemical testing device; the elastic member is in a stretched state when connected to the probe arm, and the probe arm can make the metal probe contact with the collector under the action of the rebound force of the elastic member.

[0010] The in-situ sample stage for thin film growth and electrochemical testing of the above-mentioned embodiment of the present invention has at least the following advantages: 1. The in-situ sample stage can be used for thin film growth equipment such as pulsed laser deposition equipment, magnetron sputtering equipment or evaporation coating equipment to prepare electrode thin film samples, and obtain electrode thin films with dense structure and clear interface; 2. During the thin film growth process, the substrate is clamped between the first annular insulating pressing plate and the second annular insulating pressing plate, the substrate is not in direct contact with the thermal conductive sample holder, and no electrical connection is formed between the substrate and the finally obtained electrode thin film sample and the insulating pressing plate and the metal sample stage, which can further ensure the accuracy of the measurement results; 3. The substrate can be fixed by fasteners in combination with the insulating pressing plate, and the probe bracket and elastic member in the probe assembly can be used to achieve contact between the probe and the substrate collector When testing the sample, the metal probe needs to contact the collector of the substrate to ensure that the metal probe can be electrically connected to the electrode film sample. At this time, before preparing the sample, the elastic member can be used to apply a certain pulling force to the probe arm to make the metal probe stop at the collector of the substrate. When the substrate or sample needs to be replaced, the elastic member can be separated from the probe arm so that the probe arm can move up and down and / or left and right around the probe arm channel for easy operation; 4. The in-situ sample stage can be disassembled or moved as a whole for easy operation; 5. After the electrode film is grown, there is no need to transfer the electrode film sample to the outside of the film growth equipment. The probe assembly can be directly electrically connected to the electrochemical testing device to realize the electrochemical test of the electrode film sample. This can not only eliminate the H in the external environment atmosphere during the transfer of the electrode film sample, but also eliminate the H in the external environment atmosphere during the transfer of the electrode film sample. 2 O、SO2 and CO 2 The influence of pollution sources such as sulfur dioxide and other pollutants on the surface reaction can achieve environmental cleanliness of oxide thin film samples during preparation, transfer and testing, realize ultra-clean electrochemical performance analysis, and improve the accuracy of the test; it can also directly test the prepared electrode thin film samples at high temperature, thereby avoiding the problem that when the film samples are transformed from high temperature to low temperature, the film samples of the same material will lead to inconsistent electrode film structures under different cooling conditions, thereby affecting the reliability and accuracy of the measurement and analysis results; on the other hand, it can save the cooling process and greatly improve the test efficiency; 6. During the use of the in-situ sample stage, the thermally conductive sample seat is directly attached to the heater of the thin film growth equipment. During the test, the test temperature of the thin film sample (such as the temperature required for impurity reaction) can be flexibly adjusted by adjusting the heater temperature of the thin film growth equipment, which can further help to improve the accuracy of the test analysis.

[0011] In addition, the in-situ sample stage for thin film growth and electrochemical testing according to the above embodiment of the present invention may also have the following additional technical features:

[0012] In some embodiments of the present invention, the in-situ sample stage for thin film growth and electrochemical testing further includes: a thermocouple, wherein the thermocouple penetrates the probe arm bracket and extends into the first annular insulating pressing sheet.

[0013] In some embodiments of the present invention, the fastener is connected to the fixing hole by threading, snapping or plugging.

[0014] In some embodiments of the present invention, the first annular insulating pressing plate is provided with a plurality of first through holes evenly arranged along its circumference, and the number of the second through holes is the same as that of the first through holes.

[0015] In some embodiments of the present invention, the probe arm channel is a third through hole passing through the probe arm bracket, and the aperture of the third through hole is larger than the outer diameter of the probe arm; or, the probe arm channel is a groove provided on the top of the probe arm bracket, and the groove accommodates and supports the probe arm.

[0016] In some embodiments of the present invention, the elastic member is a spring, one end of which is connected to the probe arm bracket via a fastening screw, and the other end is detachably connected to the probe arm, and the free length of the spring is no greater than the vertical distance between the fastening screw and the probe arm.

[0017] In some embodiments of the present invention, the thermally conductive sample holder is a metal sample holder, the first annular insulating pressing plate and the second annular insulating pressing plate are independently distributed as high-purity alumina pressing plates with a purity of not less than 99.8%, the probe arm is a high-purity alumina probe arm with a purity of not less than 99.8%, the metal probe is a platinum-iridium alloy probe with a purity of not less than 99.9%; and the metal wire is a platinum wire with a purity of not less than 99.9%.

[0018] In another aspect of the present invention, the present invention proposes a thin film growth device. According to an embodiment of the present invention, the thin film growth device includes the above-mentioned in-situ sample stage for thin film growth and electrochemical testing. Similar to the prior art, the use of the thin film growth device has at least the following advantages: 1. Electrode thin film samples with dense structure and clear interface can be produced; 2. The environmental cleanliness and test conditions during the thin film growth and testing process can be accurately controlled; 3. The coupling of the electrochemical testing system and the thin film growth device can be achieved through the in-situ sample stage for thin film growth and electrochemical testing. After the electrode film is grown, there is no need to transfer the electrode thin film sample to the outside of the thin film growth device. The probe assembly can be directly electrically connected to the electrochemical testing device to achieve electrochemical testing of the electrode thin film sample, thereby not only eliminating the H in the external environment atmosphere during the transfer of the electrode thin film sample, but also eliminating the H in the external environment atmosphere during the transfer of the electrode thin film sample. 2 O, SO 2 and CO 2 The influence of pollution sources such as oxide thin film on surface reaction can be reduced, and the environmental cleanliness of oxide thin film samples in the process of preparation, transfer and testing can be achieved, and ultra-clean electrochemical performance analysis can be achieved, so as to improve the accuracy of the test; the prepared electrode thin film samples can also be tested directly at high temperature, so as to avoid the problem that when the film samples are transformed from high temperature to low temperature, the film samples of the same material will lead to inconsistent electrode film structure under different cooling conditions, thereby affecting the reliability and accuracy of the measurement and analysis results; on the other hand, the cooling process can be omitted, greatly improving the test efficiency; 4. The in-situ sample stage can be moved as a whole, which is convenient for installation and disassembly; in addition, the elastic parts in the sample stage can be used to realize the contact and separation of the probe and the substrate collector, which is convenient for sample replacement and makes the metal probe and the electrode of the electrode film sample contact during the test.

[0019] In some embodiments of the present invention, the thin film growth equipment is a pulsed laser deposition equipment, a magnetron sputtering equipment or an evaporation coating equipment.

[0020] In another aspect of the present invention, the present invention proposes an in-situ measurement system. According to an embodiment of the present invention, the in-situ measurement system includes: the above-mentioned thin film growth equipment; and an electrochemical testing device, which is detachably connected to the in-situ sample stage for thin film growth and electrochemical testing. Compared with the prior art, the system can simultaneously realize the preparation and testing of electrode thin film samples, and during the test process, the electrode thin film samples do not need to be transferred outside the thin film growth equipment, which is conducive to ensuring the environmental cleanliness during the thin film growth and testing process and avoiding impurity contamination, and is also convenient for controlling the test conditions, and improving the test efficiency and the accuracy and reliability of the test analysis.

[0021] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0023] Figure 1 Schematic diagram of the structure of an in-situ sample stage for thin film growth and electrochemical testing according to an embodiment of the present invention.

[0024] Figure 2 It is a schematic structural diagram of an in-situ sample stage for thin film growth and electrochemical testing according to yet another embodiment of the present invention.

[0025] Figure 3 FIG. 4 is a top view of an in-situ sample stage for thin film growth and electrochemical testing according to an embodiment of the present invention.

[0026] Figure 4 It is a schematic structural diagram of a collector electrode on a substrate used in an in-situ sample stage for thin film growth and electrochemical testing according to an embodiment of the present invention.

[0027] Figure 5 It is a schematic structural diagram of a collector electrode on a substrate used in an in-situ sample stage for thin film growth and electrochemical testing according to yet another embodiment of the present invention. DETAILED DESCRIPTION

[0028] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.

[0029] In the description of the present invention, it should be understood that the terms "length", "thickness", "upper", "lower", "horizontal", "top", "bottom", "inner", "outer", "radial", "circumferential" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined. In the present invention, unless otherwise clearly specified and limited, the terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be fixed connection, detachable connection, or integrated; it can be mechanical connection or electrical connection; it can be directly connected or indirectly connected through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly specified. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances. In the present invention, unless otherwise clearly specified and limited, the first feature "above" or "below" the second feature can be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature "above", "above" and "above" the second feature can mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. The first feature "below", "below" and "below" the second feature can be that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.

[0030] In one aspect of the present invention, the present invention provides an in-situ sample stage for thin film growth and electrochemical testing. Figure 1It is understood that the in-situ sample stage includes: a thermally conductive sample holder 10, a first annular insulating pressing sheet 20, a second annular insulating pressing sheet 30, a fastener 40 and two sets of probe assemblies 50. Among them, the in-situ sample stage can be used in pulsed laser deposition, magnetron sputtering, evaporation coating and other equipment to prepare thin film samples, and the probe assembly can be directly electrically connected to the electrochemical testing device to realize the test of the prepared thin film sample, that is, after the thin film electrode material is prepared in the thin film growth equipment, the high-temperature electrochemical performance test is directly carried out, avoiding the pollution of the electrode material by the external environment after the sample is taken out from the preparation chamber, which causes the degradation of the electrode material, and improves the reliability and efficiency of the test; at the same time, during use, the two metal probes in the probe assembly contact the two high-precision collectors on the surface of the thin film sample, and transmit the test signal to the electrochemical testing device through the metal wire, which improves the accuracy of the test; it should be noted that the thin film sample (grown on the substrate) is pressed by the upper and lower annular insulating pressing sheets and placed on the thermally conductive sample holder, and the thermally conductive sample holder is placed on the heater of the thin film growth equipment. Therefore, it is possible to prepare electrode film samples in an ultra-clean environment and to conduct precise in-situ electrochemical performance testing on the prepared electrode film samples.

[0031] Reference below Figures 1 to 5 The in-situ sample stage for thin film growth and electrochemical testing according to the above embodiment of the present invention is described in detail.

[0032] According to an embodiment of the present invention, Figures 1 to 3 It is understood that a fixing hole 11 is provided on the thermal conductive sample holder 10; a first through hole 21 corresponding to the fixing hole 11 is provided on the first annular insulating pressing plate 20, and the first annular insulating pressing plate 20 is suitable for being attached to the thermal conductive sample holder 10 and supporting a substrate 60 (when preparing an electrode film, an electrode film sample is grown on the substrate 60), and two collecting electrodes 61 are provided on a side of the substrate 60 away from the first annular insulating pressing plate 20; a second through hole 31 corresponding to the first through hole 21 is provided on the second annular insulating pressing plate 30, and the second annular insulating pressing plate 30 is suitable for covering the circumferential edge of the substrate 60 and exposing the collecting electrode 61; the fastener 40 is suitable for penetrating the second through hole 31 and the first through hole 21 and being detachably connected to the fixing hole 11. During the thin film preparation process, the thermally conductive sample holder 10 can be directly in contact with the heater 80 of the thin film growth equipment to provide a high-temperature environment for thin film growth and control the temperature conditions in subsequent thin film sample testing; in addition, the first annular insulating pressing plate and the second annular insulating pressing plate can be used in combination to clamp a substrate with two collecting electrodes between the two (the substrate does not contact the thermally conductive sample holder), and the collector exposed substrate is kept away from one side of the sample holder; in addition, the first annular insulating pressing plate and the second annular insulating pressing plate can be fixed to the sample holder by using fasteners, thereby fixing the substrate and the thin film sample subsequently grown on the substrate.

[0033] According to some specific embodiments of the present invention, the thermally conductive sample holder 10 can be a metal sample holder. The inventors have found that metal has high thermal conductivity and fast thermal conductivity. The use of a metal sample holder can not only improve the preparation efficiency of the thin film sample, but also shorten the temperature adjustment time. Further, the thermally conductive sample holder 10 can also be a stainless steel metal sample holder or a high-purity metal (purity not less than 99.5%) sample holder. The inventors have found that metal samples may rust due to environmental impurities during use, and impurities in the metal sample may also precipitate under high temperature conditions, both of which will cause contamination of the sample holder and further contamination of the thin film sample to be tested. In the present invention, by selecting a stainless steel metal sample holder or a high-purity metal sample holder, the thermal conductivity efficiency can be guaranteed and the cleanliness in the chamber of the thin film growth equipment can be further improved. Preferably, the thermally conductive sample holder 10 can be a pure copper holder with a purity not less than 99.7% or 99.8%, so that the thermally conductive sample holder has both good thermal conductivity and cleanliness.

[0034] According to some further specific embodiments of the present invention, the connection mode between the fastener 40 and the fixing hole 11 is not particularly limited, and those skilled in the art can select it according to actual needs. For example, the fastener 40 and the fixing hole 11 can be connected by thread, by clamping or by plugging, etc. Further, in order to further improve the fixing effect of the annular insulating pressing piece and the substrate, the gap between the first through hole and the second through hole and the fastener can be made as small as possible. Preferably, the second through hole 31 and the first through hole 21 can be independently connected to the fastener 40 by thread, thereby further ensuring the fixing effect. In addition, it should be noted that the material of the fastener 40 is also not particularly limited, and those skilled in the art can select it according to actual needs, as long as it can meet the fixing of the insulating pressing piece and the substrate without introducing impurities. For example, the material of the fastener 40 can be a metal material (preferably stainless steel) or an insulating material (such as ceramic, preferably high-purity alumina ceramic, etc.), thereby further improving the cleanliness of the film growth and test environment under the premise of ensuring the fixing effect. In addition, according to a specific example of the present application, the fastener 40 can be a bolt with a nut; according to another specific example of the present application, when the fastener 40 is made of metal, due to the substrate, there is a certain gap between the first annular insulating pressing plate and the second annular insulating pressing plate. In order to avoid impurities brought by the metal fastener exposed between the two insulating pressing plates, an insulating sleeve can be further provided on the fastener located between the first annular insulating pressing plate and the second annular insulating pressing plate, preferably a high-purity alumina sleeve with a purity of not less than 99.8%, thereby further ensuring the cleanliness of the film growth and testing environment.

[0035] According to some further specific embodiments of the present invention, the material and shape of the first annular insulating pressing sheet 20 and the second annular insulating pressing sheet 30 are not particularly limited, and those skilled in the art can flexibly select them according to actual needs. For example, the first annular insulating pressing sheet 20 and the second annular insulating pressing sheet 30 can be independently rectangular rings, circular rings or elliptical rings, etc.; the first annular insulating pressing sheet 20 and the second annular insulating pressing sheet 30 can be independently high-purity ceramic pressing sheets, preferably high-purity alumina pressing sheets with a purity of not less than 99.8%, thereby further ensuring the cleanliness of the film growth and testing environment, and ensuring the insulation effect, strength and fixing effect of the insulating pressing sheet on the electrode film sample. More preferably, the first annular insulating pressing sheet 20 and the second annular insulating pressing sheet 30 can be completely fitted together, thereby achieving effective fixing of the film sample even if the film sample is very thin.

[0036] According to some other specific embodiments of the present invention, the number of the fixing hole 11, the first through hole 21 and the second through hole 31 is not particularly limited, and the skilled person in the art can select according to actual needs, and preferably all three include a plurality, thereby further ensuring the fixing effect of the insulating pressing plate and the substrate. More preferably, the first annular insulating pressing plate 20 can be provided with a plurality of first through holes 21 evenly arranged along its circumference, the number of the second through holes 31 is the same as the first through holes 21, and the number of the second through holes 31 is also the same as the number of the fixing holes 11, thereby more conducive to achieving the fixing effect of the insulating pressing plate and the substrate.

[0037] According to the embodiment of the present invention, it should be noted that in the present invention, when preparing the electrode film sample, the structure of the two collectors on the substrate is not particularly limited, and those skilled in the art can select according to actual needs. For example, the collector can be a rectangular (such as Figure 4 as shown) or interdigitated (as Figure 5 As shown), it should be noted that the two collectors with the interdigitated structure are not in contact with each other.

[0038] According to an embodiment of the present invention, Figures 1 to 3It is understood that each probe assembly 50 independently comprises a metal probe 51, a metal wire 52, a probe arm 53 and a probe arm bracket 54: the probe arm bracket 54 is arranged adjacent to the end of the thermally conductive sample holder 10, a probe arm channel 55 is arranged at the upper part of the probe arm bracket 54 and an elastic member 56 is arranged at the middle part, the probe arm 53 passes through the probe arm channel 55 and can move up and down and / or rotate horizontally; one end of the elastic member 56 is connected to the probe arm bracket 54, and the other end of the elastic member 56 is detachably connected to the probe arm 53; the metal wire 52 passes through the probe arm 53 and one end thereof is connected to the metal probe 51, and the other end is suitable for connecting to the electrochemical testing device; the elastic member 56 is in a stretched state when connected to the probe arm 53, and the probe arm 53 can make the metal probe 51 contact with the collector 61 under the action of the rebound force of the elastic member 56. Among them, when testing the thin film sample, the two metal probes can be made to contact with the two collectors on the surface of the thin film sample, and the test signal is transmitted to the electrochemical testing instrument through the metal wire. Specifically, the probe holder and elastic member in the probe assembly can be used to achieve contact and separation between the probe and the substrate collector. When testing the sample, the metal probe needs to contact the substrate collector to ensure that the metal probe can be electrically connected to the electrode film sample. At this time, before preparing the sample, the elastic member can be used to apply a certain pulling force to the probe arm so that the metal probe stops at the substrate collector. When the substrate or sample needs to be replaced, the elastic member can be separated from the probe arm so that the probe arm can move up and down and / or left and right around the probe arm channel for easy operation.

[0039] According to a specific embodiment of the present invention, the specific structure of the probe arm channel 55 in the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. For example, refer to Figure 1 Or 2 understands that the probe arm channel 55 can be a third through hole that passes through the probe arm bracket 54, and the aperture of the third through hole can be larger than the outer diameter of the probe arm 53, thereby allowing the probe arm to move up and down and left and right around the probe arm channel, thereby enabling the metal probe to contact or separate with the collector. For another example, the probe arm channel 55 can also be a groove provided at the top of the probe arm bracket 54, which can accommodate and support the probe arm, wherein the groove setting can not only fix the probe arm in the groove under the pulling force of the elastic member, but also enable the probe arm to have a larger movable space when the elastic member is not connected to the probe arm, thereby being more conducive to the replacement of the substrate or sample.

[0040] According to another specific embodiment of the present invention, the type of the elastic member 56 in the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. For example, the elastic member 56 can be a spring. Specifically, one end of the spring can be connected to the probe arm bracket 54 by a fastening screw 57, and the other end can be detachably connected to the probe arm 53 (can be directly hung and connected or connected through an intermediate connecting member). In order to ensure that the elastic member 56 is in a stretched state when connected to the probe arm 53, the free length of the spring can also be made not greater than the vertical distance between the fastening screw 57 and the probe arm 53 (can be understood as the minimum vertical distance between the two), thereby more flexibly controlling the connection or separation of the elastic member and the probe arm.

[0041] According to another specific embodiment of the present invention, the metal probe 51, the metal wire 52, the probe arm 53 and the probe arm bracket 54 can be independently made of high-purity materials, for example, the metal probe 51 and the metal wire 52 can be independently made of high-purity metal or alloy, the probe arm 53 and the probe arm bracket 54 can be independently made of high-purity ceramics, and the probe arm bracket 54 can also be made of high-purity metal or alloy, thereby further improving the cleanliness of the film sample preparation and test environment, and eliminating the contamination of the electrode film sample to be tested by impurity elements. For another example, the probe arm can be a high-purity alumina probe arm with a purity of not less than 99.8%, the metal probe can be a platinum-iridium alloy probe with a purity of not less than 99.9%; the metal wire can be a platinum wire with a purity of not less than 99.9%; the probe arm bracket 54 can be a pure copper bracket with a purity of not less than 99.7% or 99.8%, thereby further ensuring the cleanliness of the film sample preparation and test environment.

[0042] According to another specific embodiment of the present invention, referring to Figure 2It is understood that the in-situ sample stage for thin film growth and electrochemical testing may also include: a thermocouple 70, wherein the thermocouple 70 may penetrate the probe arm bracket 54 and extend into the first annular insulating pressing sheet 20, thereby using the thermocouple to perform real-time temperature measurement of the electrode thin film sample. The inventors have discovered that when the temperature measuring end of the thermocouple is in direct contact with the sample to be tested for temperature measurement, it will affect the uniformity of the sample temperature, thereby affecting the accuracy of the test. In the chamber of the thin film growth equipment, the temperature of the first annular insulating pressing piece is very close to the temperature of the thin film sample. The temperature of the first annular insulating pressing piece can be measured by a thermocouple to indirectly obtain the temperature of the thin film sample. In addition, there is a one-to-one correspondence between the conductivity and temperature of the thin film sample. The conductivity of the thin film sample can be obtained based on the impedance spectrum. During the test, the thin film sample temperature (i.e., the temperature of the first annular insulating pressing piece) measured by the thermocouple (indirectly) can be calibrated in advance with the actual temperature of the thin film sample to obtain the difference between the thin film sample temperature measured by the thermocouple (indirectly) and the actual temperature of the thin film sample, and the correspondence between the thin film sample temperature measured by the thermocouple (indirectly) and the measured sample impedance spectrum can be obtained. The one-to-one correspondence of the conductivity of the film sample is obtained by using a thermocouple 70 to indirectly obtain the temperature of the film sample by contacting the first annular insulating pressing piece 20 in the present invention. On the one hand, the problem of affecting the uniformity of the sample temperature due to the direct contact of the thermocouple temperature measuring end with the film sample can be avoided. The approximate temperature of the film sample can be indirectly obtained by measuring the temperature near the film sample, or the precise temperature of the film sample can be obtained by further combining the difference between the temperature of the first annular insulating pressing piece near the film sample and the actual temperature of the film sample; the one-to-one correspondence between the conductivity of the sample to be tested measured by an impedance meter and the temperature of the first annular insulating pressing piece near the film sample measured by the thermocouple can also be obtained in advance by calibration. The temperature corresponding to the conductivity of the film sample and the temperature displayed by the thermocouple can be used for mutual calibration, thereby further improving the accuracy of the test results. Among them, the type of thermocouple 70 in the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. For example, it can be an S-type thermocouple, in which the end of the thermocouple 70 away from the first annular insulating pressing piece 20 is connected to an external temperature measuring device through a terminal, etc., so that the temperature signal can be transmitted in time according to actual needs.

[0043] In summary, the in-situ sample stage for thin film growth and electrochemical testing in the above-mentioned embodiment of the present invention has at least the following advantages: 1. The in-situ sample stage can be used for thin film growth equipment such as pulsed laser deposition equipment, magnetron sputtering equipment or evaporation coating equipment to prepare electrode thin film samples, so as to obtain electrode thin films with dense structure and clear interface; 2. During the thin film growth process, the substrate is clamped between the first annular insulating pressing plate and the second annular insulating pressing plate, the substrate is not in direct contact with the thermal conductive sample holder, and no electrical connection is formed between the substrate and the finally obtained electrode thin film sample and the insulating pressing plate and the metal sample stage, which can further ensure the accuracy of the measurement results; 3. The substrate can be fixed by fasteners in combination with the insulating pressing plate, and the probe bracket and elastic member in the probe assembly can be used to realize the connection between the probe and the substrate collector. Contact and separation. When testing the sample, the metal probe needs to contact the collector of the substrate to ensure that the metal probe can be electrically connected to the electrode film sample. At this time, before preparing the sample, the elastic member can be used to apply a certain pulling force to the probe arm to make the metal probe stop at the collector of the substrate. When the substrate or sample needs to be replaced, the elastic member can be separated from the probe arm so that the probe arm can move up and down and / or left and right around the probe arm channel for easy operation; 4. The in-situ sample stage can be disassembled or moved as a whole for easy operation; 5. After the electrode film is grown, there is no need to transfer the electrode film sample to the outside of the film growth equipment. The probe assembly can be directly electrically connected to the electrochemical testing device to realize the electrochemical test of the electrode film sample. This can not only eliminate the H in the external environment atmosphere during the transfer of the electrode film sample, but also eliminate the H in the external environment atmosphere during the transfer of the electrode film sample. 2 O、SO 2 and CO 2 The influence of pollution sources such as sulfur dioxide and other pollutants on the surface reaction can achieve environmental cleanliness of oxide thin film samples during preparation, transfer and testing, realize ultra-clean electrochemical performance analysis, and improve the accuracy of the test; it can also directly test the prepared electrode thin film samples at high temperature, thereby avoiding the problem that when the film samples are transformed from high temperature to low temperature, the film samples of the same material will lead to inconsistent electrode film structures under different cooling conditions, thereby affecting the reliability and accuracy of the measurement and analysis results; on the other hand, it can save the cooling process and greatly improve the test efficiency; 6. During the use of the in-situ sample stage, the thermally conductive sample seat is directly attached to the heater of the thin film growth equipment. During the test, the test temperature of the thin film sample (such as the temperature required for impurity reaction) can be flexibly adjusted by adjusting the heater temperature of the thin film growth equipment, which can further help to improve the accuracy of the test analysis.

[0044] In another aspect of the present invention, the present invention proposes a thin film growth device. According to an embodiment of the present invention, the thin film growth device includes the above-mentioned in-situ sample stage for thin film growth and electrochemical testing. Similar to the prior art, the use of the thin film growth device has at least the following advantages: 1. Electrode thin film samples with dense structure and clear interface can be produced; 2. The environmental cleanliness and test conditions during the thin film growth and testing process can be accurately controlled; 3. The coupling of the electrochemical testing system and the thin film growth device can be achieved through the in-situ sample stage for thin film growth and electrochemical testing. After the electrode film is grown, there is no need to transfer the electrode thin film sample to the outside of the thin film growth device. The probe assembly can be directly electrically connected to the electrochemical testing device to achieve electrochemical testing of the electrode thin film sample, thereby not only eliminating the H in the external environment atmosphere during the transfer of the electrode thin film sample, but also eliminating the H in the external environment atmosphere during the transfer of the electrode thin film sample. 2 O、SO 2 and CO 2 The influence of pollution sources such as the above on the surface reaction can achieve the environmental cleanliness of the oxide film sample during the preparation, transfer and testing process, achieve ultra-clean electrochemical performance analysis, and improve the accuracy of the test; the prepared electrode film sample can also be tested directly at high temperature, so that on the one hand, it can avoid the problem that when the film sample changes from high temperature to low temperature, the film sample of the same material causes the electrode film structure to be inconsistent under different cooling conditions, thereby affecting the reliability and accuracy of the measurement and analysis results. On the other hand, it can save the cooling process and greatly improve the test efficiency; 4. The in-situ sample stage can be moved as a whole, which is convenient for installation and disassembly; in addition, the elastic parts in the sample stage can be used to realize the contact and separation of the probe and the substrate collector, which is convenient for sample replacement and the contact of the metal probe and the electrode film sample electrode during the test. It should be noted that the type of thin film growth equipment in the present invention is not particularly limited, and those skilled in the art can choose according to actual needs. For example, the thin film growth equipment can be a pulsed laser deposition equipment, a magnetron sputtering equipment or an evaporation coating equipment. In addition, it should be noted that the features and effects described for the in-situ sample stage for thin film growth and electrochemical testing are also applicable to the thin film growth equipment, and will not be repeated here.

[0045] In yet another aspect of the present invention, the present invention proposes an in-situ measurement system. According to an embodiment of the present invention, the in-situ measurement system includes: the above-mentioned thin film growth equipment; and an electrochemical testing device, which is detachably connected to an in-situ sample stage for thin film growth and electrochemical testing. Compared with the prior art, the system can simultaneously realize the preparation and testing of electrode thin film samples, and during the test process, the electrode thin film samples do not need to be transferred outside the thin film growth equipment, which is conducive to ensuring the environmental cleanliness during the thin film growth and testing process and avoiding impurity contamination, and is also convenient for controlling the test conditions, and improving the test efficiency and the accuracy and reliability of the test analysis. It should be noted that the features and effects described for the above-mentioned thin film growth equipment are also applicable to the in-situ measurement system, and will not be repeated here.

[0046] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used that do not specify the manufacturer are all conventional products that can be obtained commercially.

[0047] Example 1

[0048] An in-situ sample stage for thin film growth and electrochemical testing, which is used to perform high-temperature electrochemical performance testing in-situ after the thin film electrode material is prepared. Figure 2 The specific test operation steps are as follows: a substrate 60 with a collector 61 is placed on a first annular high-purity alumina pressed sheet 20, such as Figure 4 As shown, the shape of the collector 61 is rectangular, the second annular high-purity alumina press piece 30 is placed on the substrate 60, and the first annular high-purity alumina press piece 20, the substrate 60 and the second annular high-purity alumina press piece 30 are fixed on the stainless steel sample holder 10 with four fastening screws 40, the S-type thermocouple 70 passes through the probe arm bracket 54 and is inserted into the first annular high-purity alumina press piece 20, the high-purity Pt wire 52 passes through the high-purity alumina probe arm 53 and is connected to the high-purity platinum-iridium probe 51, the high-purity alumina probe arm 53 passes through the probe arm bracket 54, the high-purity platinum-iridium probe 51 is lightly pressed on the collector 61, one end of the tension spring 56 is hooked on the tension screw 57, and the other end is hooked on the probe arm 53, the in-situ sample stage is placed on the heating stage 80, the film growth process parameters are adjusted, and the film growth is carried out. After the film growth is completed, the high-purity reaction gas is introduced, the high-temperature electrochemical test parameters are adjusted, and the in-situ high-temperature electrochemical test is carried out.

[0049] Example 2

[0050] An in-situ sample stage for thin film growth and electrochemical testing, which is used to perform high-temperature electrochemical performance testing in-situ after the thin film electrode material is prepared. Figure 2 The specific test operation steps are as follows: a substrate 60 with a collector 61 is placed on a first annular high-purity alumina pressed sheet 20, such as Figure 5 As shown, the shape of the collector 61 is a forked finger shape, the second annular high-purity alumina press piece 30 is placed on the substrate 60, and the first annular high-purity alumina press piece 20, the substrate 60 and the second annular high-purity alumina press piece 30 are fixed on the stainless steel sample holder 10 with four fastening screws 40, the S-type thermocouple 70 passes through the probe arm bracket 54 and is inserted into the first annular high-purity alumina press piece 20, the high-purity Pt wire 52 passes through the high-purity alumina probe arm 53 and is connected to the high-purity platinum-iridium probe 51, the high-purity alumina probe arm 53 passes through the probe arm bracket 54, the high-purity platinum-iridium probe 51 is lightly pressed on the collector 61, one end of the tension spring 56 is hooked on the tension screw 57, and the other end is hooked on the probe arm 53, the in-situ sample stage is placed on the heating stage 80, the film growth process parameters are adjusted, and the film growth is carried out. After the film growth is completed, the high-purity reaction gas is introduced, the high-temperature electrochemical test parameters are adjusted, and the in-situ high-temperature electrochemical test is carried out.

[0051] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0052] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. An in-situ sample stage for thin film growth and electrochemical testing, characterized in that: include: A thermally conductive sample holder, wherein a fixing hole is provided on the thermally conductive sample holder; a first annular insulating pressing sheet, wherein the first annular insulating pressing sheet is provided with a first through hole corresponding to the fixing hole, the first annular insulating pressing sheet is suitable for being attached to the thermally conductive sample holder and supporting a substrate, and two collecting electrodes are provided on a side of the substrate away from the first annular insulating pressing sheet; a second annular insulating pressing sheet, wherein the second annular insulating pressing sheet is provided with a second through hole corresponding to the first through hole, and the second annular insulating pressing sheet is suitable for covering the circumferential edge of the substrate and exposing the collector; A fastener, the fastener is adapted to pass through the second through hole and the first through hole and be detachably connected to the fixing hole; Two groups of probe assemblies, each group of the probe assemblies independently comprises a metal probe, a metal wire, a probe arm and a probe arm bracket: the probe arm bracket is arranged adjacent to the end of the thermally conductive sample holder, the upper part of the probe arm bracket is provided with a probe arm channel and the middle part is provided with an elastic member, the probe arm passes through the probe arm channel and can move up and down and / or rotate horizontally; one end of the elastic member is connected to the probe arm bracket, and the other end of the elastic member is detachably connected to the probe arm; the metal wire passes through the probe arm, and one end of the metal wire is connected to the metal probe, and the other end of the metal wire is suitable for being connected to an electrochemical testing device; the elastic member is in a stretched state when connected to the probe arm, and the probe arm can make the metal probe contact with the collector under the action of the rebound force of the elastic member; Also included: a thermocouple, the thermocouple passing through the probe arm bracket and extending into the first annular insulating pressing sheet; The fastener is connected to the fixing hole by thread, by snapping or by plugging.

2. The in-situ sample stage for thin film growth and electrochemical testing according to claim 1, characterized in that: The first annular insulating pressing plate is provided with a plurality of first through holes evenly arranged along its circumference, and the number of the second through holes is the same as that of the first through holes.

3. The in-situ sample stage for thin film growth and electrochemical testing according to claim 1, characterized in that: The probe arm channel is a third through hole penetrating the probe arm bracket, and the aperture of the third through hole is larger than the outer diameter of the probe arm; or, the probe arm channel is a groove arranged on the top of the probe arm bracket, and the groove accommodates and supports the probe arm.

4. The in-situ sample stage for thin film growth and electrochemical testing according to claim 1, characterized in that: The elastic member is a spring, one end of which is connected to the probe arm bracket via a fastening screw, and the other end is detachably connected to the probe arm. The free length of the spring is not greater than the vertical distance between the fastening screw and the probe arm.

5. The in-situ sample stage for thin film growth and electrochemical testing according to claim 1, characterized in that: The thermally conductive sample seat is a metal sample seat, the first annular insulating pressing plate and the second annular insulating pressing plate are independently distributed high-purity alumina pressing plates with a purity of not less than 99.8%, the probe arm is a high-purity alumina probe arm with a purity of not less than 99.8%, the metal probe is a platinum-iridium alloy probe with a purity of not less than 99.9%; the metal wire is a platinum wire with a purity of not less than 99.9%.

6. A thin film growth device, characterized in that: include: An in-situ sample stage for thin film growth and electrochemical testing according to any one of claims 1 to 5.

7. The thin film growth device according to claim 6, characterized in that: The thin film growth equipment is a pulse laser deposition equipment, a magnetron sputtering equipment or an evaporation coating equipment.

8. An in-situ measurement system, characterized in that: include: The thin film growing device according to claim 6 or 7; as well as An electrochemical testing device is detachably connected to the in-situ sample stage for thin film growth and electrochemical testing.

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