CN115201307B - Environmental PLD growth and electrochemical performance test system, method and application - Google Patents

Environmental PLD growth and electrochemical performance test system, method and application Download PDF

Info

Publication number
CN115201307B
CN115201307B CN202210651353.2A CN202210651353A CN115201307B CN 115201307 B CN115201307 B CN 115201307B CN 202210651353 A CN202210651353 A CN 202210651353A CN 115201307 B CN115201307 B CN 115201307B
Authority
CN
China
Prior art keywords
electrode
target
shielding box
gas
laser deposition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210651353.2A
Other languages
Chinese (zh)
Other versions
CN115201307A (en
Inventor
陈迪
赵云
许建兵
苏虹阳
刘鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN202210651353.2A priority Critical patent/CN115201307B/en
Publication of CN115201307A publication Critical patent/CN115201307A/en
Application granted granted Critical
Publication of CN115201307B publication Critical patent/CN115201307B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses an environmental PLD growth and electrochemical performance test system, method and application. The system comprises: the device comprises a pulse laser deposition chamber, a target shielding box, a laser emission device, an electrochemical workstation, a reflection high-energy electron diffractometer, a screen and a CCD camera which are matched for use, a vacuum glove box and vacuumizing equipment, wherein a sample holder is driven by a motor to rotate clockwise or anticlockwise in the vertical direction, the target shielding box can move periodically, an eccentric through hole is formed in the top wall of the target shielding box, a plurality of sub-shielding areas which are circumferentially arranged along the target shielding box are arranged in the top wall of the target shielding box, and the sub-shielding areas are not communicated with each other and can rotate relative to the top wall of the target shielding box. The system can obtain the electrochemical performance of the electrode material in an ultra-clean environment, eliminate the pollution of gas phase impurities in the process of transferring samples before the sample test, simultaneously can introduce different kinds of gases into the system, regulate the humidity of the gases, study the influence of the gases on the electrode material, and improve the accuracy of the test.

Description

Environmental PLD growth and electrochemical performance test system, method and application
Technical Field
The invention belongs to the technical field of film preparation and characterization, and particularly relates to an environmental PLD growth and electrochemical performance test system, method and application.
Background
One of the major challenges in developing a clean, environmentally friendly Solid Oxide Fuel Cell (SOFC) is performance degradation at high temperatures. Cathode of cell and gas phase impurity (H) 2 O、CO 2 And SO 2 ) The reaction of (2) results in a significant decrease in the oxygen exchange kinetics of the electrode, and therefore, it is important to investigate the effect of gas phase impurities on the composition and performance of the cathode material.
However, most of the current researches adopt porous composite electrode structures, the surface morphology of the electrode cannot be precisely defined, and various interfaces exist, such as a gas-electrode interface, a gas-electrolyte interface, an electrode-electrolyte interface, and the like. In the case of mixing various interfaces, the electrochemical reaction interface cannot be clarified, and it is difficult to accurately confirm the reaction details of the gas-phase impurities and the electrode interfaceThe method comprises the steps of carrying out a first treatment on the surface of the And, during the transfer of the sample to the test chamber after preparation, it is inevitably exposed to H in the ambient atmosphere 2 O、SO 2 And CO 2 Impurities are removed, and the precision and accuracy of sample testing are affected; moreover, the counter electrode of the sample is mostly noble metal slurry, and volatilizes pollutants when heated at high temperature, and meanwhile, the electrochemical test furnace is polluted by impurities such as Si and the like. All the reasons can influence the precision and accuracy of the test, and the influence of gas-phase impurities on the components and the performance of the cathode material cannot be accurately studied. How to directly research the influence of specific environmental atmosphere on the material composition and performance of a sample on the premise of not being polluted by impurity gas in the external environment is an important problem to be solved urgently. In addition, the film sample is usually obtained by manually rotating the sample holder to find the optimal observation angle during the growth process, and the problems of inconvenient operation and difficulty in obtaining the optimal observation angle are also encountered.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, one purpose of the invention is to provide an environmental PLD growth and electrochemical performance test system, method and application, after the system is adopted to prepare the oxide film electrode, the electrochemical performance of the electrode material can be obtained under ultra-clean environment, the pollution of gas phase impurities in the process of transferring the sample before the sample test is eliminated, meanwhile, different kinds of gases can be introduced into the system, the humidity of the gases is regulated, the influence of the gases on the electrode material is researched, and the test accuracy is improved.
In one aspect, the invention provides an environmental PLD growth and electrochemical performance testing system. According to an embodiment of the invention, the system comprises:
the pulse laser deposition device comprises a pulse laser deposition chamber, wherein a sample holder is arranged in the upper part of the pulse laser deposition chamber, a connecting rod is arranged on the upper part of the sample holder, the connecting rod is connected with a motor, the motor is positioned outside the pulse laser deposition chamber, a sealing flange is arranged at the connection position of the motor and the connecting rod, and the motor drives the sample holder to rotate clockwise or anticlockwise in the vertical direction; the pulsed laser deposition chamber is also provided with a laser incidence window, an electron gun inlet, a gas inlet and a gas outlet, wherein the gas inlet is in switchable connection with the reaction gas supply device and the impurity gas supply device;
the target shielding box is arranged in the lower part of the pulse laser deposition chamber and can move periodically, an eccentric through hole is formed in the top wall of the target shielding box, a plurality of sub-shielding areas which are circumferentially arranged along the target shielding box are arranged in the target shielding box, and the sub-shielding areas are not communicated and can rotate relative to the top wall of the target shielding box;
a laser emitting device adapted to emit laser light through the laser incidence window and the eccentric through hole toward a target disposed in the sub-shielding region so as to sputter the target onto a substrate disposed on the sample holder and deposit an electrode thin film;
an electrochemical workstation comprising a first lead and a second lead, the first lead and the second lead being adapted to be connected to the sample holder by the sealing flange such that the first lead is connected to a working electrode of the deposited electrode film and the second lead is connected to a counter electrode of the deposited electrode film;
the high-energy reflection electron diffractometer comprises an electron gun and a differential pump, wherein the electron gun stretches into the pulsed laser deposition cavity through an electron gun inlet and points to the sample holder;
the screen is arranged on the pulse laser deposition chamber and is suitable for displaying light spots formed by electron diffraction on the screen in the process of depositing the electrode film, and the CCD camera is arranged outside the pulse laser deposition chamber and is suitable for recording the dynamic change process of the light spots displayed on the screen so as to obtain the surface structure change in the process of depositing the electrode film;
the vacuum glove box is hermetically connected with the pulse laser deposition cavity;
and the vacuumizing device is connected with the gas outlet.
The environmental PLD growth and electrochemical performance test system of the embodiment of the invention has at least the following advantages: 1) According to the system, targets can be placed in the shielding box, on one hand, through the arrangement of the plurality of sub-shielding areas, cross contamination to other targets can be prevented when the targets are sputtered by laser when multiple targets are needed, on the other hand, sputtering of the targets can be realized through the arrangement of the eccentric through holes, and baking of the targets and the transmission mechanism by the heat source can be reduced by using the top wall of the shielding box; furthermore, the rotating speed of the sub shielding area relative to the top wall of the shielding box can be set according to the frequency of the laser sputtering target material, and the target material can form a motion state similar to rotation and revolution by combining the periodical moving frequency of the shielding box, so that the effect of improving the uniform sputtering of laser on the surface of the whole target material is achieved; 2) The motor drives the sample holder to rotate clockwise or anticlockwise in the vertical direction, so that the strongest signal of energy can be automatically, accurately and rapidly found, the observation angle is determined, a clearer observation effect is obtained on the CCD camera, the surface structure of the sample film can be better determined, and the growth process of the film is guided; 3) The Pulse Laser Deposition (PLD) is adopted to replace the traditional casting method for preparing the film, so that a more complex oxide electrode film can be accurately prepared, and an ultra-clean film pattern electrode with compact structure and clear interface is obtained, thereby effectively solving the interference of various interfaces in the existing porous composite electrode structure on the reaction of gas phase impurities and electrode interfaces; 4) Through integrating an electrochemical characterization system, the test and analysis of electrochemical performance under different atmospheres and different humidity can be performed in situ, and H in the external environment atmosphere is eliminated 2 O、SO 2 And CO 2 The influence of pollution sources on the surface reaction can be equal, the ultra-clean electrochemical performance analysis of the oxide film can be realized, and the accuracy of the test is improved; 5) The electrode film is not required to be cooled from high temperature (up to 700 ℃ or even higher) to normal temperature after growth, the temperature in the chamber can be directly regulated to the temperature required by impurity reaction, the test efficiency can be greatly improved, and the structural change of the electrode film structure possibly occurring during the transition from high temperature to low temperature can be avoided, which can lead toThe structure of the electrode film is inconsistent with the structure observed in the process of generating the electrode film, so that the accuracy of test analysis is affected; 6) The system is connected with the vacuum glove box, so that vacuum interconnection of the glove box and the PLD cavity can be realized, samples are transferred in the glove box in a plastic package manner, cleanliness in the sample transferring process can be guaranteed to the greatest extent, samples with high cleanliness are provided for subsequent other performance characterization, and the accuracy of testing is improved; 7) The ultra-clean film pattern electrode with clear interface can be accurately prepared, and electrochemical performances under different gas-phase impurities can be accurately tested in situ, so that the method has very important significance for understanding failure reasons and improving performances of devices and industrial production and application of the devices.
In addition, the environmental PLD growth and electrochemical performance testing system according to the above-described embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, a turbine is disposed on the motor, a turbine rod is disposed on the connecting rod, and the turbine drives the sample holder to rotate through the turbine rod.
In some embodiments of the invention, the motor is a stepper motor having a step size of 0.002 to 0.2 degrees/step.
In some embodiments of the present invention, the number of the sub-shielding areas is 2 to 5, and the rotation speed of the sub-shielding areas is not greater than 50 rpm.
In some embodiments of the present invention, the top wall of the target shielding box includes at least two layers of metal plates arranged up and down, and a closed interlayer is disposed between two adjacent layers of metal plates, and the thickness of the closed interlayer is 3-5 mm.
In some embodiments of the invention, the metal plates are stainless steel plates, and each layer of the metal plates has a thickness of 1.5-2 mm.
In some embodiments of the invention, the number of channels of the electrochemical workstation is 1-4; and/or 1-4 connection positions connected with the first lead are arranged on the sample support, and each connection position is respectively and independently corresponding to a working electrode of the electrode film obtained by deposition.
In some embodiments of the invention, a first gas flow meter is disposed between the reactant gas supply and the gas inlet, and a second gas flow meter is disposed between the impurity gas supply and the gas inlet; and/or a first valve is arranged between the reaction gas supply device and the gas inlet, and a second valve is arranged between the impurity gas supply device and the gas inlet.
In some embodiments of the invention, the impurity gas supply means comprises a water vapour supply means and a dry impurity gas supply means, the water vapour supply means and/or the dry impurity gas supply means being connected to the gas inlet.
In some embodiments of the invention, the water vapor supply is connected to a vacuum apparatus.
In some embodiments of the invention, the water stored in the water vapor supply device is ultrapure water.
According to a second aspect of the present invention, the present invention provides a method for preparing an electrode thin film and/or testing the electrochemical performance of an electrode thin film using the above-described environmental PLD growth and electrochemical performance testing system. The method has all the features and effects described in the above-mentioned environmental PLD growth and electrochemical performance test system, and will not be described here again. In general, the method can accurately prepare the oxide film, can accurately test the electrochemical performance of the film under different gas phase impurities, and has great significance in understanding the failure reasons and performance improvement of devices and industrial production and application of the devices.
According to a third aspect of the present invention, the present invention provides a use of the above-described environmental PLD growth and electrochemical performance test system for preparing an electrode thin film and testing the electrochemical performance of the electrode thin film. The application has all the features and effects described in the above-mentioned environmental PLD growth and electrochemical performance test system, and will not be described here again.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of an environmental PLD growth and electrochemical performance testing system according to one embodiment of the invention.
Fig. 2 is a schematic diagram showing the rotation direction when the motor rotates the sample holder according to an embodiment of the present invention.
Fig. 3 is a top view of a target shielding cage according to one embodiment of the present invention.
FIG. 4 is a RHEED pattern of SrO grown at 270 pulses of laser sputtered in example 1 of the present invention.
FIG. 5 is a RHEED pattern of SrO grown at 270 pulses of laser sputtered in example 1 of the present invention after 30 minutes of residence in an aqueous atmosphere.
FIG. 6 is a graph showing the comparison of electrochemical impedance spectra before and after stopping SrO grown in an aqueous atmosphere at 270 pulses of laser sputtering in example 1 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "upper," "lower," "top," "bottom," "inner," "outer," "circumferential," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the present invention, unless explicitly specified and limited otherwise, terms such as "mounted," "connected," "secured," and the like are to be construed broadly and may be, for example, fixedly attached, detachably attached, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In one aspect, the invention provides an environmental PLD growth and electrochemical performance testing system. According to an embodiment of the invention, the system comprises: the apparatus comprises a pulsed laser deposition chamber 10, a target shielding box 50, a laser emitting device (not shown), an electrochemical workstation 20, a reflective high-energy electron diffractometer 30, a screen 40 and a CCD camera 60 for matching use, a vacuum glove box (not shown) and a vacuum pumping device (not shown). After the system is used for preparing the oxide film electrode, the electrochemical performance of the electrode material can be obtained in an ultra-clean environment, the pollution of gas phase impurities in the process of transferring samples before the sample test is eliminated, different types of gases can be introduced into the system, the humidity of the gases is regulated, the influence of the gases on the electrode material is researched, and the accuracy of the test is improved. Therefore, the method has great significance for understanding the failure reason and the performance improvement of the device and the industrial production and application of the device. It should be noted that PLD referred to in the present invention refers to pulsed laser deposition. The environmental PLD growth and electrochemical performance testing system according to the above-described embodiment of the present invention will be described in detail with reference to fig. 1 to 3.
According to the embodiment of the invention, as understood by referring to fig. 1, a sample holder 11 is arranged in the upper part of a pulse laser deposition chamber 10, a connecting rod 12 is arranged on the upper part of the sample holder 11, the connecting rod 12 is connected with a motor 13, the motor 13 is positioned outside the pulse laser deposition chamber 10, a sealing flange 14 is arranged at the connecting position of the motor 13 and the connecting rod 12, and the motor 13 drives the sample holder 11 to rotate clockwise or anticlockwise in the vertical direction (understood by referring to fig. 2); the pulsed laser deposition chamber 10 is further provided with a laser incidence window 15, an electron gun inlet 16, a gas inlet 17 and a gas outlet (not shown), wherein the gas inlet 17 is switchably connected with the reaction gas supply device 70 and the impurity gas supply device 80, the connecting rod 12 is detachably connected with the motor 13, and the motor 13 can rotate positively and negatively; the target shielding box 50 is arranged at the lower part of the pulse laser deposition chamber 10 and can move periodically, and is preferably arranged below the sample holder 11 and corresponds to the sample holder 11; as will be appreciated in connection with fig. 1 and 3, the top wall of the target shielding case 50 is provided with an eccentric through hole 51, and a plurality of sub-shielding regions 52 arranged along the circumferential direction of the target shielding case 50 are provided in the target shielding case 50, and the plurality of sub-shielding regions 52 are not communicated with each other and are rotatable relative to the top wall of the target shielding case 50. The laser emitting device is adapted to emit laser light through the laser incidence window 15 and the eccentric through-hole 51 toward the target disposed in the sub-shielding region 52 so as to sputter the target onto the substrate disposed on the sample holder 11 and deposit the electrode thin film. That is, when preparing the electrode film, the laser emitting device can be turned on and the laser is driven onto the target 53, the target 53 is subjected to plasma sputtering and chemical vapor deposition coating film is performed on the substrate positioned on the sample holder 11, wherein the target 53 is arranged in the sub-shielding region 52 of the target shielding box 50, so that a more complex oxide electrode film can be precisely prepared, an ultra-clean film pattern electrode with compact structure and clear interface can be obtained, and the interference of various interfaces existing in the prior porous composite electrode structure on the reaction of gas phase impurities and electrode interfaces can be effectively solved.
It should be noted that the kind of the target material in the present invention is not particularly limited, and a person skilled in the art may select the target material according to actual needs, for example, the target material may be determined by the cathode material of the battery to be tested; the target material may be metal, for example, in the electrode film growing process, oxygen may be introduced into the chamber through the gas inlet as reaction gas, and in order to keep the pressure in the chamber stable, a vacuum pumping device (not shown) may be used to perform vacuum pumping treatment while the reaction gas is introduced, so that the two reach dynamic balance. Further, in order to ensure the junction purity of the deposited electrochemical thin film, when the target material is subjected to laser sputtering, vacuum pumping equipment can be adopted in advance to perform vacuum pumping treatment on the PLD chamber through a gas outlet (not shown), preferably, reaction gas is introduced after vacuum pumping, and the process is repeated for 2-3 times, so that impurity gas in the chamber can be fully discharged, and the cleanliness of the finally prepared electrode thin film is further improved. In addition, the targets are placed in the shielding box provided with a plurality of sub-shielding areas, so that on one hand, when a plurality of targets are needed, cross contamination to other targets can be prevented when the targets are sputtered by laser, on the other hand, sputtering of the targets can be realized by arranging the eccentric through holes, and the baking of the targets and the transmission mechanism by the heat source can be reduced by utilizing the top wall of the shielding box; furthermore, the rotating speed of the sub shielding area relative to the top wall of the shielding box can be set according to the frequency of the laser sputtering target material, and the target material can form a motion state similar to rotation and revolution by combining the periodical moving frequency of the shielding box, so that the effect of improving the uniform sputtering of laser on the surface of the whole target material is achieved; on the other hand, the motor drives the sample holder to rotate in the clockwise direction or the anticlockwise direction in the vertical direction, so that the strongest energy signal can be automatically, accurately and quickly found, the observation angle is determined, a clearer observation effect is obtained on the CCD camera, the surface structure of the sample film can be better determined, and the growth process of the film is guided.
According to an embodiment of the present invention, as understood with reference to fig. 1,according to the invention, the electrochemical workstation 20 is integrated into PLD equipment, so that the prepared electrode film sample 18 can be accurately tested and characterized in situ under different atmospheres and different humidities, and the electrode film is not required to be transferred to the outside of the PLD cavity for testing, thereby not only effectively eliminating the unavoidable contact of the sample to be tested with H in the external environmental atmosphere during the transfer process 2 O、SO 2 And CO 2 The problems of negative effects such as interference and the like on the surface reaction of the electrode film caused by the pollution sources and the like can be avoided, and the problems of influence on the testing precision and accuracy caused by the existence of impurity pollution sources such as Si and the like in the electrochemical testing furnace can be avoided; meanwhile, in the deposition and growth process of the electrode film, only the gas required by the reaction is contacted without introducing any impurity, and H in the external environment atmosphere is further eliminated 2 O、SO 2 And CO 2 The interference influence of pollution sources on the surface reaction of the electrode film can be realized, so that the ultra-clean electrochemical performance analysis of the oxide electrode film can be realized, and the test accuracy can be improved. The electrochemical workstation 20 may include a first lead 21 and a second lead 22, where the first lead 21 and the second lead 22 are adapted to be connected to the sample holder 11 through the sealing flange 14 such that the first lead 21 is connected to a working electrode of the deposited electrode thin film and the second lead 22 is connected to a counter electrode of the deposited electrode thin film, whereby the electrochemical performance of the electrode thin film can be tested. The first lead and the second lead are connected with the electrode film through the sealing flange, and the sealing performance of the cavity can be further guaranteed, so that the interference of external impurity gas on the preparation and testing of the electrode film is further avoided. In addition, the first lead wire 21 and the second lead wire 22 can be platinum lead wires independently, so that the requirements of electrochemical performance test of the electrode film in a high-temperature environment can be met. Further, the sealing flange 14 may further comprise electrodes (not shown) adapted to be connected to the sample holder 11, the first lead 21 and the second lead 22 such that the first lead 21 is connected to the working electrode of the deposited electrode film and the second lead 22 is connected to the counter electrode of the deposited electrode film, whereby when an electrochemical performance test is required for the prepared electrode film,it is only necessary to connect the first lead 21 and the second lead 22 to the electrodes of the sealing flange correspondingly.
As will be appreciated with reference to fig. 1, in accordance with an embodiment of the present invention, the reflective high-energy electron diffractometer 30 includes an electron gun 31 and a differential pump 32, the electron gun 31 extending into the pulsed laser deposition chamber 10 through the electron gun inlet 16 and directed toward the sample holder 11; the screen 40 is disposed on the pulsed laser deposition chamber 10 and adapted to display light spots formed by electron diffraction impinging thereon during the deposition of the electrode thin film, and the CCD camera 60 is disposed outside the pulsed laser deposition chamber 10 and adapted to record a dynamic change process of the light spots displayed on the screen 40 so as to obtain a change in the surface structure during the deposition of the electrode thin film. In the process of depositing and growing the electrode film, light spots formed by diffraction of electrons glancing on the electrode film are also continuously changed, and the invention can obtain the surface structure change in the process of depositing and growing the electrode film by recording the dynamic change process of the light spots displayed on a screen by combining a CCD camera. Wherein the screen and the CCD camera are arranged based on the relative positions of the sample holder and the electron gun. In addition, the reflective high-energy electron diffractometer 30 may include two differential pumps 32, the differential pumps 32 being adapted to locally evacuate the PLD chamber so that the portion of the electron gun that emits electrons is in a vacuum or high vacuum environment, leaving the partial region at a slightly lower pressure, which does not react with oxygen in the chamber. Since the electron gun has a very small volume of the portion emitting electrons, even if partial vacuum is applied by a differential pump, the dynamic balance of the gas in the chamber is not adversely affected.
According to the embodiment of the invention, as understood by referring to fig. 1, the vacuum glove box is in sealing connection with the pulse laser deposition chamber 10, so that vacuum interconnection of the glove box and the PLD chamber can be realized, the prepared film sample is subjected to plastic package transfer in the glove box, the cleanliness in the sample transfer process can be ensured to the greatest extent, a high-cleanliness sample is provided for subsequent other performance characterization, and the test accuracy is improved. In addition, the vacuumizing equipment is connected with the gas outlet, so that the cleanliness of the reaction environment in the chamber can be further realized.
According to an embodiment of the present invention, the pulsed laser deposition chamber 10 may further be provided with: and a pressure sensor (not shown), whereby, when it is required to introduce a reaction gas or impurity gas into the PLD chamber while satisfying the dynamic balance of maintaining the gas pressure in the chamber, the gas pressure condition in the chamber can be judged by observing the value of the pressure sensor, and the flow rates of the gas introduced into the chamber and the gas discharged from the chamber can be adjusted according to the actual condition, so that the gas pressure in the chamber is maintained stable.
According to the embodiment of the invention, the turbine can be arranged on the motor 13, and the turbine rod can be arranged on the connecting rod 12, so that the turbine can drive the sample holder 11 to rotate through the turbine rod, and the sample holder can drive the sample to rotate anticlockwise or clockwise in the vertical direction. Further, the motor 13 may be a stepping motor, the step length of the stepping motor is 0.002-0.2 degrees/step, that is, each step rotates the sample holder by 0.002-0.2 degrees, and the inventor finds that if the step length is too large, the problem that the light spot displayed on the screen is difficult to capture or the light spot signal with stronger energy is difficult to capture exists, and if the step length is too small, the time required for capturing the light spot on the CCD camera is longer.
According to the embodiment of the present invention, the number of the sub-shielding areas 52 in the target shielding box 50 is not particularly limited, and a person skilled in the art can flexibly select the number according to actual needs, for example, the number of the sub-shielding areas 52 may be 2 to 5, and the rotation speed of the sub-shielding areas 52 is preferably not greater than 50 rpm. Therefore, the effect of uniform sputtering of the laser on the whole target surface can be improved, and the switching of multiple target types can be realized.
According to an embodiment of the present invention, the top wall of the target shielding case 50 may include at least two metal plates disposed one above the other, and a closed interlayer may be disposed between two adjacent metal plates, and the thickness of the closed interlayer may be 3 to 5mm, and preferably may include three metal plates and two closed interlayers. The heat conduction effect of the top wall of the target shielding box 50 can be obviously reduced after the airtight interlayer is arranged, the baking of the heat source for heating the sample above the shielding box to the target and the transmission mechanism is avoided, and the heat insulation effect of the shielding box can be further improved by adopting a plurality of layers of heat insulation steel plates on the upper part of the shielding box. In addition, the material of the metal plate can be preferably stainless steel plate, so that impurities possibly introduced in the production process of the film sample can be further reduced; in addition, the thickness of each metal plate is not particularly limited, and may be flexibly selected according to actual needs by those skilled in the art, for example, may be 1.5 to 2mm, etc.
According to the embodiment of the invention, the number of the channels of the electrochemical workstation 20 can be 1-4, so that the data of the electrode film samples can be collected through a plurality of independent test channels in the test process, the rapid statistics of the sample data is improved, the measurement error is reduced, and the reliability and the efficiency of the test are improved. When the number of channels is not less than 2, the test parameters of the plurality of channels may be the same or different. Further, 1 to 4 connection positions connected with the first lead 21 may be provided on the sample holder 11, and each connection position may correspond to the working electrode of the electrode film obtained by deposition independently, so that measurement errors may be reduced by collecting data of different positions of the electrode film sample, and reliability of the test may be improved.
According to an embodiment of the present invention, a first gas flow meter 71 may be provided between the reactant gas supply means 70 and the gas inlet 17, and a second gas flow meter (not shown) may be provided between the impurity gas supply means 80 and the gas inlet 17, whereby the flow rate of the reactant gas or impurity gas supplied into the PLD cavity may be monitored in real time to control the gas pressure or the partial pressure of each gas component in the cavity. Wherein, when preparing the electrode film sample, the reactant gas can be introduced into the PLD chamber by the reactant gas supply device 70; when investigating the effect of impurity gas on the composition and performance of the electrode thin film sample, the impurity gas supply device 80 may be used to supply a selected impurity gas into the PLD chamber. Further, a first valve 72 may be provided between the reactant gas supply device 70 and the gas inlet 17, for example, the first valve 72 may be provided between the reactant gas supply device 70 and the first gas flow meter 71, and a second valve 81 may be provided between the impurity gas supply device 80 and the gas inlet 17, for example, the second valve 81 may be provided between the impurity gas supply device 80 and the second gas flow meter, whereby switching between supplying the reactant gas and the impurity gas into the PLD chamber can be achieved by opening and closing the first valve and the second valve.
According to a specific embodiment of the present invention, the impurity gas supply means 80 may further comprise a water vapor supply means and a dry impurity gas supply means (wherein only the water vapor supply means is shown in fig. 1), wherein the water vapor supply means and the dry impurity gas supply means may be connected to the gas inlet 17 of the PLD chamber at the same time or separately, and may be specifically selected according to the composition of the impurity gas to be studied, wherein the dry impurity gas supply means may further comprise a carbon dioxide supply means and/or a sulfur dioxide supply means. Further, the water vapor supply device may be connected to the gas inlet 17 of the PLD chamber through a micro-leak valve, whereby the humidity of the reaction atmosphere or the test atmosphere in the chamber may be adjusted through the micro-leak valve; the dry impurity gas supply means may be connected to the gas inlet 17 of the PLD chamber through the second valve 81 and the gas flow meter in sequence, whereby the composition of the impurity gas to be introduced into the PLD chamber may be selected according to actual needs. Further, the water vapor supply device can be connected with the vacuumizing equipment, the water vapor supply device comprises a quartz bottle suitable for containing (ultra-pure) water, when water vapor is introduced into the PLD cavity, the water in the water vapor supply device can be frozen and frozen first, air in the ice is pumped out by the vacuumizing equipment, and then the ice is melted to form water, so that the cleanliness of a prepared sample or test atmosphere can be further improved, and the accuracy of a test result is ensured.
In accordance with an embodiment of the present invention, as understood with reference to FIG. 1, an electrochemical workstation 20 is integrated onto a Pulsed Laser Deposition (PLD) chamber 10, and an electrical signal from the electrochemical workstation 20 is applied to the counter and working electrodes of a sample 18 through leads 21 and 22 extending into the PLD chamber 10; depositing a thin film on a substrate fixed by the sample holder 11 through the laser sputtering target 53, wherein the thin film is deposited by the laser sputtering target 53, the target 53 is arranged in the shielding box 50, and the shielding box 50 is arranged at the lower part of the PLD chamber 10 and is oppositely arranged below the sample holder 11; the stepper motor 13 drives the sample holder 11 to rotate clockwise or anticlockwise in the vertical direction, and a reflective high-energy electron diffractometer (RHEED) 30 is adopted to analyze the surface structure in the film growth process; the flow rate of the gas entering the chamber 10 is controlled by a gas flow meter, the humidity of the gas is controlled by a micro-leakage valve, and the gas inlet end of the micro-leakage valve is connected with a quartz bottle of the water vapor supply device.
In summary, the environmental PLD growth and electrochemical performance testing system according to the above embodiment of the present invention has at least the following advantages: 1) According to the system, targets can be placed in the shielding box, on one hand, through the arrangement of the plurality of sub-shielding areas, cross contamination to other targets can be prevented when the targets are sputtered by laser when multiple targets are needed, on the other hand, sputtering of the targets can be realized through the arrangement of the eccentric through holes, and baking of the targets and the transmission mechanism by the heat source can be reduced by using the top wall of the shielding box; furthermore, the rotating speed of the sub shielding area relative to the top wall of the shielding box can be set according to the frequency of the laser sputtering target material, and the target material can form a motion state similar to rotation and revolution by combining the periodical moving frequency of the shielding box, so that the effect of improving the uniform sputtering of laser on the surface of the whole target material is achieved; 2) The motor drives the sample holder to rotate clockwise or anticlockwise in the vertical direction, so that the strongest signal of energy can be automatically, accurately and rapidly found, the observation angle is determined, a clearer observation effect is obtained on the CCD camera, the surface structure of the sample film can be better determined, and the growth process of the film is guided; 3) The Pulse Laser Deposition (PLD) is adopted to replace the traditional casting method for preparing the film, so that a more complex oxide electrode film can be accurately prepared, and an ultra-clean film pattern electrode with compact structure and clear interface is obtained, thereby effectively solving the interference of various interfaces in the existing porous composite electrode structure on the reaction of gas phase impurities and electrode interfaces; 4) By integrating the electrochemical characterization system, one canIn-situ test and analysis of electrochemical performance under different atmospheres and different humidity are carried out to eliminate H in the external environment atmosphere 2 O、SO 2 And CO 2 The influence of pollution sources on the surface reaction can be equal, the ultra-clean electrochemical performance analysis of the oxide film can be realized, and the accuracy of the test is improved; 5) After the electrode film is grown, the process of cooling from high temperature (up to 700 ℃ or even higher) to normal temperature is not required, the temperature in the chamber can be directly regulated to the temperature required by impurity reaction, the test efficiency can be greatly improved, the structural change of the electrode film structure during the transition from high temperature to low temperature can be avoided, and the structural change can cause the inconsistency of the obtained electrode film structure and the structure observed in the electrode film generating process, so that the accuracy of test analysis is affected; 6) The system is connected with the vacuum glove box, so that vacuum interconnection of the glove box and the PLD cavity can be realized, samples are transferred in the glove box in a plastic package manner, cleanliness in the sample transferring process can be guaranteed to the greatest extent, samples with high cleanliness are provided for subsequent other performance characterization, and the accuracy of testing is improved; 7) The ultra-clean film pattern electrode with clear interface can be accurately prepared, and electrochemical performances under different gas-phase impurities can be accurately tested in situ, so that the method has very important significance for understanding failure reasons and improving performances of devices and industrial production and application of the devices.
According to a second aspect of the present invention, the present invention provides a method for preparing an electrode thin film and/or testing the electrochemical performance of an electrode thin film using the above-described environmental PLD growth and electrochemical performance testing system. The method has all the features and effects described in the above-mentioned environmental PLD growth and electrochemical performance test system, and will not be described here again. In general, the method can accurately prepare the oxide film, can accurately test the electrochemical performance of the film under different gas phase impurities, and has great significance in understanding the failure reasons and performance improvement of devices and industrial production and application of the devices.
According to a third aspect of the present invention, the present invention provides a use of the above-described environmental PLD growth and electrochemical performance test system for preparing an electrode thin film and testing the electrochemical performance of the electrode thin film. The application has all the features and effects described in the above-mentioned environmental PLD growth and electrochemical performance test system, and will not be described here again.
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
As understood with reference to fig. 1, the environmental PLD growth and electrochemical performance testing system is used for preparing solid oxide electrode materials and testing electrochemical performance of samples under different gas types and humidity, and specific operation steps are as follows:
connecting the two-channel electrode of electrochemical workstation 20 with the electrode of sealing flange 14 in PLD chamber 10, the electrode on sealing flange 14 being connected with the counter electrode and the double working electrode of sample 18; the quartz bottle of the water vapor supply device (80 is understood by referring to FIG. 1) is filled with ultra-pure water, then is connected with the air inlet end of the micro-leakage valve (81 is understood by referring to FIG. 1), the ultra-pure water in the quartz bottle is frozen and frozen by adopting liquid nitrogen, and impurity gas in the ice is pumped out; turning on a reflective high-energy electron diffractometer (RHEED) 30 and a stepper motor 13, wherein the stepper motor 13 drives the sample holder 11 to rotate anticlockwise or clockwise in the vertical direction, a gas flowmeter is regulated, after a set atmosphere and temperature are reached, a target 53 in the laser sputtering chamber 10 is used for depositing a film (the growth atmosphere is oxygen atmosphere, the air pressure is 133 Pa), the target is positioned in a sub-shielding region 52 of the shielding box 50, and the surface structure of the film in the growth process is monitored through the reflective high-energy electron diffractometer (RHEED) 30; after the growth of the sample 18 is finished, the temperature of the test is regulated, the atmosphere of the test is regulated through a gas flowmeter, the gas micro-leakage valve 10 is regulated, and the water vapor in the quartz bottle is introduced into the chamber 10, so that the gas humidity in the chamber 10 is regulated, the electrochemical workstation 20 is opened, the parameters of the instrument test are set, and the electrochemical performance test is carried out on the sample 18 under different temperatures, different atmospheres and different humidities; wherein the target 53 is SrO, the frequency of the periodic movement of the target shielding box 50 is 1Hz, the rotation speed of the target sub-shielding area is 30 rpm, the top wall of the target shielding box 50 comprises three layers of stainless steel plates, a closed interlayer is arranged between every two adjacent layers of stainless steel plates, the thickness of the interlayer is 3mm, the thickness of the steel plates is 2mm, and the step size of the step motor 13 for driving the sample holder 11 to rotate clockwise and anticlockwise in the vertical direction is 0.02 DEG/step.
After sample preparation is completed, oxygen and water vapor are introduced into the cavity, the water introducing time is 30min, the air pressure in the cavity is 0.399Pa, the water vapor partial pressure is 30%, the temperature is 650 ℃, fig. 4 and fig. 5 are RHEED maps of SrO growing 270 laser pulse numbers before and after water introducing respectively, and compared with fig. 4 and fig. 5, the signal intensity and definition of the sample are reduced after water introducing for 30min, which means that the crystallinity of the film before water introducing is better, and the film quality is reduced after water introducing; fig. 6 is a graph showing the comparison of the changes in electrochemical impedance spectra of SrO films before and after water passage (multiple measurements), and it can be seen from fig. 6 that the impedance of the films after water passage is increased and the electrochemical performance is decreased.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (12)

1. An environmental PLD growth and electrochemical performance testing system, comprising:
the pulse laser deposition device comprises a pulse laser deposition chamber, wherein a sample holder is arranged in the upper part of the pulse laser deposition chamber, a connecting rod is arranged on the upper part of the sample holder, the connecting rod is connected with a motor, the motor is positioned outside the pulse laser deposition chamber, a sealing flange is arranged at the connection position of the motor and the connecting rod, and the motor drives the sample holder to rotate clockwise or anticlockwise in the vertical direction; the pulsed laser deposition chamber is also provided with a laser incidence window, an electron gun inlet, a gas inlet and a gas outlet, wherein the gas inlet is in switchable connection with the reaction gas supply device and the impurity gas supply device;
the target shielding box is arranged in the lower part of the pulse laser deposition chamber and can move periodically, an eccentric through hole is formed in the top wall of the target shielding box, a plurality of sub-shielding areas which are circumferentially arranged along the target shielding box are arranged in the target shielding box, and the sub-shielding areas are not communicated and can rotate relative to the top wall of the target shielding box;
a laser emitting device adapted to emit laser light through the laser incidence window and the eccentric through hole toward a target disposed in the sub-shielding region so as to sputter the target onto a substrate disposed on the sample holder and deposit an electrode thin film;
an electrochemical workstation comprising a first lead and a second lead, the first lead and the second lead being adapted to be connected to the sample holder by the sealing flange such that the first lead is connected to a working electrode of the deposited electrode film and the second lead is connected to a counter electrode of the deposited electrode film;
the high-energy reflection electron diffractometer comprises an electron gun and a differential pump, wherein the electron gun stretches into the pulsed laser deposition cavity through an electron gun inlet and points to the sample holder;
the screen is arranged on the pulse laser deposition chamber and is suitable for displaying light spots formed by electron diffraction on the screen in the process of depositing the electrode film, and the CCD camera is arranged outside the pulse laser deposition chamber and is suitable for recording the dynamic change process of the light spots displayed on the screen so as to obtain the surface structure change in the process of depositing the electrode film;
the vacuum glove box is hermetically connected with the pulse laser deposition cavity;
and the vacuumizing device is connected with the gas outlet.
2. The system of claim 1, wherein a turbine is provided on the motor, a worm is provided on the connecting rod, and the turbine rotates the sample holder through the worm.
3. The system of claim 1 or 2, wherein the motor is a stepper motor having a step size of 0.002-0.2 degrees/step.
4. The system of claim 1, wherein the number of sub-shielding areas is 2-5, and the rotation speed of the sub-shielding areas is not greater than 50 rpm.
5. The system according to claim 1 or 4, wherein the top wall of the target shielding box comprises at least two layers of metal plates arranged up and down, a closed interlayer is arranged between two adjacent layers of metal plates, and the thickness of the closed interlayer is 3-5 mm.
6. The system of claim 5, wherein the metal plates are stainless steel plates, each layer of the metal plates having a thickness of 1.5-2 mm.
7. The system of claim 1, wherein the number of channels of the electrochemical workstation is 1-4; and/or 1-4 connection positions connected with the first lead are arranged on the sample support, and each connection position is respectively and independently corresponding to a working electrode of the electrode film obtained by deposition.
8. The system of claim 1, wherein a first gas flow meter is disposed between the reactant gas supply and the gas inlet, and a second gas flow meter is disposed between the impurity gas supply and the gas inlet; and/or the number of the groups of groups,
a first valve is arranged between the reaction gas supply device and the gas inlet, and a second valve is arranged between the impurity gas supply device and the gas inlet.
9. The system according to claim 1 or 7, wherein the impurity gas supply means comprises a water vapour supply means and a dry impurity gas supply means, the water vapour supply means and/or the dry impurity gas supply means being connected to the gas inlet.
10. The system of claim 9, wherein the water vapor supply is coupled to a vacuum apparatus.
11. The system of claim 9, wherein the water stored in the water vapor supply device is ultrapure water.
12. Use of the system according to any one of claims 1 to 11 for the preparation of electrode films and for testing the electrochemical performance of electrode films.
CN202210651353.2A 2022-06-09 2022-06-09 Environmental PLD growth and electrochemical performance test system, method and application Active CN115201307B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210651353.2A CN115201307B (en) 2022-06-09 2022-06-09 Environmental PLD growth and electrochemical performance test system, method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210651353.2A CN115201307B (en) 2022-06-09 2022-06-09 Environmental PLD growth and electrochemical performance test system, method and application

Publications (2)

Publication Number Publication Date
CN115201307A CN115201307A (en) 2022-10-18
CN115201307B true CN115201307B (en) 2023-07-14

Family

ID=83577040

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210651353.2A Active CN115201307B (en) 2022-06-09 2022-06-09 Environmental PLD growth and electrochemical performance test system, method and application

Country Status (1)

Country Link
CN (1) CN115201307B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116988014B (en) * 2023-09-27 2023-12-22 中国科学技术大学 Combined centralized vacuum interconnection system device

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7879410B2 (en) * 2004-06-09 2011-02-01 Imra America, Inc. Method of fabricating an electrochemical device using ultrafast pulsed laser deposition
US20080254235A1 (en) * 2007-04-10 2008-10-16 Jeonggoo Kim Pulsed laser deposition of high quality photoluminescent GaN films
US9249502B2 (en) * 2008-06-20 2016-02-02 Sakti3, Inc. Method for high volume manufacture of electrochemical cells using physical vapor deposition
CN102965625A (en) * 2012-11-09 2013-03-13 同济大学 Method for preparing platy nano cobalt oxide array electrode material through pulsed laser deposition and application of method

Also Published As

Publication number Publication date
CN115201307A (en) 2022-10-18

Similar Documents

Publication Publication Date Title
CN115201307B (en) Environmental PLD growth and electrochemical performance test system, method and application
JP4312289B2 (en) Organic thin film forming equipment
TWI277164B (en) Leak detector and process gas monitor
US4854264A (en) Vacuum evaporating apparatus
KR20100119726A (en) Plasma process apparatus and plasma process method
CN109246860A (en) In situ, dynamic observation material high temperature service under the microscope can be achieved
KR20190072389A (en) Cooling member and vacuum coating device
JP4735813B2 (en) Combined heat treatment equipment and vapor deposition equipment
CN112864039B (en) In-situ electrical performance monitoring equipment for organic semiconductor device
CN217112167U (en) In situ cleaning PLD electrochemical characterization system
CN111272654A (en) Low-temperature to high-temperature controllable-temperature infrared in-situ reaction tank based on high vacuum condition
US9103032B2 (en) Apparatus and method for forming thin films in solar cells
CN218969355U (en) Microwave plasma reaction cavity and equipment for chemical vapor deposition
JP3441002B2 (en) Sputtering equipment
JP2010217012A (en) Infrared detector and device manufacturing apparatus
CN101210311A (en) System for preparing composite film
CN112596560B (en) Temperature control device and test method for testing thermal admittance spectrum of perovskite solar cell
CN114959627A (en) Ultra-clean PLD sample preparation and transfer system and method
JP4720234B2 (en) L-type evaporation boat and evaporation apparatus
CN214830780U (en) Thin film preparation device integrating coating and vacuum-assisted crystallization
CN111424238A (en) Thermal evaporation equipment for realizing low-temperature coating and low-melting-point film material
JP3036895B2 (en) Sputtering equipment
CN220265811U (en) Semiconductor film deposition equipment
JPH059728A (en) Formation of thin film
EP4300029A1 (en) Measuring device for measuring a thickness of a film of material deposited on a substrate and film deposition apparatus with at least one such measuring device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant