X-ray photoelectron spectroscopy in-situ test sample table for high-temperature electrochemistry

Abstract

An X-ray photoelectron spectroscopy in-situ test sample table for high-temperature electrochemistry comprises a base, a gasket, a lower electrode, a lower gold ring, an upper gold ring and an upper electrode which are sequentially arranged from bottom to top. A sample is positioned between the upper gold ring and the lower gold ring; the lower electrode and the upper electrode are arranged in an annular structure, and the upper gold ring and the lower gold ring are located at the annular structure; the annular structure extends outwards and is provided with a contact part, so that the annular structure can be conveniently connected with an instrument sample injection support and a thermocouple; a gap is formed in the inner circumference of the annular structure of the upper electrode so that the upper gold ring can be exposed. The X-ray photoelectron spectroscopy in-situ testing device can be used for in-situ testing of the X-ray photoelectron spectroscopy of a sample under the conditions of high temperature, certain atmosphere and pressure intensity and external voltage or current, so that deep research can be better carried out in the subject fields of solid electrochemistry, photoelectrochemistry, film preparation and the like.

Description

Technical Field

[0001] The utility model relates to the technical field of X-ray photoelectron spectroscopy analysis and testing, in particular to an in-situ test sample stage for X-ray photoelectron spectroscopy in high-temperature electrochemistry. Background Art

[0002] X-ray photoelectron spectroscopy (XPS) is based on the photoionization effect. When a beam of photons irradiates the surface of a sample, the photons can be absorbed by the electrons in the atomic orbit of a certain element in the sample, causing the electrons to break free from the bondage of the atomic nucleus and emit from the inside of the atom with a certain kinetic energy to become free photoelectrons, while the atom itself becomes an excited-state ion. The photoelectrons can be detected by the energy analyzer of the system. The analyzer records and counts the number of electrons with different kinetic energies, and the binding energy information of the electrons can be obtained. These information reflect the elemental composition and chemical state information inside the sample.

[0003] In ordinary X-ray photoelectron spectrometers, MgK and AlK X-rays are generally used as excitation sources, and the energy of the photons is sufficient to cause photoionization of all elements except hydrogen and helium. It can be seen that the X-ray photoelectron spectroscopy technology is a method that can perform a full analysis of all elements at one time, which is very effective for the qualitative analysis of unknown substances. After irradiation with X-rays, the intensity of the photoelectrons emitted from the sample surface has a linear relationship with the concentration of the atoms in the sample, and it can be used for semi-quantitative analysis of elements. Since the intensity of the photoelectrons is related not only to the concentration of the atoms, but also to the mean free path of the photoelectrons, the surface roughness of the sample, the chemical state of the elements, the intensity of the X-ray source, and the state of the instrument, generally, the X-ray photoelectron spectroscopy technology cannot give the absolute content of the analyzed elements, but only provides the relative content of each element. It should also be pointed out that X-ray photoelectron spectroscopy is a surface-sensitive analysis method with a very high surface detection sensitivity, which can reach 10 -3 atomic monolayers, but the detection sensitivity for the bulk phase is only about 0.1%.

[0004] The surface sampling depth of X-ray photoelectron spectroscopy (XPS) is from 1 nanometer to 10 nanometers. An X-ray photoelectron spectrometer mainly consists of five parts: an excitation source, a sample, an electron energy analyzer, a detection system (including an electron multiplier), and an ultra-high vacuum (UHV) system. The excitation source irradiates the sample, causing it to emit electrons with different energy distributions. Then, the electrons are analyzed by the electron energy analyzer, and the test results are given by the detection system. The entire system requires an ultra-high vacuum system. In addition, X-ray photoelectron spectroscopy has the characteristics of not damaging the sample, being pollution-free, fast, and having high measurement accuracy. Therefore, it has become one of the most important means in the research of material surface science and is widely used in academic fields such as chemical analysis, material development and application research, and physical research, as well as industrial fields such as machining, printed circuit technology, coating material process control, and nano-functional material development. The currently booming near-ambient pressure photoelectron spectroscopy further narrows the pressure gap in photoelectron spectroscopy, extending the test environment of photoelectron spectroscopy from a single ultra-high vacuum environment to a near-ambient pressure environment, and further broadening the application scenarios of photoelectron spectroscopy.

[0005] Most of the current mainstream commercial photoelectron spectroscopy sample stages are unable to simultaneously meet the in-situ testing of samples under high temperature, in a certain atmosphere environment, and with an applied voltage or current. Moreover, due to the limitations of the sample stage volume and the instrument structure, there are very few sample stages that can meet the four-probe testing on the basis of the above conditions. How to stably output voltage or current to the sample on a sample stage of limited size, and in a high-temperature and certain atmosphere environment, input and output electrical signals in real time, while in-situ revealing the electrochemical, photoelectrochemical properties and surface physicochemical changes of the sample to be tested remains a difficult and hot topic in current research. Summary of the Invention

[0006] The purpose of the present utility model is to provide a sample stage for in-situ testing of X-ray photoelectron spectroscopy, thereby solving the problem that the sample stage in the prior art cannot stably output voltage or current to the sample in a high-temperature and certain atmosphere environment.

[0007] To achieve the above purpose, the present utility model adopts the following technical solutions:

[0008] An X-ray photoelectron spectroscopy in-situ testing sample stage for high-temperature electrochemistry, comprising a base, a gasket, a lower electrode, a lower gold ring, an upper gold ring, and an upper electrode, which are arranged in sequence from bottom to top;

[0009] The sample is located between the upper gold ring and the lower gold ring;

[0010] Both the lower electrode and the upper electrode are arranged in a ring structure, and the upper gold ring and the lower gold ring are located at the ring structure;

[0011] The ring structure extends outwardly with a contact portion for facilitating connection with the instrument sample holder and the thermocouple;

[0012] A notch is provided on the inner circumference of the annular structure of the upper electrode to facilitate the exposure of the upper gold ring.

[0013] The base includes a placement portion and a connection portion provided at one end of the placement portion. The connection portion is used to connect with the sample loading tray of the instrument; the placement portion is used to place the gasket.

[0014] A plurality of fixing portions that warp upward are provided on the outer circumference of the annular structure of the lower electrode.

[0015] There are 4 fixing portions, and they are symmetrically arranged left and right.

[0016] The base, the upper electrode and the lower electrode are made of stainless steel; the gasket is made of ceramic material.

[0017] Corresponding connection holes extending outward are provided in the annular structures of the upper electrode and the lower electrode, and corresponding channels are provided on the base. The upper electrode, the lower electrode and the base are connected by bolts and nuts.

[0018] There are three groups of connection holes, and the positions of the three groups of connection holes are arranged in a triangular shape; one group of connection holes is provided at the inward extension of the contact portion.

[0019] The utility model further includes a washer, and the washer is provided at the connection part between the upper electrode, the lower electrode and the base.

[0020] The bolts, nuts and washers are made of ceramic material. The washer is used to support the sample stage and insulate the upper electrode and the lower electrode.

[0021] Regarding the application of a sample stage for in-situ X-ray photoelectron spectroscopy testing in high-temperature electrochemistry, the sample stage is installed in a photoelectron spectrometer to realize an in-situ testing environment at different temperatures and external electric field polarization intensities, or the sample stage is combined with a near-ambient pressure photoelectron spectroscopy device to realize the regulation of the atmosphere and pressure of the testing environment, so as to realize the in-situ X-ray photoelectron spectroscopy testing of the sample.

[0022] Compared with the prior art, the beneficial effects obtained by the technical solution of the utility model are as follows:

[0023] 1. Expand the application range of X-ray photoelectron spectroscopy technology: The utility model provides a sample stage for in-situ X-ray photoelectron spectroscopy testing under high temperature, certain atmosphere and pressure, and external voltage or current conditions, which greatly expands the application range of traditional XPS technology. This enables researchers to conduct in-depth research on samples under conditions closer to the actual working environment, improving the authenticity and reliability of the research.

[0024] 2. Enhanced the depth of electrochemical and photoelectrochemical research: The design of this sample stage allows the application of voltage or current and the real-time measurement of the electrochemical and photoelectrochemical properties of the sample under high-temperature and atmosphere conditions. This capability provides strong technical support for research in disciplines such as solid electrochemistry, photoelectrochemistry, and thin-film preparation, and helps to reveal more unknown scientific phenomena and mechanisms.

[0025] 3. Enhanced the stability and reliability of sample testing: The sample stage of this utility model has a compact structure and uses high-temperature and corrosion-resistant materials such as stainless steel and ceramics, ensuring long-term stable operation under high-temperature and complex atmosphere conditions. At the same time, through the tight connection of bolts, nuts, and washers, the stability of the sample stage is further improved, reducing vibration and drift during the testing process and improving the accuracy and reliability of the test data.

[0026] 4. Supports multiple testing environments: This sample stage can not only be tested in a traditional ultra-high vacuum environment but also be combined with near-ambient pressure photoelectron spectroscopy equipment to achieve the regulation of the testing environment atmosphere and pressure. This flexibility enables researchers to select appropriate testing environments according to different research needs, thus obtaining more comprehensive and in-depth research results.

[0027] 5. Improved experimental efficiency: The sample stage of this utility model has a clever structural design, making it easy to disassemble, assemble, and replace samples. At the same time, by externally connecting instruments to control the voltage and current intensity, the testing parameters can be conveniently adjusted, greatly improving the experimental efficiency and research progress.

[0028] 6. Facilitated the research and application of new materials: In the field of materials science and engineering, the research and application of new materials often require in-depth studies on the surface and interface properties of materials. The sample stage of this utility model provides a powerful tool for these studies, enabling researchers to more precisely control the testing conditions, reveal the physical and chemical change processes on the material surface and interface, and providing strong support for the research and application of new materials. Description of the Drawings

[0029] Figure 1 is the exploded structural schematic diagram of this utility model;

[0030] Figure 2 is the overall structural schematic diagram of this utility model;

[0031] Figure 3 is the structural schematic diagram of the base;

[0032] Figure 4 is the structural schematic diagram of the lower electrode;

[0033] Figure 5 is the structural schematic diagram of the upper electrode;

[0034] Figure 6 It is the C1s photoelectron spectroscopy diagram of the cathode surface of a solid oxide electrolytic cell;

[0035] Figure 7 It is the impedance spectroscopy diagram of a solid oxide electrolytic cell. Specific implementation manners

[0036] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present utility model clearer and more understandable, the following further elaborates on the present utility model in conjunction with the accompanying drawings and embodiments.

[0037] As Figures 1 to 5 shown, a sample stage for in-situ X-ray photoelectron spectroscopy for high-temperature electrochemistry in this embodiment includes a base 1, a gasket 2, a lower electrode 3, a lower gold ring 4, an upper gold ring 6, and an upper electrode 7 that are sequentially arranged from bottom to top;

[0038] A sample 5 is located between the upper gold ring 6 and the lower gold ring 4; in this way, the upper gold ring and the lower gold ring serve as current collectors through physical contact with the sample;

[0039] Both the lower electrode 3 and the upper electrode 7 are arranged in a ring structure, and the upper gold ring 6 and the lower gold ring 4 are located at the ring structure;

[0040] The ring structure extends outwardly with contact parts for facilitating connection with the instrument sample holder and the thermocouple; specifically, the lower electrode 3 is provided with a contact part 31, and the upper electrode 7 is provided with a contact part 71; in this way, the entire sample stage can form a circuit, and the input and output of voltage and current signals can be carried out simultaneously. The applied voltage and current intensity are controlled by an external instrument, and in-situ X-ray photoelectron spectroscopy testing for this sample can be achieved;

[0041] A notch 72 is provided on the inner circumference of the ring structure of the upper electrode 7 to facilitate exposure of the upper gold ring 6;

[0042] The base 1 includes a placement part 11 and a connection part 12 provided at one end of the placement part 11, and the connection part 12 is used for connecting with the instrument sample holder; the placement part 11 is used for placing the gasket 2;

[0043] A plurality of fixing parts 32 that are warped upward at a certain angle are provided on the outer circumference of the ring structure of the lower electrode 3. In this embodiment, there are 4 fixing parts 32, and they are symmetrically arranged left and right. In this way, the sample can be conveniently fixed through the fixing parts and the sample can be rotated at any angle relative to the base 1;

[0044] Corresponding connection holes extending outward are provided on the ring structures of both the upper electrode 7 and the lower electrode 3, and corresponding channels are provided on the base. The upper electrode 7, the lower electrode 3 and the base 1 are connected by bolts and nuts.

[0045] Specifically, in this embodiment, the upper electrode 7 is provided with three groups of connection holes 73. Correspondingly, the lower electrode 3 is provided with three groups of connection holes 33, and the base 1 is provided with three groups of channels 31. The positions of the three groups of connection holes and channels are arranged in a triangular pattern; one group of connection holes is provided at the inward extension of the contact part.

[0046] This embodiment further includes a washer 8, which is disposed at the connection between the upper electrode 7, the lower electrode 3, and the base 1 to isolate the upper electrode 7, the lower electrode 3, and the base 1 from each other; the thickness of the washer 8 is selected according to the thickness of the sample, such as 1 mm, 2 mm, 2.5 mm, etc. The cooperation mode of the washer 8 with the lower electrode 3, the upper electrode 7, and the base 1 can be changed as needed, and no specific limitation is made here.

[0047] The base, the upper electrode, and the lower electrode are made of stainless steel; the gasket, the bolt, the nut, and the washer are made of ceramic material.

[0048] In this embodiment, the notch 72 can be semicircularly arranged to facilitate the exposure of the upper gold ring 6, that is, data correction can be achieved during the in-situ X-ray photoelectron spectroscopy test for this sample.

[0049] The fixing part 32 can make a certain adjustment to the warping angle according to the different shapes of the samples, and no limitation is made here.

[0050] The steps of performing an in-situ X-ray photoelectron spectroscopy test using the above sample stage in this embodiment are as follows:

[0051] Step 1: Place the gasket 2 on the base 1; place the lower electrode 3 on the gasket 2; place the lower gold ring 4 at the annular part of the lower electrode 3; place the sample 5 on the lower gold ring 4, and firmly fix the sample 5 through the fixing part 32. Select a suitable washer 8 according to the thickness of the sample 5; place the upper gold ring 6 on the sample 5; place the upper electrode 7 on the upper gold ring 6.

[0052] Step 2: Pass the bolt through the connection holes and channels and then fix it with the nut, and then the sample stage can be placed on the sample transfer rod in the cavity of the X-ray photoelectron spectroscopy equipment.

[0053] Step 3: Transfer the sample stage into the analysis chamber of the X-ray photoelectron spectroscopy instrument to achieve an in-situ test environment under different temperatures, different atmospheres, and external electric field polarization intensities, and start the in-situ test.

[0054] The present utility model can also combine the sample stage with a near-ambient pressure photoelectron spectroscopy equipment to realize the regulation of the atmosphere and pressure of the test environment.

[0055] In the present utility model, the base can be heated by infrared laser heating, electron beam, etc., so as to control the temperature of the sample in the temperature range from room temperature to 1073 K.

[0056] Specific application test cases are given below.

[0057] In the device research of solid oxide electrolytic cells, this sample stage is used to study the surface carbon deposition behavior of electrolytic cell devices under the actual electrolysis conditions of CO 2 . In-situ tests of X-ray photoelectron spectroscopy and impedance spectroscopy are carried out under different atmospheres and applied electric fields. The test data are as follows Figure 6 and Figure 7 shown. The in-situ X-ray photoelectron spectroscopy in-situ test is carried out on a SPECS system, where a gold ring is used to calibrate the binding energy position (binding energy (BE) = 84.0 eV). Before introducing the sample, the base pressure in the analysis chamber is ~1×10 -8 Torr. After the electron gun is aligned with the sample, the sample surface is cleaned in 1 mbar of oxygen at 400 °C. After cleaning, the chamber is evacuated again to ~1×10 -8 Torr, and then the gas is switched to 50% CO / 50% CO 2 for testing. The temperature is controlled by adjusting the power of the infrared laser heating installed on the back panel of the sample holder. The pressure in the chamber is 0.4 mbar. The results show that at 700 °C, no carbon deposition occurs on the surface of the perovskite cathode material under the condition of a mixed atmosphere of CO 2 / CO without applying a reduction bias. After applying a bias to the cathode surface, from the data of the impedance spectrum, it can be seen that as the bias increases in the negative direction, the value of the impedance spectrum on the X-axis becomes smaller, which means that an electrolysis reaction begins to occur on the device surface and the polarization impedance becomes smaller. When the bias is lower than -400 mV, the carbon deposition peak (285 eV) appears in the photoelectron spectroscopy diagram, and the intensity of this peak increases with time, indicating an increase in carbon deposition.

[0058] In summary, the present utility model can be used for in-situ testing of X-ray photoelectron spectroscopy of samples under high temperature, certain atmosphere, pressure, and applied voltage or current conditions, so as to better conduct in-depth research on disciplines such as solid electrochemistry, photoelectrochemistry, and thin film preparation.

Claims

1. A sample stand for in-situ testing of X-ray photoelectron spectroscopy for high temperature electrochemistry, characterized in that: It includes a base, a gasket, a lower electrode, a lower gold ring, an upper gold ring, and an upper electrode which are arranged in sequence from bottom to top; The sample is located between the upper and lower gold rings; The lower electrode and the upper electrode are both arranged in a ring structure, and the upper gold ring and the lower gold ring are located in the ring structure; The annular structure is extended outwardly to be provided with a contact portion so as to be connected with the instrument sample feeding tray and the thermocouple; A notch is provided on the inner periphery of the annular structure of the upper electrode to expose the upper gold ring; The base comprises a placement portion and a connecting portion provided at one end of the placement portion, wherein the connecting portion is used to be connected to the instrument sample introduction tray; the placement portion is used to place the gasket; The upper electrode and the lower electrode are made of stainless steel.

2. The X-ray photoelectron spectroscopy in-situ test sample platform for high temperature electrochemistry according to claim 1, characterized in that: A plurality of upwardly warped fixing parts are arranged on the outer periphery of the annular structure of the lower electrode.

3. The X-ray photoelectron spectroscopy in-situ test sample platform for high temperature electrochemistry according to claim 2, characterized in that: The fixing parts are provided with four and are arranged in a bilaterally symmetrical manner.

4. The X-ray photoelectron spectroscopy in-situ test sample stand for high temperature electrochemistry according to claim 1, characterized in that: The base is made of stainless steel.

5. The X-ray photoelectron spectroscopy in-situ test sample platform for high temperature electrochemistry according to claim 1, characterized in that: The gasket is made of ceramic material.

6. The X-ray photoelectron spectroscopy in-situ test sample stand for high temperature electrochemistry according to claim 1, characterized in that: The annular structures of the upper electrode and the lower electrode are both provided with corresponding connection holes extending outwards, and the base is provided with corresponding holes, and the upper electrode, the lower electrode and the base are connected by bolts and nuts.

7. The X-ray photoelectron spectroscopy in-situ test sample stand for high temperature electrochemistry according to claim 6, characterized in that: The connection holes are provided in three groups, and the positions of the three groups of connection holes are arranged in a triangle; one group of connection holes is arranged at the inward extension of the contact part.

8. The X-ray photoelectron spectroscopy in-situ test sample stand for high temperature electrochemistry according to claim 6, characterized in that: The invention also comprises a gasket, which is arranged at the connection between the upper electrode, the lower electrode and the base.

9. The X-ray photoelectron spectroscopy in-situ test sample stand for high temperature electrochemistry according to claim 8, characterized in that: The bolts, nuts and washers are made of ceramic material.

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