In-situ sample stage for high temperature electrochemistry x-ray photoelectron spectroscopy and its applications

Abstract

The application discloses an in-situ test sample stage for X-ray photoelectron spectroscopy of high-temperature electrochemistry and application thereof, which comprises, from bottom to top, a base, a gasket, a lower electrode, a lower gold ring, an upper gold ring and an upper electrode; a sample is located between the upper gold ring and the lower gold ring; 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; the ring structure is outwardly extended with a contact part so as to be connected with an instrument sample holder and a thermocouple; and an inner periphery of the ring structure of the upper electrode is provided with a notch so as to expose the upper gold ring. The application can be used for in-situ test of X-ray photoelectron spectroscopy of a sample under conditions of high temperature, a certain atmosphere and pressure and an applied voltage or current, so that the fields of solid-state electrochemistry, photoelectrochemistry and thin film preparation can be better researched.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photoelectron spectroscopy analysis testing, and particularly relates to an X-ray photoelectron spectroscopy in-situ testing sample stage for high-temperature electrochemistry and application thereof. BACKGROUND

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

[0003] In a general X-ray photoelectron spectrometer, 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. As can be seen, the X-ray photoelectron spectroscopy technology is a method that can analyze all elements once, which is very effective for qualitative analysis of unknown substances. After X-ray irradiation, the intensity of the photoelectrons emitted from the surface of the sample is linearly related to 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 not only related to the concentration of the atoms, but also related to the average free path of the photoelectrons, the surface roughness of the sample, the chemical state of the element, the intensity of the X-ray source and the state of the instrument, therefore, the X-ray photoelectron spectroscopy technology generally cannot give the absolute content of the analyzed element, and can only provide the relative content of each element. It should be noted that X-ray photoelectron spectroscopy is a surface-sensitive analysis method with high surface detection sensitivity, which can reach 10 -3 atomic monolayer, but the bulk detection sensitivity is only about 0.1%.

[0004] X-ray photoelectron spectroscopy (XPS) can sample surfaces at depths ranging from 1 to 10 nanometers. An X-ray photoelectron spectrometer primarily consists of five components: 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 varying energy distributions. These electrons are then analyzed by the electron energy analyzer, and the detection system provides the test results. The entire system requires an UHV system. Furthermore, X-ray photoelectron spectroscopy (XPS) is non-destructive, pollution-free, fast, and offers high measurement accuracy. Therefore, it has become one of the most important tools for studying material surface science and is widely used in academic fields such as chemical analysis, materials development and application research, and physics research, as well as in industrial fields such as machining, printed circuit technology, process control of coating materials, and the development of nanofunctional materials. The booming development of near-ambient-pressure photoelectron spectroscopy (NAPPS) has further narrowed the pressure gap in PPS, extending the PPS testing environment from a single UHV to near-ambient-pressure environments, further broadening the application of PPS.

[0005] However, most current commercial photoelectron spectroscopy sample stages are unable to simultaneously meet the requirements for in-situ testing of samples at high temperatures, in a specific atmosphere, and under applied voltage or current. Furthermore, due to limitations in sample stage size and instrument structure, very few sample stages exist that can simultaneously meet these requirements for four-probe testing. The challenge of achieving a stable output voltage or current to the sample on a limited sample stage, as well as real-time input and output of electrical signals at high temperatures and in a specific atmosphere, while simultaneously revealing in situ the electrochemical and photoelectrochemical properties and surface physicochemical changes of the sample under test, remains both a difficult and a hot topic in current research. Summary of the Invention

[0006] The purpose of the present invention is to provide a sample stage for in-situ testing of X-ray photoelectron spectroscopy and its application, so as to solve the problem that the sample stage in the prior art cannot achieve stable output of sample voltage or current in an environment with high temperature and certain atmospheric conditions.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A sample stand for in-situ testing of X-ray photoelectron spectroscopy 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 and lower gold rings;

[0010] 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;

[0011] The annular structure is provided with a contact portion extending outwardly to facilitate connection with the instrument sample feed tray and the thermocouple;

[0012] A notch is provided on the inner periphery of the annular structure of the upper electrode to expose the upper gold ring.

[0013] The base includes 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; and the placement portion is used to place the gasket.

[0014] A plurality of upwardly curved fixing portions are provided on the outer periphery of the annular structure of the lower electrode.

[0015] There are four fixing parts, which are arranged in a bilaterally symmetrical manner.

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

[0017] 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.

[0018] There are three groups of connection holes, 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.

[0019] The present invention further comprises a gasket, which is arranged at the connection between the upper electrode, the lower electrode and the base.

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

[0021] The application of the X-ray photoelectron spectroscopy in-situ test sample stage for high-temperature electrochemistry is to install the sample stage in a photoelectron spectrometer to realize an in-situ test environment under different temperatures and external electric field polarization intensities, or to combine the sample stage with a near-normal-pressure photoelectron spectroscopy device to realize the regulation of the atmosphere and pressure of the test environment to realize in-situ X-ray photoelectron spectroscopy testing of the sample.

[0022] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0023] 1. Expanding the application scope of X-ray photoelectron spectroscopy: This invention provides an in-situ X-ray photoelectron spectroscopy (XPS) sample stage capable of high temperature, a specific atmosphere and pressure, and applied voltage or current. This significantly expands the application scope of traditional XPS technology. This allows researchers to conduct in-depth studies of samples under conditions closer to actual working environments, improving the authenticity and reliability of their research.

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

[0025] 3. Enhanced Stability and Reliability of Sample Testing: The compact sample stage of this invention utilizes high-temperature and corrosion-resistant materials such as stainless steel and ceramic, ensuring long-term stable operation under high-temperature and complex atmospheres. Furthermore, the tight connection of bolts, nuts, and washers further enhances the stability of the sample stage, reducing vibration and drift during testing and improving the accuracy and reliability of test data.

[0026] 4. Support for Multiple Testing Environments: This sample stage not only supports testing in traditional ultra-high vacuum environments, but can also be combined with near-ambient pressure photoelectron spectroscopy equipment to achieve control of the test environment atmosphere and pressure. This flexibility allows researchers to select the appropriate testing environment based on their research needs, resulting in more comprehensive and in-depth research results.

[0027] 5. Improved experimental efficiency: The sample stage of the present invention has an ingenious structural design, making it easy to disassemble and replace samples. At the same time, by controlling the voltage and current intensity through external instruments, test parameters can be easily adjusted, greatly improving experimental efficiency and research progress.

[0028] 6. Promotes the R&D and application of new materials: In the fields of materials science and engineering, the R&D and application of new materials often require in-depth studies of the surface and interface properties of materials. The sample stage of this invention provides a powerful tool for such research, enabling researchers to more precisely control testing conditions and reveal the physical and chemical changes on the material surface and interface, providing strong support for the R&D and application of new materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the decomposition structure of the present invention;

[0030] Figure 2 It is a schematic diagram of the overall structure of the present invention;

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

[0032] Figure 4 Schematic diagram of the structure of the lower electrode;

[0033] Figure 5 Schematic diagram of the structure of the upper electrode;

[0034] Figure 6This is the C1s photoelectron spectrum of the cathode surface of the solid oxide electrolysis cell;

[0035] Figure 7 This is the impedance spectrum of the solid oxide electrolytic cell. DETAILED DESCRIPTION

[0036] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0037] like Figures 1 to 5 As shown, in this embodiment, a sample platform for in-situ testing of high-temperature electrochemistry using X-ray photoelectron spectroscopy 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, which are arranged in sequence from bottom to top;

[0038] The sample 5 is located between the upper gold ring 6 and the lower gold ring 4; thus, the upper and lower gold rings act as current collectors by being in physical contact with the sample;

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

[0040] The annular structure extends outwardly and is provided with a contact portion to facilitate connection with the instrument sample holder and thermocouple. Specifically, the lower electrode 3 is provided with a contact portion 31, and the upper electrode 7 is provided with a contact portion 71. In this way, the entire sample stage can form a loop, and voltage and current signals can be input and output simultaneously. The applied voltage and current intensity can be controlled by an external instrument to achieve in-situ X-ray photoelectron spectroscopy testing of the sample.

[0041] The inner periphery of the annular structure of the upper electrode 7 is provided with a notch 72 to expose the upper gold ring 6;

[0042] The base 1 includes a placement portion 11 and a connecting portion 12 provided at one end of the placement portion 11, wherein the connecting portion 12 is used to connect to the instrument sample tray; the placement portion 11 is used to place the gasket 2;

[0043] The outer periphery of the annular structure of the lower electrode 3 is provided with a plurality of fixing portions 32 that are bent upward at a certain angle. In this embodiment, there are four fixing portions 32, which are arranged symmetrically. In this way, the fixing portions can easily fix the sample and realize the sample rotation at any angle relative to the base 1.

[0044] The annular structures of the upper electrode 7 and the lower electrode 3 are both provided with corresponding connection holes extending outward, and the base is provided with corresponding channels, and 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 shape; one group of connection holes is provided at the inward extension of the contact part.

[0046] This embodiment also includes a gasket 8, which is provided 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; the thickness of the gasket 8 is selected according to the thickness of the sample, such as 1 mm, 2 mm, 2.5 mm, etc. The matching mode of the gasket 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, upper electrode and lower electrode are made of stainless steel; the gasket, bolts, nuts and washers are made of ceramic.

[0048] In this embodiment, the notch 72 may be arranged in a semicircular shape to facilitate exposing the upper gold ring 6 , thereby enabling data correction during in-situ X-ray photoelectron spectroscopy testing of the sample.

[0049] The fixing portion 32 can adjust the warping angle according to different shapes of the sample, which is not limited here.

[0050] The steps for performing in-situ X-ray photoelectron spectroscopy testing using the above-mentioned 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 on the ring 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, and select a suitable gasket 8 according to the thickness of the sample 5; place the upper gold ring 6 on the sample 5; and place the upper electrode 7 on the upper gold ring 6.

[0052] Step 2: Pass the bolts through the connecting holes and the channels and secure them with the nuts. Then, place the sample stage onto the sample transfer rod in the cavity of the X-ray photoelectron spectroscopy equipment.

[0053] Step 3: The sample stage is introduced into the analysis cavity of the X-ray photoelectron spectrometer to realize the in-situ test environment under different temperatures, different atmospheres and external electric field polarization intensities, and start the in-situ test.

[0054] The present invention can also combine the sample stage with a near-normal-pressure photoelectron spectroscopy device to achieve regulation of the atmosphere and pressure of the test environment.

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

[0056] The following is a specific application test example.

[0057] In the device research of solid oxide electrolysis cell, this sample stage was used to study the surface carbon deposition behavior of electrolysis cell devices under the actual electrolysis conditions of CO2. In-situ X-ray photoelectron spectroscopy and impedance spectroscopy were performed under different atmospheres and applied electric fields. The test data are as follows Figure 6 and Figure 7 In situ X-ray photoelectron spectroscopy (XPS) measurements were performed on a SPECS system, where a gold ring was used to calibrate the binding energy position (binding energy (BE) = 84.0 eV). Before the sample was introduced, the base pressure in the analysis chamber was ~1×10 -8 After the electron gun was aligned with the sample, the sample surface was cleaned in 1 mbar oxygen at 400 °C. After cleaning, the chamber was evacuated to 1 × 10 -8 Torr, and then the gas was switched to 50% CO / 50% CO2 for testing. The temperature was controlled by adjusting the power of the infrared laser heating installed on the back plate of the sample holder. The pressure in the chamber was 0.4 mbar. The results show that at 700°C, no carbon deposition occurred on the surface of the perovskite cathode material in a mixed atmosphere of CO2 / CO without applying a reducing bias. After applying a bias to the cathode surface, it can be seen from the impedance spectrum data that as the bias increases in the negative direction, the value of the impedance spectrum on the X-axis becomes smaller, which means that electrolysis reaction begins to occur on the surface of the device and the polarization impedance becomes smaller. When the bias is lower than -400mV, the carbon deposition peak (285eV) in the photoelectron energy spectrum begins to appear, and the peak intensity increases with time, which means that carbon deposition increases.

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

Claims

1. A sample stand for in-situ testing of high-temperature electrochemical X-ray photoelectron spectroscopy, characterized by: It includes a base, a gasket, a lower electrode, a lower gold ring, an upper gold ring, and an upper electrode arranged in sequence from bottom to top; The base includes a placement portion and a connecting portion provided at one end of the placement portion, wherein the connecting portion is used to connect to the instrument sample tray; the placement portion is used to place the gasket; 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 provided with a contact portion extending outwardly to facilitate connection with the instrument sample feed 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 outer periphery of the annular structure of the lower electrode is provided with a plurality of upwardly warped fixing portions; The annular structures of the upper and lower electrodes are each provided with corresponding connecting holes extending outward, and the base is provided with corresponding holes, and the upper and lower electrodes and the base are connected by bolts and nuts; the connecting holes are provided in three groups, and the positions of the three groups of connecting holes are arranged in a triangular shape; one group of connecting holes is provided at the inward extension of the contact portion; The invention also includes a gasket, which is arranged at the connection between the upper electrode, the lower electrode and the base.

2. The X-ray photoelectron spectroscopy in-situ test sample stand for high-temperature electrochemistry according to claim 1, characterized in that: There are four fixing parts, which are arranged in a bilaterally symmetrical manner.

3. The X-ray photoelectron spectroscopy in-situ test sample stand for high-temperature electrochemistry according to claim 1, characterized in that: The base, upper electrode and lower electrode are made of stainless steel; the gasket is made of ceramic.

4. The X-ray photoelectron spectroscopy in-situ test sample stand for high-temperature electrochemistry according to claim 1, characterized in that: The bolts, nuts and washers are made of ceramic material.

5. Use of the sample stand for in-situ testing of high-temperature electrochemical X-ray photoelectron spectroscopy according to any one of claims 1 to 4, characterized in that: The sample stage is installed in a photoelectron spectrometer to realize an in-situ test environment under different temperatures and external electric field polarization intensities, or the sample stage is combined with a near-normal pressure photoelectron spectroscopy device to realize the regulation of the atmosphere and pressure of the test environment, so as to realize in-situ X-ray photoelectron spectroscopy testing of the sample.

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