Method for removing high-surface-energy molecules adsorbed on surface of sample in X-ray photoelectron spectroscopy test
By transferring the sample stage to a petri dish of activated carbon and performing vacuum drying in a vacuum drying oven, the problem of difficulty in removing high surface energy molecules on the sample surface in the existing technology is solved, and effective cleaning and contamination of the sample surface is achieved. control.
Patent Information
- Application Number
- CN202411314227.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-20
- Publication Date
- 2025-01-24
AI Technical Summary
The prior art is difficult to effectively remove high surface energy molecules adsorbed on the sample surface without destroying the surface composition of the material, making it difficult to obtain real sample information and may contaminate instruments and other samples.
Transfer the sample stage to a Petri dish with activated carbon and vacuum dry it in a vacuum drying oven. Control the vacuum degree at -0.6~-1.0bar and the temperature at 40~70°C. Keep it for a certain period of time to remove high surface energy molecules. .
This method can minimize the residue of the adsorption molecules on the surface, reduce the pollution of the instrument analysis room and nearby samples, and does not cause any damage to the surface of the sample.
Smart Images
Figure CN119355019A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of material surface analysis and X-ray photoelectron spectroscopy analysis and testing, and specifically relates to a method for removing high surface energy molecules adsorbed on a sample surface in an X-ray photoelectron spectroscopy test. Background Art
[0002] The surface properties of materials play a vital role in technological innovation and social progress, and are the key to solving many important scientific problems. The chemical behavior and biological effects of elements are largely affected by their valence states, and detecting the valence states of elements is of great significance for studying material properties and applications. X-ray photoelectron spectroscopy (XPS) is the only surface analysis technology that can detect the elemental composition of the material surface and provide information on the valence state or chemical state of the elements on the material surface.
[0003] XPS technology is extremely sensitive to the elemental composition of 5 to 10 nm on the surface of the material. Since most samples are exposed to the atmosphere before XPS analysis, the surface is prone to adsorbing foreign pollutants, especially gas molecules with relatively high surface energy, such as chlorine. In order to obtain real information about the sample surface, the sample surface needs to be cleaned. The commonly used surface cleaning technology is ion beam etching (or sputtering); however, both single-atom ion beam etching and cluster ion beam etching will damage the sample surface; current surface cleaning technology is difficult to remove surface contamination caused by the adsorption of high surface energy molecules without destroying the surface components.
[0004] The adsorption of high surface energy molecules will affect the detection of the real surface of the sample on the one hand, and will also contaminate the analysis room of the instrument and other samples in the analysis room on the other hand, and may even cause unpredictable chemical reactions, which are difficult to accept in material analysis research; therefore, how to effectively remove the adsorbed molecules on the sample surface has always been a technical problem faced by the field of surface analysis. Summary of the invention
[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.
[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.
[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing.
[0008] In order to solve the above technical problems, the present invention provides the following technical solutions: comprising:
[0009] The sample stage with the high surface energy molecules attached is transferred to a culture dish with activated carbon; the culture dish is covered and then transferred to a vacuum drying oven to maintain the vacuum degree; after setting the temperature of the vacuum drying oven, vacuum drying is performed while maintaining the temperature.
[0010] As a preferred solution of the method for removing high surface energy molecules adsorbed on the sample surface in the X-ray photoelectron spectroscopy test of the present invention, the high surface energy molecules include one or more high surface energy molecules such as fluorine molecules, chlorine molecules, and bromine molecules.
[0011] As a preferred solution of the method for removing high surface energy molecules adsorbed on the sample surface in the X-ray photoelectron spectroscopy test of the present invention, the vacuum degree of the vacuum drying oven is -0.6 to -1.0 bar.
[0012] As a preferred solution of the method for removing high surface energy molecules adsorbed on the sample surface in the X-ray photoelectron spectroscopy test of the present invention, the temperature of the vacuum drying oven is 40-70°C.
[0013] As a preferred solution of the method for removing high surface energy molecules adsorbed on the sample surface in the X-ray photoelectron spectroscopy test of the present invention, the vacuum drying time is 4 to 8 hours.
[0014] Beneficial effects of the invention: The invention explores a method for removing high surface energy molecules adsorbed on the sample surface during X-ray photoelectron spectroscopy testing. The method can minimize the residue of adsorbed molecules on the surface and reduce the contamination of the instrument analysis room and nearby samples without causing any damage to the sample surface. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:
[0016] Figure 1 (a) A photo of the sample stage on which the sample is pasted; (b) A photo of the culture dish on which the sample stage and activated carbon are placed; (c) A photo of a vacuum drying oven with a vacuum degree of -0.8 bar and a temperature setting of 60°C.
[0017] Figure 2The XPS spectra of samples obtained by different treatment methods of the present invention are: 1# is the XPS spectrum corresponding to the sample with chlorine molecules adsorbed on the surface in Example 1, which is vacuum treated in the presence of activated carbon in an oven at 60°C; 2# is the XPS spectrum corresponding to the sample with chlorine molecules adsorbed on the surface and not desorbed in Comparative Example 1; 3# is the XPS spectrum corresponding to the sample with chlorine molecules adsorbed on the surface in Comparative Example 2, which is vacuum treated for 6 hours at room temperature; 4# is the XPS spectrum corresponding to the sample with chlorine molecules adsorbed on the surface in Comparative Example 3, which is treated with activated carbon in a semi-closed space for 6 hours; 5# is the XPS spectrum corresponding to the sample with chlorine molecules adsorbed on the surface in Comparative Example 4, which is vacuum treated in the presence of activated carbon at room temperature.
[0018] Figure 3 The XPS spectra of the Sb-containing samples with chlorine molecules adsorbed on the surface of the present invention are as follows: 1# is the sample treated by vacuum in the presence of activated carbon in a 60°C oven; 2# is the sample without desorption treatment; the boxes in the spectra compare the Cl 2p and Cl2s signals of the samples before and after treatment.
[0019] Figure 4 The XPS spectra of the Fe-containing samples with chlorine molecules adsorbed on the surface of the present invention are as follows: 1# is the sample treated by vacuum in the presence of activated carbon in a 60°C oven; 2# is the sample without desorption treatment; the boxes in the spectrum compare the Cl 2p and Cl2s signals of the samples before and after treatment. DETAILED DESCRIPTION
[0020] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.
[0021] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0022] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.
[0023] The raw materials used in the present invention are all commercially available unless otherwise specified.
[0024] Sample preparation: Paste the sample (powder sample tablet) with high surface energy molecules (chlorine molecules) adsorbed on the surface on the sample stage;
[0025] Sample transfer: Slowly open the vent of the vacuum drying oven, wait for the internal and external air pressures to be balanced, then open the drying oven door; transfer the sample stage to the XPS instrument injection chamber and start vacuuming; wait until the vacuum degree of the injection chamber is better than 1×10 -7 mbar, the sample stage is transferred to the instrument analysis room;
[0026] Set up the test procedure: The vacuum degree of the analysis chamber should be better than 1×10 -8 mbar, set up the test program on the instrument control computer: (1) Set the X-ray source to "Mono Anode (XR6)" monochromatized aluminum target, and select "Momo 500μm" for the spot size; (2) Add a test point Point, and select "Standard Electrostatic" for Lens Mode; (3) Select "ChargeComp Electrostatic" for nuclear power neutralization Beam Mode; (4) Add a full spectrum Survey, select "150" for Pass Energy (eV), fill in "2" for Number of Scans, and select "Standard Electrostatic" for Lens Mode; (5) Add Gun Shutdown;
[0027] Sample test: Select "Point" in the test program, adjust the sample to move up, down, left, and right, find a flat non-edge area, and set it as the test point; adjust the sample height (Z axis), focus on the best field of view, and after adjusting the height, check "DefinedPoint" and "Enable Auto-Height", click the "Read" and "Apply" buttons; perform the test according to the set program, and after the test is completed, save the data and turn off the X-ray gun, neutralization gun and etching ion gun;
[0028] Data processing and analysis: Convert the data into EXCEL format for export, and use the corresponding data to make XPS spectra.
[0029] Example 1
[0030] This example tests the removal effect of a sample with chlorine adsorbed on its surface after vacuum treatment in a 60° C. oven in the presence of activated carbon.
[0031] The sample obtained through the above preparation process in this example is marked as sample 1#;
[0032] Sample processing: transfer the sample table to a culture dish containing 1.0g of activated carbon; cover the culture dish and transfer it to a vacuum drying oven and close the door and vent holes; turn on the vacuum pump of the drying oven to evacuate the sample; when the vacuum degree reaches -0.8bar, turn off the vacuum pump and maintain the vacuum degree; set the temperature of the vacuum drying oven to 60℃ and maintain vacuum drying at this temperature for 6h;
[0033] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0034] Figure 2 Figure 1# is the XPS spectrum obtained from the test of the sample in this example.
[0035] Comparative Example 1
[0036] This comparative example is based on the sample whose surface is adsorbed with chlorine and has not been subjected to desorption treatment.
[0037] The sample obtained through the above preparation process in this comparative example is marked as sample 2#;
[0038] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0039] Figure 2 The XPS spectrum of sample 2# is obtained from the test of this comparative example.
[0040] Comparative Example 2
[0041] This comparative example is used to test the removal effect of chlorine adsorbed on the surface of the sample after vacuuming for 6 hours at room temperature.
[0042] The sample obtained through the above preparation process in this comparative example is marked as sample 3#;
[0043] Sample processing: transfer the sample table to a culture dish without activated carbon; cover the culture dish and transfer it to a vacuum drying oven and close the door, close the vent, and turn on the vacuum pump of the drying oven to evacuate; when the vacuum degree reaches -0.8 bar, turn off the vacuum pump and maintain the vacuum for 6 hours;
[0044] Sample transfer, test procedure setting, and sample testing step process all refer to the above contents.
[0045] Data processing and analysis: The data was converted into EXCEL format and exported. Figure 2 As shown in Figure 3#, compared with the untreated sample spectrum of Figure 2#, the Cl 2p and Cl 2s peak intensities are reduced by about 50%, indicating that vacuuming can reduce the adsorption of chlorine molecules on the sample surface.
[0046] Figure 2 The 3# in the middle is the XPS spectrum obtained from the test of the sample of this comparative example.
[0047] Comparative Example 3
[0048] This comparative example is used to test the removal effect of samples with surface adsorbed chlorine after being treated with activated carbon in a semi-closed space for 4 hours.
[0049] The sample obtained through the above preparation process in this comparative example is marked as sample 4#;
[0050] Sample treatment: transfer the above sample stage to a culture dish, put activated carbon in the culture dish, cover the culture dish with a lid, and keep it for 4 hours;
[0051] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0052] Figure 2 The XPS spectrum of sample 4# is obtained from the test of this comparative example.
[0053] Comparative Example 4
[0054] This comparative example is used to test the removal effect of a sample with chlorine adsorbed on its surface after vacuum treatment in the presence of activated carbon at room temperature.
[0055] The sample obtained through the above preparation process in this comparative example is marked as sample 5#;
[0056] Sample processing: transfer the sample table to a culture dish, put activated carbon in the culture dish, and cover the culture dish with a lid; transfer the covered culture dish to a vacuum drying oven, close the door, and close the vent; start the vacuum pump of the vacuum drying oven to evacuate the vacuum until the vacuum reaches -0.8 bar, then turn off the vacuum pump and maintain the vacuum for 6 hours;
[0057] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0058] Figure 2 The XPS spectrum of sample 5# is obtained from the test of this comparative example.
[0059] Example 2
[0060] The difference between this embodiment and embodiment 1 is that the vacuum degree of the vacuum drying oven is adjusted to -0.6 bar and -1.0 bar, and the remaining steps and processes are all referred to embodiment 1. Experimental results show that there is no obvious difference between the XPS spectrum of the samples treated under the vacuum degree of -0.6 bar or -1.0 bar and the XPS spectrum of the samples treated under the vacuum degree of -0.8 bar.
[0061] Comparative Example 5
[0062] The difference between this comparative example and Example 1 is that the vacuum degree of the vacuum drying oven is adjusted to -0.5 bar and -1.1 bar, and the remaining steps and processes are all referred to Example 1. The XPS spectrum shows that when the vacuum degree is -0.5 bar and -1.1 bar, a large amount of chlorine molecules adsorbed on the sample surface cannot be effectively removed.
[0063] Example 3
[0064] The difference between this embodiment and embodiment 1 is that the temperature of the vacuum drying oven is adjusted to 40°C and 70°C, and the remaining steps and processes are all referred to embodiment 1. The experimental results show that there is no obvious difference between the XPS spectra of the samples treated at a drying oven temperature of 40°C or 70°C and the XPS spectra of the samples treated at a drying oven temperature of 60°C.
[0065] Comparative Example 6
[0066] The difference between this comparative example and Example 1 is that the temperature of the vacuum drying oven is adjusted to 30°C and 70°C, and the remaining steps and processes are all referred to Example 1. The XPS spectrum shows that when the temperature of the drying oven is 30°C and 70°C, a large amount of chlorine molecules adsorbed on the sample surface cannot be effectively removed.
[0067] Example 4
[0068] The difference between this embodiment and embodiment 1 is that the vacuum drying time is adjusted to 4h and 8h, and the remaining steps and processes are all referred to embodiment 1. The experimental results show that there is no obvious difference between the XPS spectrum of the sample obtained by vacuum drying time of 4h or 8h and the XPS spectrum of the sample obtained by vacuum drying time of 6h.
[0069] Comparative Example 7
[0070] The difference between this comparative example and Example 1 is that the vacuum drying time is adjusted to 3h and 9h, and the remaining steps and processes are all referred to Example 1. The XPS spectrum shows that when the vacuum drying time is 3h and 9h, a large amount of chlorine molecules adsorbed on the sample surface cannot be effectively removed.
[0071] Example 5
[0072] This example tests the removal effect of a Sb-containing sample with chlorine molecules adsorbed on its surface after vacuum treatment in an oven at 60° C. in the presence of activated carbon.
[0073] The sample obtained through the above preparation process in this example is marked as sample 1#;
[0074] The sample processing, sample transfer, test program setting, sample testing, data processing and analysis steps and processes are all based on Example 1.
[0075] Figure 3 Figure 1# is the XPS spectrum obtained from the test of the sample in this example.
[0076] Comparative Example 8
[0077] This comparative example is to test the Sb-containing sample whose surface adsorbs chlorine molecules and has not been subjected to desorption treatment.
[0078] The sample obtained through the above preparation process in this comparative example is marked as sample 2#;
[0079] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0080] Figure 3 The XPS spectrum of sample 2# is obtained from the test of this comparative example.
[0081] Example 6
[0082] This example tests the removal effect of a Fe-containing sample with chlorine molecules adsorbed on its surface after vacuum treatment in an oven at 60° C. in the presence of activated carbon.
[0083] The sample obtained through the above preparation process in this example is marked as sample 1#;
[0084] The sample processing, sample transfer, test program setting, sample testing, data processing and analysis steps and processes are all based on Example 1.
[0085] Figure 4 Figure 1# is the XPS spectrum obtained from the test of the sample in this example.
[0086] Comparative Example 9
[0087] This comparative example is to test the Fe-containing sample on the surface of which chlorine molecules are adsorbed and no desorption treatment is performed.
[0088] The sample obtained through the above preparation process in this comparative example is marked as sample 2#;
[0089] The sample transfer, test procedure setting, sample testing, data processing and analysis steps and processes all refer to the above contents.
[0090] Figure 4 The XPS spectrum of sample 2# is obtained from the test of this comparative example.
[0091] From the XPS full spectrum of the above samples, it can be seen that the spectrum of the untreated sample ( Figure 2 Middle 2#, Figure 3 Zhong 2# and Figure 4 There are obvious Cl 2p (~200eV) and Cl 2s (~270eV) signals in both samples (2#), indicating that a large number of chlorine molecules are adsorbed on the sample surface. Comparing the XPS data of samples treated in different ways, it is clear that the presence of activated carbon, vacuum treatment and appropriate increase in temperature are three important conditions for the effective desorption of high surface energy molecules.
[0092] From the effects of the above embodiments, it can be seen that the method for removing adsorbed molecules on the surface of a material disclosed in the present invention is simple to operate, low in cost, has low requirements for experimental conditions, and more importantly, has a significant removal effect and has exciting application potential.
[0093] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.
Claims
1. A method for removing high surface energy molecules adsorbed on the surface of a sample in an X-ray photoelectron spectroscopy test, characterized in that: include, The sample stage with the sample attached is transferred to the culture dish containing activated carbon; After the culture dish is covered, it is transferred to a vacuum drying oven and the vacuum degree is maintained; after the temperature of the vacuum drying oven is set, vacuum drying is performed at the temperature to remove the high surface energy molecules adsorbed on the sample surface.
2. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 1, characterized in that: The high surface energy molecules include one or more of high surface energy molecules such as fluorine molecules, chlorine molecules, and bromine molecules.
3. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 1, characterized in that: The vacuum degree of the vacuum drying oven is -0.6 to -1.0 bar.
4. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 3, characterized in that: The vacuum degree of the vacuum drying oven is -0.7 to -0.9 bar.
5. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 1, characterized in that: The temperature of the vacuum drying oven is 40-70°C.
6. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 5, characterized in that: The temperature of the vacuum drying oven is 50-60°C.
7. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 1, characterized in that: The vacuum drying time is 4 to 8 hours.
8. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claim 7, characterized in that: The vacuum drying time is 5 to 7 hours.
9. The method for removing high surface energy molecules adsorbed on the sample surface in X-ray photoelectron spectroscopy testing according to claims 1 to 8, characterized in that: The method can remove the residual adsorbed molecules on the sample surface without causing any damage to the sample surface.