Tungsten oxide nano-film prepared by modulating reaction atmosphere magnetron sputtering and preparation method of tungsten oxide nano-film

Abstract

The invention provides a tungsten oxide nano-film prepared by magnetron sputtering in a modulation reaction atmosphere and a preparation method thereof. The preparation method comprises the following steps: cleaning and drying a substrate; fixing the dried substrate on a sample support, and mounting the sample support on a sample table; vacuumizing the sputtering chamber and the deposition chamber at the same time; adjusting the distance between the target material and the nozzle in the sputtering chamber, so that the distance between the target material and the nozzle is 95-120 cm; the height of the sample support is adjusted in the deposition chamber through a lifting table; heating the substrate on the sample table; coating the heated sample with a film; and after coating is finished, completely opening the gate valve of the sputtering chamber and the gate valve of the deposition chamber, vacuumizing the chamber to a high-vacuum state, keeping the high-vacuum state for 2-3 minutes, turning off a heating power supply, and cooling the sample to room temperature. The method has the technical effects that the tungsten oxide nanocrystalline film which is consistent in grain size, compact in structure, uniform and flat and high in film-substrate binding force can be obtained on the surface of the substrate, and the method has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of thin film and high-energy beam processing technology, specifically relating to a tungsten oxide nanofilm prepared by magnetron sputtering in a modulated reactive atmosphere and its preparation method. Background Technology

[0002] Tungsten oxide thin films, with their unique crystal structure and chemical bonds, possess excellent physicochemical properties. Even under extreme conditions such as strong acids, strong alkalis, or high temperatures, they retain their original physical and chemical characteristics. Furthermore, their mechanical properties are also remarkable; high hardness and high toughness allow them to withstand certain external impacts and remain intact. These diverse properties make tungsten oxide thin films highly valuable for applications. In recent years, an increasing number of researchers have focused on the preparation of tungsten oxide nanocrystalline thin films. Their nanocrystalline structure can significantly improve the mechanical strength and high-temperature resistance of the films, making them suitable for surface strengthening of precision mechanical parts, high-temperature protection, and refractory coatings, showing broad application prospects.

[0003] Magnetron sputtering is widely used in the preparation of metal oxide materials, and reactive magnetron sputtering using metal targets offers advantages such as rapid deposition and easy adjustment of material composition. However, the preparation of metal oxides using reactive magnetron sputtering is relatively complex. Deposition conditions such as sputtering power, working pressure, reactive gas flow rate, and substrate temperature are interdependent and interact with each other on the prepared oxide film. Determining these interactions and their corresponding control over the oxide structure is crucial but remains unclear, leading to a narrow process window and insufficient reproducibility.

[0004] Therefore, how to precisely control the oxidation reaction and nucleation growth during the deposition process has become a key issue that urgently needs to be addressed. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art, and to provide a new technical solution for preparing tungsten oxide nanofilms by magnetron sputtering in a modulated reactive atmosphere and the preparation method thereof.

[0006] According to a first aspect of the present invention, a method for preparing tungsten oxide nanofilms by magnetron sputtering in a modulated reactive atmosphere is provided, comprising the following steps:

[0007] Step S1: Cleaning and drying of the substrate;

[0008] Step S2: Fix the dried substrate at the center of the sample holder and install the sample holder on the sample stage of the deposition chamber;

[0009] S3, vacuumize the sputtering chamber and the deposition chamber at the same time, and set the sputtering chamber plug valve opening degree to 10%-15% and the deposition chamber plug valve opening degree to 40%-50%;

[0010] S4, adjust the distance between the target material and the nozzle in the sputtering chamber so that the distance between the target material and the nozzle is 95cm-120cm; adjust the height of the sample holder in the deposition chamber through the lifting platform so that the height of the sample table is 60cm-70cm;

[0011] S5, heat the substrate on the sample table;

[0012] S6, coat the heated sample; wherein the gas pressure in the coating process is 40-80Pa, the ratio of Ar to He is 1:1, the substrate bias is 5KV-8KV, the magnetron sputtering power is 200W-250W, and the oxygen flow is 0.5sccm-2sccm;

[0013] S7, after the coating is completed, fully open the plug valves of the sputtering chamber and the deposition chamber, and vacuumize the chamber to a high vacuum state and maintain for 2min-3min, turn off the heating power, and after the sample cools to room temperature, take out the sample.

[0014] Optionally, in step S1, the cleaning and drying of the substrate includes:

[0015] After ultrasonic cleaning of the substrate, place it in a vacuum drying box for use.

[0016] Optionally, in step S2, the substrate is fixed at the center position of the sample holder by using a high-temperature adhesive tape.

[0017] Optionally, in step S5, the heating temperature is 550℃-700℃.

[0018] Optionally, in step S1, the substrate cleaning process is: place the substrate in a beaker and completely immerse it in anhydrous ethanol in the beaker; wherein the anhydrous ethanol in the beaker is 25-30ml, and the ultrasonic cleaning time is 15-20min.

[0019] Optionally, in step S1, the temperature of the vacuum drying box is set to 50℃.

[0020] Optionally, in step S3, after vacuumizing the sputtering chamber and the deposition chamber, the vacuum degree of the sputtering chamber and the deposition chamber is less than 5.5x10 -5 Pa, and is maintained for 2min-4min.

[0021] Optionally, in step S6, the thin film deposition time is 40-60min.

[0022] Optionally, in step S6, the reaction atmosphere is oxygen, and the oxygen injection port is far away from the sputtering chamber.

[0023] According to a second aspect of the present application, a tungsten oxide nanometer film prepared by modulated reaction atmosphere magnetron sputtering is provided, which is prepared by the preparation method according to the first aspect.

[0024] One technical effect of the present application is that:

[0025] In the embodiments of the present application, the tungsten oxide nanometer film is prepared by modulated reaction atmosphere magnetron sputtering technology. Compared with the traditional coating process, the sputtering process and the oxidation deposition process are separated by using the oxygen injection port, the oxygen content of the film reaction and the nucleation process of the tungsten oxide are controlled, the microstructure of the coating is controlled, excellent film-substrate adhesion is obtained, and the coating internal stress is reduced, the film layer density and uniformity are improved, and the particle size and film thickness can be controlled by changing the parameter conditions.

[0026] In addition, the tungsten oxide nanocrystal film prepared by the preparation method of the tungsten oxide nanometer film prepared by modulated reaction atmosphere magnetron sputtering can be used in the technical fields of precision part surface strengthening, high-temperature structure protection, fireproof coating, etc., and has broad application prospects in industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 FIG. 1 is a flowchart of a preparation method of a tungsten oxide nanometer film prepared by modulated reaction atmosphere magnetron sputtering according to an embodiment of the present application;

[0028] Figure 2 FIG. 4 is an AFM test diagram of a sample prepared under the process parameters of an embodiment of the present application.

[0029] Figure 3 FIG. 5 is an SEM test diagram of a sample prepared under the process parameters of an embodiment of the present application. DETAILED DESCRIPTION

[0030] Various exemplary embodiments of the present application will now be described in detail with reference to the accompanying drawings. Note that the relative arrangement, numerical expressions, and numerical values of the components and steps set forth in these embodiments are not limiting to the scope of the present application unless otherwise specifically stated.

[0031] The embodiments of this application will now be described in detail. Examples of these embodiments are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0032] According to a first aspect of the invention, see Figure 1 This invention provides a method for preparing tungsten oxide nanofilms by magnetron sputtering in a modulated reaction atmosphere. The method provides a modulated microreaction atmosphere in which oxidation reaction preferentially occurs and the oxidation reaction process is precisely controlled. This method effectively solves the problem of how to increase the oxygen content and uniformity in the tungsten oxide film, thereby obtaining a dense, uniform, and flat tungsten oxide nanocrystalline film with high film-substrate adhesion on the substrate surface, which has good application prospects.

[0033] Specifically, the method for preparing tungsten oxide nanofilms using magnetron sputtering in a modulated reactive atmosphere includes the following steps:

[0034] Step S1: Cleaning and drying of the substrate;

[0035] Step S2: Fix the dried substrate at the center of the sample holder and install the sample holder on the sample stage of the deposition chamber;

[0036] Step S3: Simultaneously evacuate the sputtering chamber and the deposition chamber, and set the opening of the sputtering chamber gate valve to 10%-15% and the opening of the deposition chamber gate valve to 40%-50%.

[0037] Step S4: Adjust the distance between the target and the nozzle in the sputtering chamber to 95cm-120cm; adjust the height of the sample holder in the deposition chamber using the lifting platform to make the sample stage height 60cm-70cm.

[0038] Step S5: Heat the substrate on the sample stage;

[0039] Step S6: Coating the heated sample; wherein the gas pressure during the coating process is 40-80Pa, the ratio of Ar to He is 1:1, the substrate bias voltage is 5KV-8KV, the magnetron sputtering power supply power is 200W-250W, and the oxygen flow rate is 0.5sccm-2sccm.

[0040] Step S7: After the coating is completed, fully open the gate valves of the sputtering chamber and the deposition chamber, evacuate the chamber to a high vacuum state and maintain it for 2-3 minutes, turn off the heating power, and take out the sample after it cools to room temperature.

[0041] In the embodiments of the present application, the tungsten oxide nanometer film is prepared by modulating the reaction atmosphere magnetron sputtering technology. Compared with the traditional film plating process, the oxygen content of the film can be controlled, and the nucleation process of tungsten oxide can be controlled. The microstructure of the film can be controlled, excellent film-substrate adhesion can be obtained, and the film has significant technical advantages in reducing the internal stress of the film, improving the density and uniformity of the film, and controlling the particle size and film thickness by changing the parameter conditions.

[0042] In addition, the tungsten oxide nanometer film prepared by the preparation method of the tungsten oxide nanometer film prepared by modulating the reaction atmosphere magnetron sputtering can be used in the technical fields of precision part surface strengthening, high-temperature structure protection, fireproof coating, etc., and has broad application prospects in industrial application.

[0043] Optionally, in step S1, the cleaning and drying of the substrate include:

[0044] After the substrate is ultrasonically cleaned, it is placed in a vacuum drying box for use.

[0045] In the above embodiments, the cleaning effect of the substrate is improved. In the present application, the substrate is a base body.

[0046] Optionally, in step S2, the substrate is fixed at the center position of the sample holder by using a high-temperature adhesive tape. This can better ensure the fixing effect of the substrate.

[0047] Optionally, in step S5, the heating temperature is 550-700℃. This can significantly enhance the interaction between the film and the substrate, promote atomic-level diffusion and interface reaction, and thus improve the adhesion of the film. Moreover, during the deposition process, internal stress may occur in the film, especially when it is rapidly deposited under this temperature condition, which helps to release these stresses and reduce cracks and other defects in the film.

[0048] In addition, this temperature condition can help activate the atomic mobility, so that the deposited atoms can move more freely on the surface of the substrate, thereby forming larger and more regular grain structures. This not only improves the density of the film, but also may improve its mechanical and electrical properties.

[0049] Optionally, in step S1, the substrate cleaning process is as follows: the substrate is placed in a beaker and completely immersed in anhydrous ethanol in the beaker; wherein the anhydrous ethanol in the beaker is 25-30ml, and the ultrasonic cleaning time is 15-20min. This helps to ensure the cleanliness of the substrate cleaning and the safety of the cleaning process.

[0050] Optionally, in step S1, the temperature of the vacuum drying box is set to 50℃. This helps to quickly dry the cleaned substrate.

[0051] Optionally, in step S3, after the sputtering chamber and the deposition chamber are vacuumized, the vacuum degree of the sputtering chamber and the deposition chamber is less than 5.5*10 -5 Pa and is maintained for 2-4 min. This can better ensure the effect of magnetron sputtering and significantly improve the compactness and uniformity of the film layer.

[0052] Optionally, in step S6, the thin film deposition time is 40-60 min. This helps to ensure the uniformity and stability of thin film deposition.

[0053] Optionally, in step S6, the reaction atmosphere is oxygen, and the oxygen injection port is away from the sputtering chamber and is located at the rear quarter of the nozzle. By introducing an appropriate amount of oxygen into the sputtering chamber, chemical reactions can occur with the metal atoms sputtered from the target material, thereby depositing a metal oxide thin film on the substrate.

[0054] For example, in step S4, a circular tungsten metal target with a purity of 99.9% is used, and the nozzle aperture is 5 mm. The circular design helps to achieve more uniform magnetic field distribution, which can result in more uniform sputtering rate and better film thickness consistency. Moreover, by optimizing the magnetic field configuration of the magnetron sputtering system, the plasma distribution on the surface of the target material can be made more uniform, thereby improving the consistency and repeatability of thin film deposition.

[0055] According to a second aspect of the present application, a tungsten oxide nanometer thin film prepared by modulated reaction atmosphere magnetron sputtering is provided, which is prepared by the preparation method as described in the first aspect.

[0056] In the embodiments of the present application, the tungsten oxide nanometer thin film prepared by the preparation method of the tungsten oxide nanometer thin film prepared by modulated reaction atmosphere magnetron sputtering can be used in the technical fields of precision part surface strengthening, high-temperature structure protection, fireproof coating, etc., and has broad application prospects in industrialized applications.

[0057] Referring to Figure 2 , Figure 2 The AFM test diagram of the sample prepared under the process parameters of an embodiment of the present application is shown in FIG. 2, from which it can be seen that the particle size inside the thin film is relatively consistent and uniformly distributed; referring to Figure 2 , Figure 3 , Figure 3 The SEM test diagram of the sample prepared under the process parameters of an embodiment of the present application is shown in FIG. 3, from which it can be seen that the surface compactness and flatness of the thin film are high, and no obvious defects and cracks are seen. Figure 3

[0058] ​It is understood that the above embodiments are only exemplary for illustrating the principles of the present application, and the present application is not limited thereto. Various modifications and improvements can be made by those skilled in the art without departing from the spirit and scope of the present application, and these modifications and improvements are also considered as the protection scope of the present application.

Claims

1. A method for preparing tungsten oxide nanofilms by modulated reactive atmosphere magnetron sputtering, characterized in that, The method comprises the following steps: S1, cleaning and drying the substrate; S2, fixing the dried substrate at the center of the sample holder and installing the sample holder on the sample table of the deposition chamber; S3, simultaneously vacuumizing the sputtering chamber and the deposition chamber, and setting the sputtering chamber plug valve opening degree to 10%-15% and the deposition chamber plug valve opening degree to 40%-50%; S4, adjusting the distance between the target material and the nozzle in the sputtering chamber so that the distance between the target material and the nozzle is 95-120 cm; adjusting the height of the sample holder in the deposition chamber by the lifting platform so that the height of the sample table is 60-70 cm; S5, heating the substrate on the sample table; S6, coating the heated sample; wherein the gas pressure in the coating process is 40-80 Pa, the ratio of Ar and He is 1:1, the substrate bias is 5-8 KV, the magnetron sputtering power is 200-250 W, and the oxygen flow is 0.5-2 sccm; S7, after the coating is completed, fully open the sputtering chamber plug valve and the deposition chamber plug valve, vacuumize the chamber to high vacuum state and keep for 2-3 min, turn off the heating power, and take out the sample after the sample is cooled to room temperature.

2. The method according to claim 1, wherein the method is characterized by, In step S1, the cleaning and drying of the substrate comprises: After ultrasonic cleaning the substrate, put it into a vacuum drying box for standby. 3.The method of claim 1, wherein the method further comprises: adjusting the pressure of the reaction atmosphere to 0.1-10 Pa. In step S2, the substrate is fixed at the center of the sample holder by using high-temperature adhesive tape.

4. The method according to claim 1, wherein the method is characterized by, In step S5, the heating temperature is 550-700℃.

5. The method according to claim 2, wherein the method is characterized by, In step S1, the substrate cleaning process is: put the substrate into a beaker and immerse it completely in anhydrous ethanol in the beaker; wherein the anhydrous ethanol in the beaker is 25-30 ml, and the ultrasonic cleaning time is 15-20 min.

6. The method according to claim 2, wherein the method is characterized by, In step S1, the temperature of the vacuum drying box is set to 50℃.

7. The method according to claim 1, wherein the method is characterized by, In step S3, after the sputtering chamber and the deposition chamber are evacuated, the vacuum degree of the sputtering chamber and the deposition chamber is less than 5.5 x 10 -5 Pa and is maintained for 2 min - 4 min.

8. The method for preparing tungsten oxide nanofilms by magnetron sputtering in a modulated reactive atmosphere according to claim 1, characterized in that, In step S6, the thin film deposition time is 40-60 min.

9. The method of claim 1, wherein the method further comprises: adjusting the pressure of the reaction atmosphere to 0.1 Pa to 10 Pa. In step S6, the reaction atmosphere is oxygen, the oxygen injection port is away from the sputtering chamber, and the sputtering chamber and the deposition chamber are separated.

10. A tungsten oxide nanofilm prepared by modulated reactive atmosphere magnetron sputtering, characterized in that, Prepared by the preparation method of any one of claims 1-9.

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