Conductive TiCuO oxidation-resistant film and preparation method thereof

Abstract

The application provides a conductive TiCuO oxidation-resistant film and a preparation method thereof, and the conductive TiCuO oxidation-resistant film is prepared by a two-step method, and the two-step method for preparing the conductive TiCuO oxidation-resistant film specifically comprises the following steps: S1, a direct current reaction magnetron sputtering is adopted, nitrogen is used as a reaction gas, and a metal Cu-doped nano TiCuN film is prepared through co-sputtering of a titanium target and a copper target; S2, the prepared TiCuN film is subjected to high-temperature oxidation heat treatment in an air atmosphere, O atoms in the air replace N atoms in a TiCuN crystal lattice, and a TiCuO film is prepared; the method breaks through a traditional metal-doped oxide film method, the process is simple, the resistivity of the film is greatly reduced, the conductive performance of the film is improved, the chemical stability of the film is improved, and the method is environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of thin film preparation technology, specifically to a conductive TiCuO antioxidant thin film and its preparation method. Background Technology

[0002] Metal oxide thin films generally exhibit excellent oxidation resistance, leading to their widespread and important applications in production and daily life. Titanium dioxide (TiO2) thin films, as a type of oxide thin film, are inexpensive and possess good mechanical properties, oxidation resistance, and significant optical characteristics, making them widely used in optics, optoelectronics, and electronics. Although TiO2 belongs to a wide bandgap (E... g＝3.0eV-3.2eV It is an indirect bandgap semiconductor material, but its resistivity is relatively high and its conductivity is poor, which affects its practical application.

[0003] Metal ion doping introduces metal ions into the TiO2 lattice, introducing defects that form defect energy levels between the intrinsic energy levels of TiO2, thus altering its band structure. Simultaneously, metal ions can accept excited electrons from the TiO2 valence band, generating more excited electrons and improving the conductivity of TiO2. Currently, the main metal doping methods studied are divided into three categories: (1) metal ions react with O to form metal oxides, which accumulate around the TiO2 grains as nuclei; (2) metal ions gain electrons and deposit on the film surface in atomic form; (3) metal atoms enter the lattice to replace titanium atoms in TiO2. Types of doped metals include rare earth metal doping, transition metal doping, and noble metal doping. Therefore, finding suitable metal doping methods and types of doped metals is crucial for improving the conductivity of TiO2 films.

[0004] DC reactive magnetron sputtering is a commonly used method for preparing metal-doped oxide thin films. Metal targets are used as the target material because they have advantages such as high purity, easy manufacturing, low cost, and high deposition rate due to their reaction with oxygen. However, the nature of metals being easily oxidized means that metal targets are prone to poisoning, which has a certain impact on sputtering coating. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is significantly reduced, the conductivity of the film is improved, its chemical stability is enhanced, and it is environmentally friendly.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] A method for preparing a conductive TiCuO antioxidant thin film, comprising a two-step process, specifically including the following steps:

[0008] S1 uses DC reactive magnetron sputtering with nitrogen as the reactive gas to prepare Cu-doped nano-TiCuN thin films through co-sputtering with titanium and copper targets.

[0009] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0010] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0011] As a preferred technical solution, step S1 employs DC reactive magnetron co-sputtering with nitrogen as the reactive gas, and uses titanium and copper targets for co-sputtering to prepare a Cu-doped nano-TiCuN thin film, specifically including the following steps:

[0012] S101 involves immersing the substrate in an ethanol solution for ultrasonic excitation, followed by immersion in deionized water for ultrasonic cleaning to obtain the cleaned substrate.

[0013] S102 After cleaning the substrate surface obtained in step S101, the substrate is dried to obtain the dried substrate.

[0014] S103 The dried substrate obtained in step S102 is placed in the sputtering chamber. After confirming that all steps are correct, vacuum extraction is performed.

[0015] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, argon gas is introduced, and then Ti and Cu targets are pre-sputtered to remove impurities attached to the surface of Ti and Cu targets.

[0016] S105 After the pre-sputtering in step S104 is completed, set the sputtering parameters of the TiCuN thin film, introduce nitrogen gas, turn on the DC power supply of Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit the TiCuN thin film.

[0017] As a preferred technical solution, in step S101, the substrate is immersed in an ethanol solution for ultrasonic excitation for 10-20 minutes, and then immersed in deionized water for ultrasonic cleaning for 10-20 minutes.

[0018] As a preferred technical solution, the temperature for drying the substrate in step S102 is 50-80℃, and the drying time is 10-30 min.

[0019] As a preferred technical solution, when the Ti target and Cu target are mounted on the target base in step S103, the Ti target and Cu target are placed at an angle of 44° to 46° relative to each other, and the distance between the substrate and the sputtering target is adjusted to 40 to 60 mm; when performing vacuum extraction, low vacuum extraction is performed first, and high vacuum extraction is performed after the gas pressure in the sputtering chamber is <0.5 Pa.

[0020] As a preferred technical solution, in step S104, the pre-sputtering argon gas flow rate is 20-50 sccm, the pre-sputtering gas pressure is 0.1-0.5 Pa, the pre-sputtering power is 50-200 W, and the pre-sputtering time is 10-60 min.

[0021] As a preferred technical solution, after the pre-sputtering in step S105, the sputtering parameters of the TiCuN thin film are set, wherein the nitrogen flow rate is 1-8 sccm, the sputtering power of the Ti target is 80-200W, the sputtering power of the Cu target is 50-100W, the reactive magnetron co-sputtering deposition time is 10-60 min, and the substrate temperature is room temperature.

[0022] As a preferred technical solution, the thickness of the TiCuN thin film is 0.5 to 1 μm.

[0023] As a preferred technical solution, in step S2, the temperature for high-temperature oxidation of the TiCuN film in air atmosphere is 100-400℃, the heating rate is 1-10℃ / min, and the holding time for high-temperature oxidation is 1-5h.

[0024] The present invention also provides a conductive TiCuO antioxidant film, which is prepared according to any of the above-mentioned methods for preparing conductive TiCuO antioxidant films.

[0025] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which has the following characteristics:

[0026] Beneficial effects:

[0027] 1) The present invention provides a conductive TiCuO antioxidant thin film and its preparation method. The method uses a two-step method to prepare the conductive TiCuO antioxidant thin film. This method breaks through the traditional method of metal-doped oxide thin film. The process is simple, and the prepared film has good conductivity and chemical stability, and is environmentally friendly.

[0028] 2) The present invention provides a conductive TiCuO anti-oxidation thin film and its preparation method. The film surface is dense and the grain size is uniform. Compared with the undoped TiO2 film, the resistivity of the conductive TiCuO anti-oxidation thin film is significantly reduced, thereby improving the conductivity of the film. Attached Figure Description

[0029] Figure 1 The image shows the XRD pattern of the conductive TiCuO antioxidant thin film prepared according to the present invention.

[0030] Figure 2 This is a SEM image of the surface of the conductive TiCuO antioxidant film prepared in this invention;

[0031] Figure 3 The resistivity diagram is shown for the conductive TiCuO antioxidant thin film prepared according to the present invention. Detailed Implementation

[0032] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0033] It is understood that the present invention achieves its objectives through some embodiments.

[0034] This invention provides a method for preparing a conductive TiCuO corrosion-resistant thin film, which uses a two-step method to prepare the conductive TiCuO antioxidant thin film. The two-step method specifically includes the following steps:

[0035] S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films. The specific steps include:

[0036] S101 involves immersing a high-temperature quartz glass plate with dimensions of 20.0×20.0×1.0mm in an ethanol solution for ultrasonic excitation for 10–20 minutes, followed by immersion in deionized water for ultrasonic cleaning for 10–20 minutes to obtain the cleaned substrate.

[0037] S102 The cleaned substrate surface obtained in step S101 is wiped clean with microscope lens paper and dried in a forced-air drying oven at 50-80℃ for 10-30 minutes to obtain the dried substrate.

[0038] S103 Place the dried substrate obtained in step S102 on the sample stage of the magnetron sputtering instrument. Install Ti and Cu targets with a purity of 99.999% on the target base. The Ti and Cu targets are tilted at an angle of 44° to 46° relative to each other. Adjust the distance between the substrate and the Ti and Cu targets to 40 to 60 mm. Do not apply bias voltage to the targets. Close the sputtering chamber. After confirming that all steps are correct, first open the mechanical pump and the pre-evacuation valve to perform low vacuum evacuation. When the gas pressure in the sputtering chamber is <0.5 Pa, close the pre-evacuation valve and then open the fore-stage valve, molecular pump and gate valve in sequence to perform high vacuum evacuation.

[0039] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, set the argon flow rate to 20-50 sccm, the sputtering pressure to 0.1-0.5 Pa, and the sputtering power of Ti and Cu targets to 50-200 W. Open the substrate baffle, open the argon valve to introduce argon, turn on the DC power supply of Ti and Cu targets, and pre-sputter the Ti and Cu targets for 10-60 min to remove impurities attached to the surface of Ti and Cu targets.

[0040] S105 After the pre-sputtering in step S104 is completed, set the nitrogen flow rate to 1-8 sccm, the Ti target sputtering power to 80-200 W, the Cu target sputtering power to 50-100 W, the co-sputtering deposition time to 10-60 min, the substrate temperature to room temperature, close the substrate baffle, open the nitrogen valve to introduce nitrogen, turn on the DC power supply for the Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit a TiCuN thin film;

[0041] S106 After the sputtering in step S105 is completed, turn off the DC power supply to the Ti target and Cu target, turn off the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN thin film sample.

[0042] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The specific steps include:

[0043] The TiCuN thin film sample was placed in a heat treatment furnace, and the heat treatment temperature was set to 100-400℃, the holding time to 1-5h, and the heating rate to 1-10℃ / min. The prepared TiCuN thin film was subjected to high-temperature oxidation and holding in an air atmosphere. O atoms in the air replaced N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0044] The present invention also provides a conductive TiCuO antioxidant thin film, which is prepared according to the above-described method for preparing conductive TiCuO antioxidant thin film.

[0045] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0046] Example 1

[0047] This embodiment provides a method for preparing a conductive TiCuO corrosion-resistant thin film. The conductive TiCuO antioxidant thin film is prepared in a two-step process, which specifically includes the following steps:

[0048] S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films. The specific steps include:

[0049] S101 involves immersing a high-temperature quartz glass plate with dimensions of 20.0×20.0×1.0mm into an ethanol solution for ultrasonic excitation for 10 minutes, followed by immersion in deionized water for ultrasonic cleaning for 10 minutes to obtain the cleaned substrate.

[0050] S102 The cleaned substrate surface obtained in step S101 is wiped clean with microscope lens paper and dried in a forced-air drying oven at 50°C for 30 minutes to obtain the dried substrate.

[0051] S103 Place the dried substrate obtained in step S102 on the sample stage of the magnetron sputtering instrument. Install Ti and Cu targets with a purity of 99.999% on the target base respectively. The Ti and Cu targets are placed at a 45° angle relative to each other. Adjust the distance between the substrate and the Ti and Cu targets to 40 mm. Do not apply bias voltage to the targets. Close the sputtering chamber. After confirming that all steps are correct, first turn on the mechanical pump and the pre-evacuation valve to perform low vacuum evacuation. When the gas pressure in the sputtering chamber is <0.5 Pa, close the pre-evacuation valve and then turn on the fore-stage valve, molecular pump and gate valve in sequence to perform high vacuum evacuation.

[0052] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, set the argon flow rate to 50 sccm, the sputtering pressure to 0.1 Pa, and the sputtering power of Ti and Cu targets to 50 W. Open the substrate baffle, open the argon valve to introduce argon, turn on the DC power supply of Ti and Cu targets, and pre-sputter the Ti and Cu targets for 10 min to remove impurities attached to the surface of Ti and Cu targets.

[0053] S105 After the pre-sputtering in step S104 is completed, set the nitrogen flow rate to 1 sccm, the Ti target sputtering power to 80W, the Cu target sputtering power to 50W, the co-sputtering deposition time to 60 min, the substrate temperature to room temperature, close the substrate baffle, open the nitrogen valve to introduce nitrogen, turn on the DC power supply for the Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit a TiCuN thin film.

[0054] S106 After the sputtering in step S105 is completed, turn off the DC power supply to the Ti and Cu targets, turn off the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN thin film sample.

[0055] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The specific steps include:

[0056] The TiCuN thin film sample was placed in a heat treatment furnace, and the heat treatment temperature was set to 100℃, the holding time was 5h, and the heating rate was 1℃ / min. The prepared TiCuN thin film was subjected to high-temperature oxidation and holding in an air atmosphere. O atoms in the air replaced N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0057] The present invention also provides a conductive TiCuO antioxidant thin film, which is prepared according to the above-described method for preparing conductive TiCuO antioxidant thin film.

[0058] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0059] Example 2

[0060] This embodiment provides a method for preparing a conductive TiCuO corrosion-resistant thin film. The conductive TiCuO antioxidant thin film is prepared in a two-step process, which specifically includes the following steps:

[0061] S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films. The specific steps include:

[0062] S101 involves immersing a high-temperature quartz glass plate with dimensions of 20.0×20.0×1.0mm in an ethanol solution for ultrasonic excitation for 20 minutes, followed by immersion in deionized water for ultrasonic cleaning for 20 minutes to obtain the cleaned substrate.

[0063] S102 The cleaned substrate surface obtained in step S101 is wiped clean with microscope lens paper and dried in a forced-air drying oven at 80°C for 10 minutes to obtain the dried substrate.

[0064] S103 Place the dried substrate obtained in step S102 on the sample stage of the magnetron sputtering instrument. Install Ti and Cu targets with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a relative angle of 46°. Adjust the distance between the substrate and the Ti and Cu targets to 60 mm. Do not apply bias voltage to the targets. Close the sputtering chamber. After confirming that all steps are correct, first open the mechanical pump and the pre-evacuation valve to perform low vacuum evacuation. When the gas pressure in the sputtering chamber is <0.5 Pa, close the pre-evacuation valve and then open the fore-stage valve, molecular pump and gate valve in sequence to perform high vacuum evacuation.

[0065] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, set the argon flow rate to 20 sccm, the sputtering pressure to 0.5 Pa, and the sputtering power of Ti and Cu targets to 200 W. Open the substrate baffle, open the argon valve to introduce argon, turn on the DC power supply of Ti and Cu targets, and pre-sputter the Ti and Cu targets for 60 min to remove impurities attached to the surface of Ti and Cu targets.

[0066] S105 After the pre-sputtering in step S104 is completed, set the nitrogen flow rate to 8 sccm, the Ti target sputtering power to 200 W, the Cu target sputtering power to 100 W, the co-sputtering deposition time to 10 min, the substrate temperature to room temperature, close the substrate baffle, open the nitrogen valve to introduce nitrogen, turn on the DC power supply for the Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit a TiCuN thin film.

[0067] S106 After the sputtering in step S105 is completed, turn off the DC power supply to the Ti target and Cu target, turn off the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN thin film sample.

[0068] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The specific steps include:

[0069] The TiCuN thin film sample was placed in a heat treatment furnace, and the heat treatment temperature was set to 400℃, the holding time was 1h, and the heating rate was 10℃ / min. The prepared TiCuN thin film was subjected to high-temperature oxidation and holding in an air atmosphere. O atoms in the air replaced N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0070] The present invention also provides a conductive TiCuO antioxidant thin film, which is prepared according to the above-described method for preparing conductive TiCuO antioxidant thin film.

[0071] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0072] Example 3

[0073] This embodiment provides a method for preparing a conductive TiCuO corrosion-resistant thin film. The conductive TiCuO antioxidant thin film is prepared in a two-step process, which specifically includes the following steps:

[0074] S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films. The specific steps include:

[0075] S101 involves immersing a high-temperature quartz glass plate with dimensions of 20.0×20.0×1.0mm in an ethanol solution for ultrasonic excitation for 15 minutes, followed by immersion in deionized water for ultrasonic cleaning for 15 minutes to obtain the cleaned substrate.

[0076] S102 The cleaned substrate surface obtained in step S101 is wiped clean with microscope lens paper and dried in a forced-air drying oven at 60°C for 20 minutes to obtain the dried substrate.

[0077] S103 Place the dried substrate obtained in step S102 on the sample stage of the magnetron sputtering instrument. Install Ti and Cu targets with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a relative angle of 45°. Adjust the distance between the substrate and the Ti and Cu targets to 55 mm. Do not apply bias voltage to the targets. Close the sputtering chamber. After confirming that all steps are correct, first open the mechanical pump and the pre-evacuation valve to perform low vacuum evacuation. When the gas pressure in the sputtering chamber is <0.5 Pa, close the pre-evacuation valve and then open the fore-stage valve, molecular pump and gate valve in sequence to perform high vacuum evacuation.

[0078] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, set the argon flow rate to 35 sccm, the sputtering pressure to 0.3 Pa, and the sputtering power of Ti and Cu targets to 150 W. Open the substrate baffle, open the argon valve to introduce argon, turn on the DC power supply of Ti and Cu targets, and pre-sputter the Ti and Cu targets for 35 min to remove impurities attached to the surface of Ti and Cu targets.

[0079] S105 After the pre-sputtering in step S104 is completed, set the nitrogen flow rate to 5 sccm, the Ti target sputtering power to 140 W, the Cu target sputtering power to 75 W, the co-sputtering deposition time to 35 min, the substrate temperature to room temperature, close the substrate baffle, open the nitrogen valve to introduce nitrogen, turn on the DC power supply for the Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit a TiCuN thin film.

[0080] S106 After the sputtering in step S105 is completed, turn off the DC power supply to the Ti target and Cu target, turn off the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN thin film sample.

[0081] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The specific steps include:

[0082] The TiCuN thin film sample was placed in a heat treatment furnace, and the heat treatment temperature was set to 250℃, the holding time was 3h, and the heating rate was 5℃ / min. The prepared TiCuN thin film was subjected to high-temperature oxidation and holding in an air atmosphere. O atoms in the air replaced N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0083] The present invention also provides a conductive TiCuO antioxidant thin film, which is prepared according to the above-described method for preparing conductive TiCuO antioxidant thin film.

[0084] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0085] Example 4

[0086] This embodiment provides a method for preparing a conductive TiCuO corrosion-resistant thin film. The conductive TiCuO antioxidant thin film is prepared in a two-step process, which specifically includes the following steps:

[0087] S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films. The specific steps include:

[0088] S101 involves immersing a high-temperature quartz glass plate with dimensions of 20.0×20.0×1.0mm into an ethanol solution for ultrasonic excitation for 10 minutes, followed by immersion in deionized water for ultrasonic cleaning for 10 minutes to obtain the cleaned substrate.

[0089] S102 The cleaned substrate surface obtained in step S101 is wiped clean with microscope lens paper and dried in a forced-air drying oven at 60°C for 30 minutes to obtain the dried substrate.

[0090] S103 Place the dried substrate obtained in step S102 on the sample stage of the magnetron sputtering instrument. Install Ti and Cu targets with a purity of 99.999% on the target base respectively. The Ti and Cu targets are placed at a 45° angle relative to each other. Adjust the distance between the substrate and the Ti and Cu targets to 55 mm. Do not apply bias voltage to the targets. Close the sputtering chamber. After confirming that all steps are correct, first open the mechanical pump and the pre-evacuation valve to perform low vacuum evacuation. When the gas pressure in the sputtering chamber is <0.5 Pa, close the pre-evacuation valve and then open the fore-stage valve, molecular pump and gate valve in sequence to perform high vacuum evacuation.

[0091] S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, set the argon flow rate to 50 sccm, the sputtering pressure to 0.3 Pa, and the sputtering power of Ti and Cu targets to 100 W. Open the substrate baffle, open the argon valve to introduce argon, turn on the DC power supply of Ti and Cu targets, and pre-sputter the Ti and Cu targets for 15 min to remove impurities attached to the surface of Ti and Cu targets.

[0092] S105 After the pre-sputtering in step S104 is completed, set the nitrogen flow rate to 8 sccm, the Ti target sputtering power to 150 W, the Cu target sputtering power to 60 W, the co-sputtering deposition time to 40 min, the substrate temperature to room temperature, close the substrate baffle, open the nitrogen valve to introduce nitrogen, turn on the DC power supply for the Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit a TiCuN thin film.

[0093] S106 After the sputtering in step S105 is completed, turn off the DC power supply to the Ti target and Cu target, turn off the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN thin film sample.

[0094] S2 involves subjecting the prepared TiCuN thin film to high-temperature oxidation heat treatment in an air atmosphere, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The specific steps include:

[0095] The TiCuN thin film sample was placed in a heat treatment furnace, and the heat treatment temperature was set to 400℃, the holding time was 2h, and the heating rate was 8℃ / min. The prepared TiCuN thin film was subjected to high-temperature oxidation and holding in an air atmosphere. O atoms in the air replaced N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film.

[0096] The present invention also provides a conductive TiCuO antioxidant thin film, which is prepared according to the above-described method for preparing conductive TiCuO antioxidant thin film.

[0097] This invention provides a conductive TiCuO antioxidant thin film and its preparation method, which breaks through the traditional method of metal-doped oxide thin films. The process is simple, the resistivity of the film is greatly reduced, the conductivity of the film is improved, the chemical stability of the film is improved, and it is environmentally friendly.

[0098] like Figure 1 The figure shows the XRD pattern of the conductive TiCuO anti-oxidation film prepared by this invention. This application uses a two-step method to prepare the conductive TiCuO anti-oxidation film. From the figure, we can observe that after the first step of DC reactive magnetron co-sputtering in Example 4, a strong diffraction peak of the TiCuN phase appeared, indicating that the film successfully prepared by this application is a TiCuN film. After the second step of oxidation heat treatment, O atoms replaced N atoms in the TiCuN lattice, resulting in a strong diffraction peak of the TiCuO phase. This indicates that the TiCuO film was successfully prepared by the method of preparing the conductive TiCuO corrosion-resistant film of this application.

[0099] like Figure 2 As shown in the figure, the SEM image of the conductive TiCuO antioxidant film prepared by the present invention shows that the conductive TiCuO antioxidant film prepared in Example 4 has a smooth surface, uniform particle size, and is dense and pore-free, which can greatly improve the chemical stability of the film.

[0100] like Figure 3 As shown in the resistivity diagram of the conductive TiCuO anti-oxidation film prepared by the present invention, we can observe from the figure that the resistivity of the TiO2 film is very high, indicating that its conductivity is poor. The resistivity of the conductive TiCuO anti-oxidation film prepared in Example 4 is significantly reduced, indicating that the preparation method of the conductive TiCuO corrosion-resistant film of this application can effectively improve the conductivity of the film.

[0101] It is understood that the present invention has been described through some embodiments, and those skilled in the art will recognize that various changes or equivalent substitutions can be made to these features and embodiments without departing from the spirit and scope of the invention. Furthermore, under the teachings of the present invention, these features and embodiments can be modified to adapt to specific situations and materials without departing from the spirit and scope of the invention. Therefore, the present invention is not limited to the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are protected by the present invention.

Claims

1. A method for preparing a conductive TiCuO antioxidant thin film, characterized in that, A conductive TiCuO antioxidant film was prepared by a two-step method, which specifically includes the following steps: S1 employs DC reactive magnetron sputtering with nitrogen as the reactive gas, and uses co-sputtering with titanium and copper targets to prepare Cu-doped nano-TiCuN thin films; S2 involves subjecting the prepared TiCuN thin film to oxidative heat treatment in an air atmosphere at 100–400°C, where O atoms in the air replace N atoms in the TiCuN lattice, thereby preparing a TiCuO thin film. The TiCuO thin film comprises a TiCuO phase and a TiCuN phase.

2. The method for preparing the conductive TiCuO antioxidant thin film according to claim 1, characterized in that, In step S1, DC reactive magnetron co-sputtering is used with nitrogen as the reactive gas. The metal Cu-doped TiCuN nanofilm is prepared by co-sputtering with titanium and copper targets. The specific steps include: S101 involves immersing the substrate in an ethanol solution for ultrasonic excitation, followed by immersion in deionized water for ultrasonic cleaning to obtain the cleaned substrate. S102 After cleaning the substrate surface obtained in step S101, the substrate is dried to obtain the dried substrate. S103 The dried substrate obtained in step S102 is placed in the sputtering chamber. After confirming that all steps are correct, vacuum extraction is performed. S104 When the vacuum in the sputtering chamber in step S103 reaches the background vacuum of 5.0 × 10⁻⁶ -4 After Pa, argon gas is introduced, and then Ti and Cu targets are pre-sputtered to remove impurities attached to the surface of Ti and Cu targets. S105 After the pre-sputtering in step S104 is completed, set the sputtering parameters of the TiCuN thin film, introduce nitrogen gas, turn on the DC power supply of Ti target and Cu target, and perform reactive magnetron co-sputtering to deposit the TiCuN thin film.

3. The method for preparing the conductive TiCuO antioxidant thin film according to claim 2, characterized in that, Step S101: Immerse the substrate in an ethanol solution for ultrasonic excitation for 10-20 min, and then immerse it in deionized water for ultrasonic cleaning for 10-20 min.

4. The method for preparing the conductive TiCuO antioxidant thin film according to claim 2, characterized in that, In step S102, the substrate is dried at a temperature of 50–80°C for 10–30 minutes.

5. The method for preparing a conductive TiCuO antioxidant thin film according to claim 2, characterized in that, In step S103, when the Ti target and Cu target are mounted on the target base, the Ti target and Cu target are placed at an angle of 44° to 46° relative to each other, and the distance between the substrate and the sputtering target is adjusted to 40 to 60 mm. When performing vacuum extraction, low vacuum extraction is performed first, and high vacuum extraction is performed after the gas pressure in the sputtering chamber is <0.5 Pa.

6. The method for preparing a conductive TiCuO antioxidant thin film according to claim 2, characterized in that, In step S104, the pre-sputtering argon gas flow rate is 20–50 sccm, the pre-sputtering gas pressure is 0.1–0.5 Pa, the pre-sputtering power is 50–200 W, and the pre-sputtering time is 10–60 min.

7. The method for preparing a conductive TiCuO antioxidant thin film according to claim 2, characterized in that, After pre-sputtering in step S105, the sputtering parameters of the TiCuN thin film are set, including a nitrogen flow rate of 1-8 sccm, a Ti target sputtering power of 80-200 W, a Cu target sputtering power of 50-100 W, a reactive magnetron co-sputtering deposition time of 10-60 min, and a substrate temperature of room temperature.

8. The method for preparing a conductive TiCuO antioxidant thin film according to claim 1, characterized in that, The thickness of the TiCuN thin film is 0.5–1 μm.

9. The method for preparing a conductive TiCuO antioxidant thin film according to claim 1, characterized in that, In step S2, the TiCuN film is subjected to high-temperature oxidation in air at a temperature of 100–400°C, a heating rate of 1–10°C / min, and a holding time of 1–5 h.

10. A conductive TiCuO antioxidant thin film, characterized in that, The conductive TiCuO antioxidant thin film was prepared according to any one of claims 1-9.

Images