A preparation method and product of CuO nanowire and nanoparticle two-dimensional hybrid structure functional film

Abstract

The present invention discloses a method for preparing a functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles, and the product thereof. The method comprises the following steps: preparing a TiCuN / Cu bilayer film using magnetron sputtering technology; then oxidizing the TiCuN / Cu bilayer film in an air atmosphere; and controlling the oxidation temperature and time to prepare a functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles having a special structure. The functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles provided by the present invention has uniform CuO nanoparticles with a particle size of 51 to 96 nm. The CuO nanowires are uniformly distributed within the CuO nanoparticles and have varying lengths, with the longest being approximately 1175 nm. The film has a contact angle of 130.1° to 159.4°. The film exhibits excellent electrical conductivity, hydrophobicity, electromagnetic shielding, and other properties, and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of thin film preparation, and in particular relates to a method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film and a product thereof. Background Art

[0002] Nanomaterials possess unique chemical and physical properties. Compared to macroscopic solid materials, they possess unique diffusivity, strength, hardness, resistivity, conductivity, and chemical reactivity. Nano-CuO is a transition metal oxide with excellent properties in electrical, magnetic, optical, and catalytic fields, and is widely used in catalysis, sterilization, sensing, energy, optoelectronics, and other fields.

[0003] Nanomaterials have diverse morphologies and structures, such as nanoparticles, nanorods, nanochains, nanostars, nanoflowers, and nanoboxes. Each unique morphology and structure imparts distinct mechanical, physical, and chemical properties. Because different morphologies and structures impart distinct functions to nano-CuO, the preparation of nano-CuO with controllable, diverse, and mixed morphologies and structures has become a research hotspot and focus in order to enhance its multifunctionality.

[0004] At present, the preparation methods of nano-CuO mainly focus on precipitation method, electrochemical method, hydrothermal method, microwave-assisted method, solvent thermal method, sol-gel method and ultrasonic method. These methods have certain pollution to the environment, and the prepared nano-CuO is mostly powder, which limits the application range of nano-CuO. Summary of the Invention

[0005] In order to solve the technical problems existing in the prior art, the purpose of the present invention is to provide a method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film and its product.

[0006] In order to achieve the above-mentioned purpose and the above-mentioned technical effect, the technical solution adopted by the present invention is:

[0007] A method for preparing a functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles comprises the following steps:

[0008] First, a TiCuN / Cu double-layer film is prepared, and then the TiCuN / Cu double-layer film is oxidized in an air atmosphere to prepare the desired CuO nanowire and nanoparticle two-dimensional hybrid structure functional film.

[0009] Furthermore, the TiCuN / Cu double-layer film is prepared by the following steps:

[0010] Step 1: First, the substrate is mechanically polished with sandpaper, and then polished until the surface has no obvious scratches and is mirror-like;

[0011] Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation, and then immersing it in deionized water for ultrasonic cleaning;

[0012] Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and then dry it in a blast drying oven;

[0013] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, install the Ti target and Cu target on the target base, close the sputtering chamber, and after confirming that all steps are correct, perform vacuum extraction;

[0014] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, open the argon valve to introduce argon, then turn on the DC power supply of Ti and Cu targets respectively to pre-sputter the Ti and Cu targets to remove impurities attached to the surface of the Ti and Cu targets;

[0015] Step 6: After the pre-sputtering in step 5 is completed, the Cu thin film sputtering parameters are set, the Cu target DC power supply is turned on, and magnetron sputtering is performed to deposit a pure Cu thin film;

[0016] Step 7: After the sputtering in step 6 is completed, the TiCuN film sputtering parameters are set, the nitrogen valve is opened, nitrogen is introduced, the DC power supply of the Ti and Cu targets is turned on, and reactive magnetron co-sputtering is performed to deposit the TiCuN film;

[0017] Step 8. After the sputtering in step 7 is completed, turn off the DC power supply of the Ti and Cu targets, close the nitrogen and argon valves, open the vacuum valve, and take out the film sample.

[0018] Furthermore, in step 2, the ultrasonic excitation time using the ethanol solution is 10 to 60 minutes, and the ultrasonic cleaning time using deionized water is 10 to 60 minutes.

[0019] Furthermore, in step 3, the substrate is dried in a blast drying oven at a temperature of 50 to 100° C. and a drying time of 20 to 100 minutes.

[0020] Furthermore, in step 5, during pre-sputtering, the argon flow rate is 20-50 sccm, the sputtering pressure is 0.1-0.4 Pa, the Ti target sputtering power is 50-200 W, the Cu target sputtering power is 30-80 W, and the sputtering time is 20-60 min.

[0021] Furthermore, in step 6, the sputtering power of the Cu target is 30-80 W, the deposition time is 20-40 min, the sputtering gas pressure is 0.1-0.4 Pa, and the substrate temperature is room temperature.

[0022] Furthermore, in step 7, the sputtering power of the Ti target is 80-150 W, the sputtering power of the Cu target is 30-80 W, the deposition time is 20-60 min, the sputtering gas pressure is 0.1-0.4 Pa, and the substrate temperature is room temperature.

[0023] Furthermore, the step of oxidizing the TiCuN / Cu double-layer film in an air atmosphere includes:

[0024] The prepared TiCuN / Cu double-layer film is placed in a heat treatment furnace for oxidation. The heat treatment temperature is 300-1000°C, the holding time is 1-3h, and the heating rate is 1-8°C / min. After the holding period is completed, the heating is stopped and the furnace body is naturally cooled to room temperature.

[0025] The present invention also discloses a CuO nanowire / nanoparticle two-dimensional hybrid structure functional film prepared according to the method for preparing the CuO nanowire / nanoparticle two-dimensional hybrid structure functional film as described above.

[0026] Furthermore, the CuO nanowire and nanoparticle two-dimensional hybrid structure functional film is a nanomorphology composed of CuO nanowires and CuO nanoparticles, the particle size of the CuO nanoparticles is 51 to 96 nm, the CuO nanowires are uniformly distributed in the CuO nanoparticles and vary in size, and the contact angle of the CuO nanowire and nanoparticle two-dimensional hybrid structure functional film is 130.1° to 159.4°.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention discloses a method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film and a product thereof. The preparation method comprises the following steps: first, preparing a TiCuN / Cu double-layer film by using a magnetron sputtering technique; then, oxidizing the TiCuN / Cu double-layer film in an air atmosphere; and controlling the oxidation temperature and time so that Cu atoms with a smaller atomic radius replace Ti atoms with a larger atomic radius in a TiCuN lattice, and O atoms replace N atoms in a TiCuN lattice, thereby preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film with a special structure. The CuO nanoparticles are uniform in size, with a particle size of 51 to 96 nm and an average particle size of about 87 nm. The CuO nanowires are uniformly distributed in the CuO nanoparticles and have varying lengths, with the longest length being about 1175 nm. The film prepared by the present invention has a contact angle of 130.1° to 159.4°. The film has good electrical conductivity, hydrophobicity, electromagnetic shielding and other properties, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is the XRD pattern of Example 3 of the present invention;

[0030] Figure 2 This is a surface SEM image of Example 3 of the present invention;

[0031] Figure 3 This is a contact angle diagram of Example 3 of the present invention. DETAILED DESCRIPTION

[0032] The present invention is described in detail below so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more precise definition of the protection scope of the present invention.

[0033] The following is a brief summary of one or more aspects to provide a basic understanding of these aspects. This summary is not an exhaustive overview of all conceivable aspects and is neither intended to identify key or critical elements of all aspects nor to define the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that will be provided later.

[0034] The growth of nanostructures is related to the composition and heating temperature of the film. The present invention first sets the film composition by magnetron sputtering and then regulates the heat treatment temperature and time to obtain CuO nanowires and nanoparticles with two-dimensional mixed structure functional films with diverse morphologies and structures, thereby realizing the multifunctionality of CuO films.

[0035] A method for preparing a functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles comprises the following steps:

[0036] Step 1: First, use sandpaper to mechanically grind a substrate with a size of 20.0 mm × 20.0 mm × 1.0 mm, and then polish it until there are no obvious scratches on the surface. The substrate material is not limited, as long as it is processed to a mirror finish.

[0037] Step 2: immerse the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation for 10 to 60 minutes, and then immerse it in deionized water for ultrasonic cleaning for 10 to 60 minutes.

[0038] Step 3: Wipe the surface of the substrate obtained in step 2 clean with special paper, and dry it in a forced air drying oven at a temperature of 50 to 100° C. for 20 to 100 minutes.

[0039] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, and install a Ti target and a Cu target with a purity of 99.999% on the target base respectively. The Ti target and the Cu target are tilted at a 45° angle relative to each other. Adjust the distance between the substrate and the sputtering target to 40-60 mm. No bias is applied to the target. Close the sputtering chamber. After confirming that all links are correct, perform vacuum extraction: first open the mechanical pump and pre-extraction valve to perform low vacuum extraction. When the air pressure in the sputtering chamber is lower than 0.5 Pa, close the pre-extraction valve, and open the fore-stage valve, molecular pump and plug-in valve in sequence to perform high vacuum extraction.

[0040] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, the argon valve is opened to introduce argon, and then the DC power supplies of the Ti and Cu targets are turned on respectively to pre-sputter the Ti and Cu targets to remove impurities attached to the surfaces of the Ti and Cu targets; in this step, before turning on the DC power supplies of the Ti and Cu targets, the substrate baffle is opened to protect the substrate material from contamination by the pre-sputtered atoms; during pre-sputtering, the pre-sputtering argon flow rate is 20 to 50 sccm, the sputtering pressure is 0.1 to 0.4 Pa, the sputtering power of the Ti target is 50 to 200 W, the sputtering power of the Cu target is 30 to 80 W, and the sputtering time is 20 to 60 min.

[0041] Step 6. After the pre-sputtering in step 5 is completed, close the substrate baffle and set the Cu film sputtering parameters: the Cu target sputtering power is 30-80 W, the deposition time is 20-40 min, the sputtering gas pressure is 0.1-0.4 Pa, the substrate temperature is room temperature, turn on the Cu target DC power supply, perform magnetron sputtering, and deposit a pure Cu film.

[0042] Step 7. After the sputtering in step 6 is completed, the TiCuN film sputtering parameters are set: the Ti target sputtering power is 80-150 W, the Cu target sputtering power is 30-80 W, the deposition time is 20-60 min, the sputtering pressure is 0.1-0.4 Pa, the substrate temperature is room temperature, the nitrogen valve is opened, nitrogen is introduced, the Ti target and Cu target DC power supplies are turned on, and reactive magnetron sputtering is performed to deposit the TiCuN film.

[0043] Step 8. After the sputtering in step 7 is completed, turn off the DC power supply of the Ti target and the Cu target, close the nitrogen and argon valves, open the vacuum valve, and take out the TiCuN / Cu double-layer film sample.

[0044] Step 9: Place the film sample prepared in step 8 into a heat treatment furnace and oxidize it at a temperature of 300-1000°C for 1-3 hours at a heating rate of 1-8°C / min. After the heat preservation is completed, heating is stopped, and the furnace body is naturally cooled to room temperature before removing the sample. By controlling the oxidation temperature and time in this step, metal Cu atoms can replace Ti atoms and non-metallic O atoms can replace N atoms, thereby preparing the desired CuO nanowire and nanoparticle two-dimensional hybrid structure functional film. The particle size of the CuO nanoparticles is 51-96 nm, and the CuO nanowires are uniformly distributed in the CuO nanoparticles of varying sizes. The contact angle of the CuO nanowire and nanoparticle two-dimensional hybrid structure functional film is 130.1° to 159.4°.

[0045] Example 1

[0046] Step 1: A 304 stainless steel substrate with a size of 20.0 mm × 20.0 mm × 1.0 mm is ground with sandpaper from coarse to fine, and then polished until the surface has no obvious scratches and is mirror-smooth.

[0047] Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation for 30 minutes, and then immersing it in deionized water for ultrasonic cleaning for 40 minutes;

[0048] Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and dry it in a blast drying oven at 90° C. for 30 minutes;

[0049] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, and install a Ti target and a Cu target with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a 45° angle relative to each other. Adjust the distance between the substrate and the sputtering target to 50 mm. No bias is applied to the target. Close the sputtering chamber. After confirming that all links are correct, open the mechanical pump and the pre-evacuation valve first to perform low vacuum extraction. When the air pressure in the sputtering chamber is lower than 0.5 Pa, close the pre-evacuation valve, and open the fore valve, molecular pump and gate valve in sequence to perform high vacuum extraction.

[0050] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, the argon valve is opened to introduce argon, and then the DC power supplies of the Ti and Cu targets are turned on respectively to pre-sputter the Ti and Cu targets to remove impurities attached to the surfaces of the Ti and Cu targets; in this step, before turning on the DC power supplies of the Ti and Cu targets, the substrate baffle is opened to protect the substrate material from contamination by the pre-sputtered atoms; during pre-sputtering, the pre-sputtering argon flow rate is 50 sccm, the sputtering pressure is 0.4 Pa, the sputtering power of the Ti target is 100 W, the sputtering power of the Cu target is 50 W, and the sputtering time is 20 min;

[0051] Step 6. After the pre-sputtering in step 5 is completed, close the substrate baffle, set the Cu target sputtering power to 40 W, the deposition time to 30 min, the sputtering gas pressure to 0.3 Pa, the substrate temperature to room temperature, turn on the Cu target DC power supply, perform magnetron sputtering, and deposit a pure Cu film.

[0052] Step 7, after the sputtering in step 6 is completed, the sputtering power of the Ti target is set to 100 W, the sputtering power of the Cu target is set to 40 W, the deposition time is set to 30 min, the sputtering pressure is set to 0.3 Pa, the substrate temperature is set to room temperature, the nitrogen valve is opened, nitrogen is introduced, the DC power supply of the Ti target and the Cu target is turned on, and reactive magnetron sputtering is performed to deposit a TiCuN film;

[0053] Step 8: After the sputtering in step 7 is completed, the DC power supply of the Ti target and the Cu target is turned off, the nitrogen and argon valves are closed, the vacuum valve is opened, and the TiCuN / Cu double-layer film sample is taken out;

[0054] Step 9: Place the TiCuN / Cu double-layer film sample prepared in step 8 into a heat treatment furnace, oxidize it at a temperature of 400°C for 1 hour in a heat treatment furnace, and heat it at a rate of 3°C / min. After the insulation is completed, stop heating, and take out the sample after the furnace body cools naturally to room temperature.

[0055] Example 2

[0056] Step 1: A 304 stainless steel substrate with a size of 20.0 mm × 20.0 mm × 1.0 mm is ground with sandpaper from coarse to fine, and then polished to a mirror finish;

[0057] Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation for 30 minutes, and then immersing it in deionized water for ultrasonic cleaning for 40 minutes;

[0058] Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and dry it in a blast drying oven at 90° C. for 30 minutes;

[0059] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, and install a Ti target and a Cu target with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a 45° angle relative to each other. Adjust the distance between the substrate and the sputtering target to 50 mm. No bias is applied to the target. Close the sputtering chamber. After confirming that all links are correct, open the mechanical pump and the pre-evacuation valve first to perform low vacuum extraction. When the air pressure in the sputtering chamber is lower than 0.5 Pa, close the pre-evacuation valve, and open the fore valve, molecular pump and gate valve in sequence to perform high vacuum extraction.

[0060] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10-4 After Pa, set the argon flow rate to 50 sccm, the sputtering pressure to 0.4 Pa, the Ti power to 100 W, the Cu power to 50 W, open the substrate baffle, open the argon valve, pass argon, turn on the DC power supply of the Ti target and Cu target, and pre-sputter the Ti target and Cu target for 20 minutes to remove impurities attached to the surface of the Ti target and Cu target;

[0061] Step 6: After the pre-sputtering in step 5 is completed, the substrate baffle is closed, the Cu target sputtering power is set to 50 W, the deposition time is set to 35 min, the sputtering pressure is set to 0.3 Pa, the substrate temperature is set to room temperature, the substrate baffle is closed, the Cu target DC power supply is turned on, and magnetron sputtering is performed to deposit a Cu thin film;

[0062] Step 7. After the sputtering in step 6 is completed, set the Ti target sputtering power to 100 W, the Cu target sputtering power to 40 W, the deposition time to 30 min, the sputtering pressure to 0.3 Pa, the substrate temperature to room temperature, open the nitrogen valve, introduce nitrogen, turn on the Ti target and Cu target DC power supplies, perform reactive magnetron sputtering, and deposit a TiCuN film.

[0063] Step 8: After the sputtering in step 7 is completed, the DC power supply of the Ti target and the Cu target is turned off, the nitrogen and argon valves are closed, the vacuum valve is opened, and the TiCuN / Cu double-layer film sample is taken out;

[0064] Step 9: Place the TiCuN / Cu double-layer film sample prepared in step 8 into a heat treatment furnace, oxidize it in a heat treatment furnace at a temperature of 500°C for 2 hours, and the heating rate is 3°C / min. After the insulation is completed, stop heating, and take out the sample after the furnace body cools naturally to room temperature.

[0065] The rest is the same as Example 1.

[0066] Example 3

[0067] Step 1: A 304 stainless steel substrate with a size of 20.0 mm × 20.0 mm × 1.0 mm is ground with sandpaper from coarse to fine, and then polished to a mirror finish;

[0068] Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation for 30 minutes, and then immersing it in deionized water for ultrasonic cleaning for 40 minutes;

[0069] Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and dry it in a blast drying oven at 90° C. for 30 minutes;

[0070] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, and install a Ti target and a Cu target with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a 45° angle relative to each other. Adjust the distance between the substrate and the sputtering target to 50 mm. No bias is applied to the target. Close the sputtering chamber. After confirming that all links are correct, open the mechanical pump and the pre-evacuation valve first to perform low vacuum extraction. When the air pressure in the sputtering chamber is lower than 0.5 Pa, close the pre-evacuation valve, and open the fore valve, molecular pump and gate valve in sequence to perform high vacuum extraction.

[0071] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, set the argon flow rate to 50 sccm, the sputtering pressure to 0.4 Pa, the Ti power to 100 W, the Cu power to 50 W, open the substrate baffle, open the argon valve, pass argon, turn on the DC power supply of the Ti target and Cu target, and pre-sputter the Ti target and Cu target for 20 minutes to remove impurities attached to the surface of the Ti target and Cu target;

[0072] Step 6: After the pre-sputtering in step 5 is completed, the substrate baffle is closed, the Cu target sputtering power is set to 60 W, the deposition time is set to 40 min, the sputtering pressure is set to 0.3 Pa, the substrate temperature is set to room temperature, the substrate baffle is closed, the Cu target DC power supply is turned on, and magnetron sputtering is performed to deposit a Cu thin film;

[0073] Step 7. After the sputtering in step 6 is completed, set the Ti target sputtering power to 100 W, the Cu target sputtering power to 40 W, the deposition time to 30 min, the sputtering pressure to 0.3 Pa, the substrate temperature to room temperature, open the nitrogen valve, introduce nitrogen, turn on the Ti target and Cu target DC power supplies, perform reactive magnetron sputtering, and deposit a TiCuN film.

[0074] Step 8: After the sputtering in step 7 is completed, the DC power supply of the Ti target and the Cu target is turned off, the nitrogen and argon valves are closed, the vacuum valve is opened, and the TiCuN / Cu double-layer film sample is taken out;

[0075] Step 9: Place the TiCuN / Cu double-layer film sample prepared in step 8 into a heat treatment furnace, oxidize it in a heat treatment furnace at a temperature of 700°C for 2 hours, and the heating rate is 3°C / min. After the insulation is completed, stop heating, and take out the sample after the furnace body cools naturally to room temperature.

[0076] The rest is the same as Example 1.

[0077] Example 4

[0078] Step 1: A 304 stainless steel substrate with a size of 20.0 mm × 20.0 mm × 1.0 mm is ground with sandpaper from coarse to fine, and then polished to a mirror finish;

[0079] Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation for 30 minutes, and then immersing it in deionized water for ultrasonic cleaning for 40 minutes;

[0080] Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and dry it in a blast drying oven at 90° C. for 30 minutes;

[0081] Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, and install a Ti target and a Cu target with a purity of 99.999% on the target base respectively. The Ti and Cu targets are tilted at a 45° angle relative to each other. Adjust the distance between the substrate and the sputtering target to 50 mm. No bias is applied to the target. Close the sputtering chamber. After confirming that all links are correct, first open the mechanical pump and the pre-evacuation valve to perform low vacuum extraction. When the air pressure in the sputtering chamber is lower than 0.5 Pa, close the pre-evacuation valve, and open the fore valve, molecular pump and gate valve in sequence to perform high vacuum extraction.

[0082] Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, set the argon flow rate to 50 sccm, the sputtering pressure to 0.4 Pa, the Ti power to 100 W, the Cu power to 50 W, open the substrate baffle, open the argon valve, pass argon, turn on the DC power supply of the Ti target and Cu target, and pre-sputter the Ti target and Cu target for 20 minutes to remove impurities attached to the surface of the Ti target and Cu target;

[0083] Step 6: After the pre-sputtering in step 5 is completed, the substrate baffle is closed, the Cu target sputtering power is set to 60 W, the deposition time is set to 40 min, the sputtering pressure is set to 0.3 Pa, the substrate temperature is set to room temperature, the substrate baffle is closed, the Cu target DC power supply is turned on, and magnetron sputtering is performed to deposit a Cu thin film;

[0084] Step 7, after the sputtering in step 6 is completed, the sputtering power of the Ti target is set to 100 W, the sputtering power of the Cu target is set to 40 W, the deposition time is set to 30 min, the sputtering pressure is set to 0.3 Pa, the substrate temperature is set to room temperature, the nitrogen valve is opened, nitrogen is introduced, the DC power supply of the Ti target and the Cu target is turned on, and reactive magnetron sputtering is performed to deposit a TiCuN film;

[0085] Step 8: After the sputtering in step 7 is completed, the DC power supply of the Ti target and the Cu target is turned off, the vacuum valve is opened, and the TiCuN / Cu double-layer film sample is taken out;

[0086] Step 9: Place the TiCuN / Cu double-layer film sample prepared in step 8 into a heat treatment furnace, oxidize it at a temperature of 800°C for 2 hours, and heat up at a rate of 3°C / min. After the heat preservation is completed, stop heating, and take out the sample after the furnace body cools naturally to room temperature.

[0087] The rest is the same as Example 1.

[0088] Figure 1 The XRD pattern of the functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles prepared in Example 3 shows the presence of a CuO diffraction peak, while no other impurity peaks are detected, indicating successful production of the CuO film. This is because, after adjusting the process parameters, O atoms in the film replace N atoms in the TiCuN lattice, and Cu atoms with smaller atomic radius replace Ti atoms with larger atomic radius in the TiCuN lattice. The Ti and N atoms then escape from the film, forming the desired functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles.

[0089] Figure 2 This is a surface SEM image of the functional film with a two-dimensional hybrid structure of CuO nanowires and nanoparticles prepared in Example 3. The film is composed of CuO nanowires and CuO nanoparticles. After heat treatment, the TiCuN film in the TiCuN / Cu double-layer film generates CuO nanoparticles, while after heat treatment, the Cu film generates CuO nanowires. The CuO nanoparticles are uniform in size, with a particle size of approximately 51 to 96 nm. The CuO nanowires are evenly distributed in the CuO nanoparticles and have varying lengths. The longest surface length measured is approximately 1175 nm.

[0090] The diverse morphologies and structures give the nano CuO film multiple functions. The film prepared by the present invention has good electrical conductivity, hydrophobicity, electromagnetic shielding and other properties. Figure 3 The figure shows the contact angle of the CuO nanowire and nanoparticle two-dimensional hybrid structure functional film prepared in Example 3. The contact angle of the prepared film is about 155.4°, which can be used as a superhydrophobic material and has broad application prospects.

[0091] Parts or structures not specifically described in the present invention may adopt existing technologies or existing products and will not be described in detail here.

[0092] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film, characterized in that: The following steps are involved: First, a TiCuN / Cu bilayer film was prepared using magnetron sputtering technology. Subsequently, the TiCuN / Cu bilayer film was oxidized in an air atmosphere to replace the Ti atoms in the TiCuN lattice with Cu atoms and the N atoms in the TiCuN lattice with O atoms, thereby preparing the desired CuO nanowire and nanoparticle two-dimensional hybrid structure functional film. The steps of oxidizing the TiCuN / Cu double-layer film in an air atmosphere include: The prepared TiCuN / Cu double-layer film is placed in a heat treatment furnace for oxidation at a temperature of 300-1000°C, a holding time of 1-3 hours, and a heating rate of 1-8°C / min. After the holding period is completed, heating is stopped and the furnace body is naturally cooled to room temperature. The CuO nanowire and nanoparticle two-dimensional hybrid structure functional film has a nanomorphology composed of CuO nanowires and CuO nanoparticles. The CuO nanoparticles are uniform in size, with a particle size of 51 to 96 nm. The CuO nanowires are uniformly distributed in the CuO nanoparticles with varying lengths. The contact angle of the CuO nanowire and nanoparticle two-dimensional hybrid structure functional film is 130.1° to 159.4°.

2. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 1, characterized in that: The TiCuN / Cu double-layer film is prepared by the following steps: Step 1: First, the substrate is mechanically polished with sandpaper, and then polished until the surface has no obvious scratches and is mirror-like; Step 2: immersing the substrate obtained in step 1 in an ethanol solution for ultrasonic excitation, and then immersing it in deionized water for ultrasonic cleaning; Step 3: Wipe the surface of the substrate obtained in step 2 with special paper and then dry it in a blast drying oven; Step 4: Place the substrate obtained in step 3 on the central sample stage of the magnetron sputtering instrument, install the Ti target and Cu target on the target base, close the sputtering chamber, and after confirming that all steps are correct, perform vacuum extraction; Step 5: When the vacuum in step 4 reaches the background vacuum of 3.0×10 -4 After Pa, open the argon valve to introduce argon, then turn on the DC power supply of Ti and Cu targets respectively to pre-sputter the Ti and Cu targets to remove impurities attached to the surface of the Ti and Cu targets; Step 6: After the pre-sputtering in step 5 is completed, the Cu thin film sputtering parameters are set, the Cu target DC power supply is turned on, and magnetron sputtering is performed to deposit a pure Cu thin film; Step 7: After the sputtering in step 6 is completed, the TiCuN film sputtering parameters are set, the nitrogen valve is opened, nitrogen is introduced, the DC power supply of the Ti and Cu targets is turned on, and reactive magnetron co-sputtering is performed to deposit the TiCuN film; Step 8. After the sputtering in step 7 is completed, turn off the DC power supply of the Ti and Cu targets, close the nitrogen and argon valves, open the vacuum valve, and take out the film sample.

3. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 2, characterized in that: In step 2, the ultrasonic excitation time using the ethanol solution is 10 to 60 minutes, and the ultrasonic cleaning time using deionized water is 10 to 60 minutes.

4. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 2, characterized in that: In step 3, the substrate is dried in a blast drying oven at a temperature of 50-100° C. for 20-100 min.

5. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 2, characterized in that: In step 5, during pre-sputtering, the argon flow rate is 20-50 sccm, the sputtering pressure is 0.1-0.4 Pa, the Ti target sputtering power is 50-200 W, the Cu target sputtering power is 30-80 W, and the sputtering time is 20-60 min.

6. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 2, characterized in that: In step 6, the Cu target sputtering power is 30-80 W, the deposition time is 20-40 min, the sputtering gas pressure is 0.1-0.4 Pa, and the substrate temperature is room temperature.

7. The method for preparing a CuO nanowire and nanoparticle two-dimensional hybrid structure functional film according to claim 2, characterized in that: In step 7, the sputtering power of the Ti target is 80-150 W, the sputtering power of the Cu target is 30-80 W, the deposition time is 20-60 min, the sputtering gas pressure is 0.1-0.4 Pa, and the substrate temperature is room temperature.

8. A CuO nanowire / nanoparticle two-dimensional hybrid structure functional film prepared according to the method for preparing a CuO nanowire / nanoparticle two-dimensional hybrid structure functional film according to any one of claims 1 to 7.

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