阅读说明：本技术 一种基于Cu膜成分和结构设计的CuO多相结构材料及其制备方法 (CuO multiphase structure material based on Cu film component and structure design and preparation method thereof ) 是由 唐春梅 王红莉 黄淑琪 石倩 洪悦 许伟 汪唯 郭朝乾 林松盛 代明江 苏一凡 于 2020-12-24 设计创作，主要内容包括：本发明属于纳米材料制备技术领域,具体涉及一种基于Cu膜成分和结构设计的CuO多相结构材料及其制备方法,CuO多相结构材料由Cu膜氧化制得,Cu膜为掺杂X材料的Cu/X复合膜或Cu/X多层膜；X材料为扩散速率低于Cu或氧化温度高于Cu的金属或金属氧化物或非金属。本发明基于不同元素的热激活扩散和氧化速率的不同,结合溅射沉积和热氧化法制备CuO多相结构材料,通过掺杂和多孔网络层等增加活性位点和接触面积等方式,增强CuO多相结构材料的物理化学性能,使得通过Cu膜的成分的结构设计实现CuO多相结构材料的形貌和结构可控成为可能。(The invention belongs to the technical field of nano material preparation, and particularly relates to a CuO multiphase structure material based on Cu film component and structure design and a preparation method thereof, wherein the CuO multiphase structure material is prepared by oxidizing a Cu film, and the Cu film is a Cu/X composite film or a Cu/X multilayer film doped with an X material; the X material is a metal or a metal oxide or a nonmetal with a diffusion rate lower than Cu or an oxidation temperature higher than Cu. The CuO multiphase structure material is prepared by combining a sputtering deposition method and a thermal oxidation method based on the difference of thermal activation diffusion and oxidation rates of different elements, and the physical and chemical properties of the CuO multiphase structure material are enhanced by doping, a porous network layer and other modes of increasing active sites, contact areas and the like, so that the control of the morphology and the structure of the CuO multiphase structure material can be realized through the structural design of the components of the Cu film.)

1. The CuO multiphase structure material is characterized in that the CuO multiphase structure material is prepared by oxidizing a Cu film, wherein the Cu film is a Cu/X composite film or a Cu/X multilayer film doped with an X material; the X material is a metal or a metal oxide or a nonmetal with the diffusion rate lower than Cu or the oxidation temperature higher than Cu.

2. The CuO multiphase structure material of claim 1, wherein the X material is C or Ag or ZnO.

3. The CuO multiphase structure material according to claim 2, wherein the Cu film is any one of a Cu/C composite film, a Cu/C multilayer film, a Cu/Ag composite film, a Cu/Ag multilayer film, a Cu/ZnO composite film, and a Cu/ZnO multilayer film.

4. The CuO multi-phase structural material according to claim 3, wherein the Cu/C multi-layer film is of a Cu/C/Cu/C/Cu/C structure; the Cu/Ag multilayer film is of a Cu/Ag/Cu/Ag/Cu/Ag structure; the Cu/ZnO multilayer film is a ZnO/Cu/ZnO/Cu/ZnO/Cu structure.

5. The method for preparing the CuO multi-phase structural material according to any one of claims 1 to 4, which comprises the following steps:

(1) depositing a Cu film on a substrate by a direct current or radio frequency sputtering method;

(2) carrying out thermal oxidation treatment on the Cu film deposited on the substrate for 4-24 h at the temperature of 300-450 ℃ in an air atmosphere to prepare a CuO multi-phase structure material; the CuO multiphase structure material is a doped CuO nano rod material or a porous network layer/CuO nano rod material.

6. The method for preparing CuO multiphase structure material of claim 5, wherein the substrate is Si or foam Ni or carbon cloth.

7. The method for preparing a CuO multiphase structure material according to claim 5 or 6, wherein the Cu film is prepared by deposition at room temperature by DC sputtering a Cu target, an Ag target or a radio frequency sputtering a C target, a ZnO target in the step (1); the thickness of the Cu film is 1-10 mu m.

8. The method for preparing a CuO multiphase structure material according to claim 7, wherein the power for DC sputtering the Cu target is 150 w; the power of DC sputtering Ag target is 75 w; the power of the radio-frequency sputtering C target is 150 w; the power for radio frequency sputtering of the ZnO target is 100 w.

9. The method for preparing the CuO multiphase structure material according to claim 8, wherein specific parameters of the direct current or radio frequency sputtering are as follows: background vacuum degree of 2X 10^-4Pa～4×10^-4Pa, inert atmosphere; the sputtering pressure is 0.3 to 2Pa, and the sputtering power is 50 to 200 w.

10. The method for preparing a CuO multi-phase structural material according to claim 9, wherein the thermal oxidation process in the step (2) is an electric field assisted thermal oxidation process, and the electric field strength is 0 to 30000Vm^-1The direction of the electric field is perpendicular to the substrate upwards.

Technical Field

The invention belongs to the technical field of nano material preparation, and particularly relates to a CuO multiphase structure material based on Cu film component and structure design and a preparation method thereof.

Background

One-dimensional metal oxide nanostructures have received much attention from researchers due to their unique physicochemical properties and their value of application in functional devices. The controllable preparation of metal oxide nanomaterials with different sizes, morphologies, chemical compositions and structures is the key to the progress of nano science and nano technology. Thermal oxidation has the advantages of simplicity, high efficiency, low cost, large-scale preparation and the like, has been successfully used for preparing several single-phase metal oxide nanostructures, and has unique advantages in relevant aspects. However, most of the current work only researches the influence of the processes such as thermal oxidation temperature, time, atmosphere, stress, roughness, electric field and the like, the precise regulation of the oxide nanostructure has certain difficulty, and the work of regulating the oxide growth by designing metal source components and structures is still less.

Sputtering deposition can be used for designing thin film components and structures, such as multilayer films, composite films and the like, so that oxide-based multiphase structures are expected to be prepared by combining sputtering deposition and a thermal oxidation method based on the difference of thermal activation diffusion and oxidation rates of different elements, but the uncertainty of the growth mechanism of the thermal oxidation method and the interaction among different elements also makes the precise design and control of products by the method difficult.

Disclosure of Invention

Aiming at the defects and difficulties in the prior art, the invention aims to provide the CuO multi-phase structural material with controllable morphology and structure, and realize the controllability of the morphology and the structure of the CuO multi-phase structural material through the structural design of the components of the Cu film. The above-mentioned method for preparing a multi-phase structure material of CuO is provided as another object of the present invention.

Based on the above purpose, the technical scheme adopted by the invention is as follows:

in a first aspect, the invention provides a CuO multiphase structure material with controllable morphology and structure, wherein the CuO multiphase structure material is prepared by oxidizing a Cu film, and the Cu film is a Cu/X composite film or a Cu/X multilayer film doped with an X material; the X material is a metal or a metal oxide or a nonmetal with the diffusion rate lower than Cu or the oxidation temperature higher than Cu.

According to the invention, the CuO nano structure is successfully constructed by designing the Cu film and oxidizing the designed Cu film, so that the appearance and the structure of the CuO multi-phase structure material can be controlled by the structural design of the components of the Cu film. And based on the difference of thermal activation diffusion and oxidation rate of different elements, active sites and contact area are hopefully increased through doping, porous network layers and the like, so that the physical and chemical properties of the CuO multiphase structure material are enhanced.

Further, the X material is C or Ag or ZnO.

The Cu composite film or the multi-layer film is formed by doping C, Ag or ZnO in Cu through co-sputtering or step-by-step sputtering deposition, and the Cu composite film or the multi-layer film is used as a basis for realizing controllable morphology and structure of a CuO multi-phase structure material based on different Cu film structures.

Further, the Cu film is any one of a Cu/C composite film, a Cu/C multilayer film, a Cu/Ag composite film, a Cu/Ag multilayer film, a Cu/ZnO composite film and a Cu/ZnO multilayer film.

Further, the Cu/C multilayer film is of a Cu/C/Cu/C/Cu/C structure; the Cu/Ag multilayer film is of a Cu/Ag/Cu/Ag/Cu/Ag structure; the Cu/ZnO multilayer film is a ZnO/Cu/ZnO/Cu/ZnO/Cu structure.

In a second aspect, the present invention provides a preparation method of the CuO multi-phase structural material, including the following steps:

(1) depositing a Cu film on a substrate by a direct current or radio frequency sputtering method;

(2) carrying out thermal oxidation treatment on the Cu film deposited on the substrate for 4-24 h at the temperature of 300-450 ℃ in an air atmosphere to prepare a CuO multi-phase structure material; the prepared CuO multiphase structure material is a CuO doped nanorod material or a porous network layer/CuO nanorod material.

The CuO doped nanorod or the porous network layer/CuO nanorod material is prepared by combining a sputtering deposition method and a thermal oxidation method based on the difference of thermal activation diffusion and oxidation rates of different elements, and active sites, contact areas and the like are hopefully increased through doping, the porous network layer and the like, so that the CuO multiphase structure material with enhanced physical and chemical properties or excellent CuO multiphase structure is obtained.

In addition, the invention carries out thermal oxidation treatment on Cu films with different designs by non-chemical methods such as sputtering deposition, thermal oxidation and the like to prepare the CuO multiphase structure material, and has the advantages of simple process, low cost, no need of catalyst, large-scale preparation and environmental friendliness.

Further, the substrate is Si or foamed Ni or carbon cloth.

The invention can directly assemble the multi-phase structural material based on CuO on different substrates such as Si sheets, foam Ni or carbon cloth and the like so as to meet the requirements of devices with different functions; the Si sheet, the foam Ni and other substrates have the advantage that the structure can be kept from being damaged at the temperature of 300-450 ℃; when the carbon cloth is used as a substrate, the carbon cloth can resist the temperature of 300-400 ℃ and keep the structure from being damaged.

Further, depositing a Cu target, an Ag target or a radio frequency sputtering C target and a ZnO target at room temperature to prepare a Cu film in the step (1); the Cu film has a thickness of 1 to 10 μm.

Further, the power of DC sputtering the Cu target is 150 w; the power of DC sputtering Ag target is 75 w; the power of the radio-frequency sputtering C target is 150 w; the power for radio frequency sputtering of the ZnO target is 100 w.

Further, the specific parameters of dc or rf sputtering are as follows: background vacuum degree of 2X 10^-4Pa～4×10^{- 4}Pa, inert atmosphere; the sputtering pressure is 0.3 to 2Pa, and the sputtering power is 50 to 200 w.

Further, the specific parameters of sputtering in the preparation process of different Cu films are as follows:

when the Cu film is a Cu/C composite film, co-sputtering a Cu target and a C target, wherein the power of a DC sputtering Cu target is 150w, the power of a radio frequency sputtering C target is 150w, and the co-sputtering time is 30 min;

when the Cu film is a Cu/C multilayer film, DC sputtering a Cu target for 10min at 150w to deposit Cu; sputtering a C target at 150w power for 10min to deposit C; repeating the processes of DC sputtering the Cu target and radio frequency sputtering the C target for three times, wherein the total sputtering time is 60min, and forming a Cu/C multilayer film with a Cu/C/Cu/C/Cu/C structure;

when the Cu film is a Cu/Ag composite film, co-sputtering a Cu target and an Ag target, wherein the power of a DC sputtering Cu target is 150w, the power of a radio frequency sputtering Ag target is 75w, and the co-sputtering time is 30 min;

when the Cu film is a Cu/Ag multilayer film, DC sputtering a Cu target for 10min at 150w to deposit Cu; DC sputtering an Ag target for 10min at 75w to deposit Ag; repeating the process of DC sputtering the Cu target and the Ag target for three times, wherein the total sputtering time is 60min, and forming a Cu/Ag multilayer film with a Cu/Ag/Cu/Ag/Cu/Ag structure;

when the Cu film is a Cu/ZnO composite film, co-sputtering by adopting a Cu target and a ZnO target, wherein the power of a direct-current sputtering Cu target is 150w, the power of a radio-frequency sputtering ZnO target is 100w, and the co-sputtering time is 30 min;

when the Cu film is a Cu/ZnO multilayer film, performing radio frequency sputtering on a ZnO target for 10min at the power of 100w to deposit ZnO; DC sputtering a Cu target for 10min at 150w to deposit Cu; repeating the processes of radio frequency sputtering of the ZnO target and direct current sputtering of the Cu target for three times, wherein the total sputtering time is 60min, and forming the Cu/ZnO multilayer film with the ZnO/Cu/ZnO/Cu/ZnO/Cu structure.

Further onThe thermal oxidation treatment in the step (2) is an electric field assisted thermal oxidation method, and the electric field intensity is 0-30000 Vm^-1The direction of the electric field is perpendicular to the substrate upwards.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention uses non-chemical treatment methods such as sputtering deposition, thermal oxidation method and the like, and has the advantages of simple process, low cost, no need of catalyst, large-scale preparation and environmental friendliness.

(2) Based on the difference of thermal activation diffusion and oxidation rate of different elements, the doped CuO nanorod or the porous network layer/CuO nanorod material is prepared by combining sputtering deposition and a thermal oxidation method, and the active sites, the contact area and the like are increased by doping, the porous network layer and the like, so that the physical and chemical properties of the CuO multi-phase structure material are enhanced.

(3) The method for preparing the CuO multiphase structure material can be suitable for different substrates such as Si, foamed Ni or carbon cloth, and the like, meets the requirements of different functional devices by directly assembling the CuO multiphase structure material on the different substrates, and has the advantage of wide application range.

Drawings

FIG. 1 is a sectional scanning electron microscope topography of the Si-based Cu/C composite film of example 1;

FIG. 2 is a surface scanning electron microscope topography of the Cu/C composite film on the foam Ni after thermal oxidation in example 2;

FIG. 3 is a sectional scanning electron microscope topography of the Si-based Cu/C multilayer film of example 3;

FIG. 4 is a sectional SEM image of a thermally oxidized Si-based Cu/C multilayer film in example 4;

FIG. 5 is a surface scanning electron microscope topography of the Cu/C multilayer film on foamed Ni in example 5 after thermal oxidation;

FIG. 6 is a sectional scanning electron microscope topography of the Si-based Cu/Ag composite film of example 6;

FIG. 7 is a Scanning Electron Microscope (SEM) profile of a cross-section of the Si-based Cu/Ag composite film obtained by thermal oxidation in example 7;

FIG. 8 is a scanning electron microscope topography of the thermally oxidized Cu/Ag composite film on the foam Ni in example 8;

FIG. 9 is a surface Scanning Electron Microscope (SEM) morphology of the thermally oxidized Cu/Ag composite film on the carbon cloth in example 9;

FIG. 10 is a sectional scanning electron microscope topography of the Si-based Cu/Ag multilayer film of example 10;

FIG. 11 is a surface scanning electron microscope topography of the Cu/Ag multilayer film on foamed Ni in example 11 after thermal oxidation;

FIG. 12 is a surface scanning electron microscope topography of the thermally oxidized Cu/Ag multilayer film on the carbon cloth of example 12;

FIG. 13 is a sectional scanning electron microscope topography of the Si-based Cu/ZnO composite film of example 13;

FIG. 14 is a scanning electron microscope topography of the thermally oxidized Cu/ZnO composite film on the foam Ni in example 14;

FIG. 15 is a sectional scanning electron microscope topography of the Si-based Cu/ZnO multilayer film of example 15;

FIG. 16 is a scanning electron microscope topographical view of a cross-section of the Si-based Cu/ZnO multilayer film obtained after thermal oxidation in example 16;

FIG. 17 is a surface scanning electron microscope topography of the Cu/ZnO multilayer on foam Ni after thermal oxidation in example 17;

FIG. 18 is an X-ray diffraction pattern of different Cu-containing thin films of examples 1, 3, 6, 10, 13, and 15;

FIG. 19 is an X-ray diffraction pattern of different Cu-containing thin films of examples 2, 5, 8, 11, 14 and 17 after thermal oxidation.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments. The raw materials used in the following examples are all commercially available general-purpose products unless otherwise specified.

EXAMPLE 1 preparation of Cu/C composite film on Si base

A Cu/C composite film is deposited on an N-type Si (100) substrate by adopting a direct current/radio frequency co-sputtering method, and the preparation process comprises the following steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the C target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, sputtering pressure of 2Pa, adopting a Cu target and C target co-sputtering mode, wherein the power of a direct current sputtering Cu target is 150w, the power of a radio frequency sputtering C target is 150w, the co-sputtering time is 30min, and depositing at room temperature to prepare the Cu/C composite film.

The morphology of the cross section of the Cu/C composite film on the Si base is shown in figure 1.

Example 2 preparation of CuO nanorod from Cu/C composite film oxidized on Ni foam

In the embodiment, the CuO nanorod is prepared by thermally oxidizing a Cu/C composite film on foamed Ni, and the specific process is as follows:

(1) preparation of Cu/C composite film on foamed Ni

A Cu/C composite membrane is prepared on a foamed Ni substrate by the method described in reference example 1, and the difference from example 1 is only in the material of the substrate, and the present example takes foamed Ni as the substrate.

(2) Preparation of CuO nano rod from thermal oxidation Cu/C composite film on foamed Ni

Heating a Cu/C composite film grown on foamed Ni by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8 hours, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is CuO layer/C doped CuO nano rod.

The surface scanning electron microscope topography of the Cu/C composite film on the foam Ni after thermal oxidation is shown in figure 2.

EXAMPLE 3 preparation of a Cu/C multilayer on Si basis

The embodiment provides a method for preparing a Cu/C multilayer film on a Si base, which comprises the following specific steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the C target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, and sputtering pressure of 2 Pa; firstly, a Cu target is DC sputtered at 150w power to deposit on a Si base to form a Cu layer, a C target is RF sputtered at 150w power to form a C layer, a Cu target is DC sputtered at 150w power to deposit on the C layer to form a Cu layer, a C target is RF sputtered at 150w power to form a C layer, and the C layer is RF sputtered at 150w power to form a C layer on the Cu layer, wherein the total sputtering time is 60min, and the Cu/C multilayer film is deposited at room temperature.

The structure of the Cu/C multilayer film is a Cu/C/Cu/C/Cu/C structure, and the cross-sectional scanning electron microscope topography of the Si-based Cu/C multilayer film is shown in FIG. 3.

Example 4 preparation of CuO micro-nano-protrusions from Si-based Cu/C oxide multilayer film

In the embodiment, the CuO micro-nano bump is prepared by thermally oxidizing a Cu/C multilayer film on a Si base, and the specific preparation process is as follows:

(1) preparation of Cu/C multilayer film on Si base

A Cu/C multilayer film on Si basis was prepared as described in reference to example 3.

(2) The specific process for preparing the CuO micro-nano bump by thermally oxidizing the Cu/C multilayer film on the Si base is as follows:

preparing a CuO nanorod by adding a Cu/C multilayer film grown on a Si base by an electric field assisted thermal oxidation method, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is CuO layer/C doped CuO micro-nano bump.

The appearance of the cross section of the Si-based Cu/C multilayer film after thermal oxidation is shown in FIG. 4.

EXAMPLE 5 preparation of CuO nanorods by oxidizing Cu/C multilayer films on Ni foam

In this embodiment, CuO nanorods are prepared by thermally oxidizing Cu/C multilayer films on Ni foam, and the specific preparation process is as follows:

(1) preparation of Cu/C multilayer film on foamed Ni

A Cu/C multilayer film is prepared on a foamed Ni substrate by the method described in reference example 3, and the difference from example 3 is only the difference of the substrate material, and the present example takes foamed Ni as the substrate.

(2) The specific process for preparing the CuO nano rod by foaming the Ni thermal oxidation Cu/C multilayer film is as follows:

heating a Cu/C multilayer film grown on foamed Ni by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is CuO layer/C doped CuO nano rod.

The surface scanning electron microscope topography of the Cu/C multilayer film on the foam Ni after thermal oxidation is shown in FIG. 5.

Examples 1 to 5 show a Cu/C composite film or a Cu/C multilayer film and CuO nanorods prepared by thermal oxidation treatment, and the drawings of examples 1 to 5 are shown in FIGS. 1 to 5, respectively. It can be seen that the Cu/C composite film in fig. 1 is columnar crystal, similar to the pure Cu film, and the Cu/C multilayer film in fig. 3 is 3 layers, and no obvious C layer is found, which is caused by the slow deposition rate of the radio frequency plating C, so the structure of the Cu/C composite film or the Cu/C multilayer film is similar to that of the pure Cu. The layered structure of the Cu/C composite film or the Cu/C multilayer film after thermal oxidation is also similar to that of the pure Cu film after thermal oxidation, and CuO nanorods are successfully obtained after the Cu/C film in the figures 2 and 5 is thermally oxidized.

EXAMPLE 6 preparation of Cu/Ag composite film on Si base

A Cu/Ag composite film is deposited on an N-type Si (100) substrate by adopting a direct-current co-sputtering method, and the preparation process comprises the following steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the Ag target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, sputtering pressure of 0.6Pa, adopting a mode of co-sputtering a Cu target and an Ag target, wherein the power of the DC sputtering Cu target is 150w, the power of the DC sputtering Ag target is 75w, the co-sputtering time is 30min, and placing the chamber in a roomAnd (4) preparing the Cu/Ag composite film by warm deposition.

The cross-sectional scanning electron microscope topography of the Si-based Cu/Ag composite film is shown in FIG. 6.

Example 7 preparation of CuO micro-nano protrusions from Si-based Cu/Ag oxide composite film

In the embodiment, the method for preparing the CuO micro-nano bump by thermally oxidizing the Cu/Ag composite film on the Si base comprises the following specific steps:

(1) preparation of Cu/Ag composite film on Si base

A Cu/Ag composite film was prepared on a Si basis by the method described in example 6.

(2) The specific process for preparing the CuO micro-nano bump by thermally oxidizing the Cu/Ag composite film on the Si base is as follows:

heating a Cu/Ag composite film grown on a Si base by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8 hours, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is a porous network Ag layer/CuO micro-nano bump.

The appearance of the cross section of the Cu/Ag composite film on the Si base after thermal oxidation is shown in figure 7.

EXAMPLE 8 preparation of CuO Nanoprotrusions from Cu/Ag oxide composite films on Ni foam

In this embodiment, the method for preparing the CuO nano bump by thermally oxidizing the Cu/Ag composite film on the foamed Ni includes the following specific steps:

(1) preparation of Cu/Ag composite film on foamed Ni substrate

A Cu/Ag composite film was prepared on a foamed Ni substrate according to the method described in example 6, differing from example 6 only in the material of the substrate, which was foamed Ni.

(2) The specific process for preparing CuO nano bulges by thermally oxidizing Cu/Ag on foamed Ni is as follows:

heating a Cu/Ag composite film grown on foamed Ni by using an electric field assisted thermal oxidation method to prepare a CuO nano bump, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field strength is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The product structure is a porous netThe complex Ag layer/CuO micro-nano bump.

The surface scanning electron microscope topography of the Cu/Ag composite film on the foam Ni after thermal oxidation is shown in FIG. 8.

EXAMPLE 9 preparation of CuO nanorod from Cu/Ag oxide composite film on carbon cloth

In the embodiment, the method for preparing the CuO nanorod by thermally oxidizing the Cu/Ag composite film on the carbon cloth comprises the following specific steps:

(1) preparation of Cu/Ag composite film on carbon cloth substrate

The Cu/Ag composite film was fabricated on the carbon cloth substrate according to the method described in example 6, which is different from example 6 only in the material of the substrate, and the carbon cloth was used as the substrate in this example.

(2) The specific process for preparing the CuO nano rod by thermally oxidizing Cu/Ag on the carbon cloth is as follows:

heating a Cu/Ag composite film grown on carbon cloth by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 330 ℃, the time is 8 hours, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is porous network Ag layer/CuO nano rod.

The topography of the surface of the Cu/Ag composite film on the carbon cloth after thermal oxidation is shown in FIG. 9.

EXAMPLE 10 preparation of a Cu/Ag multilayer film on Si basis

A Cu/Ag multilayer film is deposited on an N-type Si (100) substrate by adopting a magnetron sputtering method, and the preparation process comprises the following steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the Ag target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, and sputtering pressure of 0.6 Pa; firstly, DC sputtering Cu target with 150w power to form Cu layer, DC sputtering Ag target with 75w power to form Ag layer on the Cu layer, DC sputtering Cu target with 150w power to form Cu layer on the Ag layer, and DC sputtering Cu target with 75w power to form Cu layerAnd carrying out flow sputtering on an Ag target to form an Ag layer, carrying out direct current sputtering on the Cu target at a power of 150w to deposit on the Ag layer to form a Cu layer, carrying out direct current sputtering on the Ag target at a power of 75w to form an Ag layer on the Cu layer, wherein the total sputtering time is 60min, and carrying out deposition at room temperature to obtain the Cu/Ag multilayer film.

The structure of the Cu/Ag multilayer film is a Cu/Ag/Cu/Ag/Cu/Ag structure. The cross-sectional scanning electron microscope topography of the Si-based Cu/Ag multilayer film is shown in FIG. 10.

Example 11 preparation of CuO micro-nano protrusions from a Cu/Ag multilayer film on Ni foam

In the embodiment, the CuO micro-nano bump is prepared by thermally oxidizing a Cu/Ag multilayer film on foamed Ni, and the specific preparation process is as follows:

(1) preparation of Cu/Ag multilayer film on foamed Ni

Referring to example 10, a Cu/Ag multilayer film on foamed Ni was prepared by replacing the Si group in example 10 with the foamed Ni of this example and following the same procedure as in example 10.

(2) The specific process for preparing the CuO micro-nano bump by thermally oxidizing the Cu/Ag multilayer film on the foamed Ni is as follows:

heating a Cu/Ag multilayer film grown on foam Ni by using an electric field assisted thermal oxidation method to prepare a CuO micro-nano projection, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is a porous network Ag layer/CuO micro-nano bump.

The surface scanning electron microscope topography of the Cu/Ag multilayer film on the foam Ni after thermal oxidation is shown in FIG. 11.

EXAMPLE 12 preparation of CuO nanorods by oxidizing Cu/Ag multilayer film on carbon cloth

In this embodiment, a method for preparing CuO nanorods by thermally oxidizing a Cu/Ag multilayer film on carbon cloth includes the following specific steps:

(1) preparation of Cu/Ag multilayer film on carbon cloth substrate

Referring to example 10, a Cu/Ag multilayer film on a carbon cloth was fabricated by replacing the Si group in example 10 with the carbon cloth of this example and following the same procedure as in example 10.

(2) The specific process for preparing the CuO nano rod by thermally oxidizing the Cu/Ag multilayer film on the carbon cloth is as follows:

heating a Cu/Ag multilayer film grown on carbon cloth by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 330 ℃, the time is 8h, the atmosphere is air, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is porous network Ag layer/CuO nano rod.

The surface scanning electron microscope topography of the thermally oxidized Cu/Ag multilayer film on the carbon cloth is shown in FIG. 12.

Examples 6 to 12 are Cu/Ag composite films or Cu/Ag multilayer films or CuO nanostructures prepared by thermal oxidation thereof, and corresponding figures are respectively shown in fig. 6 to 12.

Since the deposition rate of direct current Ag plating is significantly faster than that of radio frequency C plating, the Cu/Ag composite film of FIG. 6 is in the form of granular crystals rather than columnar crystals; the Cu/Ag multilayer film of fig. 10 is 6 layers, in which the Cu layer is columnar crystal and the Ag layer is granular crystal. Different from fig. 4, the layered structure of the Cu/Ag composite film in fig. 7 after thermal oxidation is a porous network Ag layer/CuO micro-nano bump. Although CuO obtained when Si or Ni foam is used as a substrate in fig. 7, 8 and 11 is a short and thick micro-nano projection, a long and thin CuO nanorod is successfully obtained when carbon cloth is used as a substrate in fig. 9 and 12.

EXAMPLE 13 preparation of Cu/ZnO composite film on Si base

A Cu/ZnO composite film is deposited on an N-type Si (100) substrate by adopting a direct current/radio frequency co-sputtering method, and the preparation process comprises the following steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the ZnO target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, sputtering pressure of 2Pa, adopting a Cu target and ZnO target co-sputtering mode, wherein the power of a direct current sputtering Cu target is 150w, the power of a radio frequency sputtering ZnO target is 100w, the co-sputtering time is 30min, and depositing at room temperature to prepare the CuA/ZnO composite film.

The cross-sectional scanning electron microscope topography of the Si-based Cu/ZnO composite film is shown in FIG. 13.

Example 14 preparation of CuO nanorods through Cu/ZnO composite film on Ni foam

In the embodiment, the CuO nanorod is prepared by oxidizing the Cu/ZnO composite film on the foamed Ni, and the preparation process specifically comprises the following steps:

(1) preparation of Cu/ZnO composite film on foamed Ni

Referring to example 13, a Cu/ZnO composite film on a foamed Ni substrate was fabricated by replacing the substrate of example 13 with foamed Ni from Si, according to the method of example 13 for fabricating a Cu/ZnO composite film on a Si substrate.

(2) Preparation of CuO nano rod by thermal oxidation Cu/ZnO composite film on foamed Ni

Heating a Cu/ZnO composite film grown on foamed Ni by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8 hours, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is ZnO layer/CuO nano rod.

The surface scanning electron microscope topography of the Cu/ZnO composite film on the foam Ni after thermal oxidation is shown in FIG. 14.

EXAMPLE 15 preparation of a Cu/ZnO multilayer film on Si group

A Cu/ZnO multilayer film is deposited on an N-type Si (100) substrate by adopting a magnetron sputtering method, and the preparation process comprises the following steps:

(1) and ultrasonically cleaning the N-type Si substrate with acetone and ethanol for 15min, drying, adhering the substrate to a sample holder, and then filling the sample holder into a vacuum cavity.

(2) And (4) polishing the target material by using sand paper to remove impurities such as oxides on the surfaces of the Cu target and the ZnO target.

(3) The following parameters were set: background vacuum degree of 2X 10^-4Pa, argon atmosphere, sputtering pressure of 2Pa, firstly, sputtering ZnO target with 100w power radio frequency to deposit on the Si substrate to form ZnO layer, sputtering Cu target with 150w power direct current to deposit on the ZnO layer to form Cu layer, sputtering ZnO target with 100w power radio frequency to form ZnO layer on the Cu layer, and sputtering with 150w power direct current to sputter ZnO layerAnd (3) shooting a Cu target to deposit on the ZnO layer to form a Cu layer, performing radio frequency sputtering on the ZnO target at the power of 100w to form the ZnO layer on the Cu layer, performing radio frequency sputtering on the Cu target at the power of 150w to form the Cu layer on the ZnO layer, wherein the total sputtering time is 60min, and depositing at room temperature to prepare the Cu/ZnO multilayer film.

The structure of the Cu/ZnO multilayer film is a ZnO/Cu/ZnO/Cu/ZnO/Cu structure. The profile of the cross section of the Cu/ZnO multilayer film on the Si base by a scanning electron microscope is shown in FIG. 15.

Example 16 preparation of CuO micro-nano protrusions from Si-based Cu/ZnO multilayer film

The embodiment provides a method for preparing a CuO micro-nano bump on a Si base by thermally oxidizing a Cu/ZnO multilayer film, which comprises the following specific preparation processes:

(1) preparation of Cu/ZnO multilayer film on Si base

A Cu/ZnO multilayer film was deposited on a Si-base according to the method described in example 15.

(2) CuO micro-nano bump prepared by thermally oxidizing Cu/ZnO multilayer film on Si base

Heating a Cu/ZnO multilayer film grown on a Si base by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is a porous network ZnO layer/CuO micro-nano bump.

The topography of the cross section of the Si-based Cu/ZnO multilayer film after thermal oxidation is shown in FIG. 16.

EXAMPLE 17 preparation of CuO nanorods by oxidizing Cu/ZnO multilayer films on Ni foam

The embodiment provides a method for preparing a CuO nanorod on foamed Ni by thermally oxidizing a Cu/ZnO multilayer film, which comprises the following specific preparation processes:

(1) preparation of Cu/ZnO multilayer film on foam Ni

Referring to example 15, the method for preparing the Cu/ZnO multilayer film by deposition on the Si base is adopted, the base in example 15 is replaced by foamed Ni from Si, and the Cu/ZnO multilayer film is prepared by deposition on the foamed Ni in the same way as in example 15.

(2) Preparation of CuO nano rod by thermal oxidation of Cu/ZnO multilayer film on foamed Ni

Heating a Cu/ZnO multilayer film grown on foamed Ni by using an electric field assisted thermal oxidation method to prepare a CuO nanorod, wherein the thermal oxidation temperature is 400 ℃, the time is 8h, the air atmosphere is adopted, and the electric field intensity is 16667Vm^-1The direction of the electric field is perpendicular to the substrate upwards. The structure of the prepared product is porous network ZnO layer/CuO nano rod.

The surface scanning electron microscope topography of the Cu/ZnO multilayer film on the foam Ni after thermal oxidation is shown in FIG. 17.

Examples 13 to 17 show Cu/ZnO composite films or multilayer films or CuO nanorods prepared by oxidizing the same, as shown in fig. 13 to 17, fig. 13 shows a Cu/ZnO composite film structure, in order to show that the Cu/ZnO composite films are grain crystals; fig. 15 shows a Cu/ZnO multilayer film structure, and it can be seen that the Cu/ZnO multilayer film is 6 layers, in which the Cu layer is columnar crystal and the ZnO layer is granular crystal.

Fig. 14, 16, and 17 are all structures of CuO nanorods, and it can be seen that the layered structure of the Cu/ZnO multilayer film in fig. 16 after thermal oxidation is a porous network ZnO layer/CuO micro-nano protrusion, and elongated CuO nanorods are also obtained after thermal oxidation in fig. 14 and 17.

The X-ray diffraction patterns of the Cu-containing thin films of examples 1, 3, 6, 10, 13 and 15 are shown in FIG. 18, and the X-ray diffraction patterns of the Cu-containing thin films of examples 2, 5, 8, 11, 14 and 17 after thermal oxidation are shown in FIG. 19.

Peaks of the Cu/C composite film of example 1, the Cu/C multilayer film of example 3 and the Cu/ZnO composite film of example 13 in FIG. 18 are all from a Cu phase, and main phases of the three films after thermal oxidation in FIG. 19 are CuO, and a weak phase NiO is from a foam Ni substrate. Although strong CuO phase and weak ZnO phase are present in the Cu/ZnO composite film of example 15 in fig. 18, no ZnO peak is evident in example 17 after thermal oxidation in fig. 19. The strong peak of the Cu/Ag composite film of example 6 in fig. 18 is located between Cu and Ag, a strong Cu phase and a strong Ag phase appear in the Cu/Ag multilayer film of example 10, and a strong CuO phase and a strong Ag phase appear in both of examples 8 and 11 after thermal oxidation of the two films in fig. 19.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.