阅读说明：本技术 一种柔性磁控溅射金属纳米复合材料的制备方法 (Preparation method of flexible magnetron sputtering metal nano composite material ) 是由 王荣福 于 2021-08-13 设计创作，主要内容包括：本发明公开了一种柔性磁控溅射金属纳米复合材料的制备方法,包括以下步骤：步骤1,将柔性基体进行表面清洗,得到清洗后的柔性基体；步骤2,在柔性基体的表面通过辊压导电聚合物膜,得到导电聚合物的复合柔性基体；步骤3,将电聚合物的复合柔性基体置于磁控溅射设备中,使用镓化钒晶体和硒化镓晶体作为双靶材,通过真空磁控溅射镀膜技术,得到柔性磁控溅射金属纳米复合材料。本发明公开了一种在柔性基材上磁控溅射金属纳米复合材料的方法,本发明的制备工艺简单、容易操作且能够具有较好的重复性。所制备得到的材料具有较好的韧性,即使不在高温下进行退火处理,也能具有较高的比容量,且基体与各镀层之间具有较强的结合性。(The invention discloses a preparation method of a flexible magnetron sputtering metal nano composite material, which comprises the following steps: step 1, cleaning the surface of a flexible substrate to obtain a cleaned flexible substrate; step 2, rolling the conductive polymer film on the surface of the flexible substrate to obtain a composite flexible substrate of the conductive polymer; and 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using the gallium arsenide crystal and the gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology. The invention discloses a method for magnetron sputtering of a metal nano composite material on a flexible substrate, which has the advantages of simple preparation process, easy operation and better repeatability. The prepared material has good toughness, can have high specific capacity even if annealing treatment is not carried out at high temperature, and has strong bonding property between the matrix and each plating layer.)

1. A preparation method of a flexible magnetron sputtering metal nano composite material is characterized by comprising the following steps:

step 1, cleaning the surface of a flexible substrate to obtain a cleaned flexible substrate;

step 2, rolling the conductive polymer film on the surface of the flexible substrate to obtain a composite flexible substrate of the conductive polymer;

and 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using the gallium arsenide crystal and the gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology.

2. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein in the step 1, the flexible substrate is one of a PET substrate, a PI substrate, a PE substrate and a TPU substrate.

3. The preparation method of the flexible magnetron sputtering metal nanocomposite as claimed in claim 1, wherein in the step 1, the surface cleaning is that the flexible substrate is sequentially placed in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.1-0.3 h, and then a plasma cleaning agent is used for treatment for 0.1-0.2 h.

4. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein in the step 2, the flexible substrate is pretreated at 60 to 80 ℃ for 0.2 to 0.4h before rolling.

5. The method of claim 1, wherein in step 2, the conductive polymer is a polymer formed by compounding chromium polynicotinate and polyaniline.

6. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein in the step 2, the thickness of the conductive polymer film is 30-100 nm.

7. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein the method for preparing the conductive polymer film comprises the following steps:

a. weighing chromium polynicotinate nanoparticles, adding the chromium polynicotinate nanoparticles into toluene, and uniformly mixing by ultrasonic waves to obtain a chromium polynicotinate solution; wherein the mass ratio of the chromium polynicotinate nanoparticles to the toluene is 1: 5-7;

b. adding aniline into a chromium polynicotinate solution, heating to 45-55 ℃, and stirring for 1-3 hours to obtain an aniline/chromium polynicotinate solution; wherein the mass ratio of the aniline to the chromium polynicotinate solution is 1: 6-8;

c. adding ammonium persulfate powder into the aniline/chromium polynicotinate solution, adjusting the pH value to 1-2 by using hydrochloric acid, placing the solution under the condition of ice-water bath, stirring and reacting for 5-10 hours, filtering, washing the collected solid product by using absolute ethyl alcohol for at least three times, and then placing the product in a drying oven for drying treatment to obtain a polyaniline/chromium polynicotinate coating; wherein the mass ratio of the ammonium persulfate powder to the aniline in the aniline/chromium polynicotinate solution is 2: 1-1.05;

d. placing the polyaniline/chromium polynicotinate coating in deionized water, uniformly mixing to form mixed liquid, then uniformly adsorbing the solid on filter paper by using the mixed liquid through a vacuum filtration method, and peeling the filter paper after drying to form a film to obtain a conductive polymer film; wherein the mass ratio of the polyaniline/chromium polynicotinate to the deionized water is 1: 3-6.

8. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 7, wherein the particle size of the chromium polynicotinate nanoparticles is 10-20 nm.

9. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein in the step 3, parameters of magnetron sputtering are as follows: dual target and flexible substrateThe distance of (a) is 100-150 mm, and the background vacuum degree is 1.5-3 multiplied by 10^-3Pa, the working pressure is 0.25-0.5 Pa, the working gas flow is 80-120 sccm argon, the sputtering power of the double targets is 150-200W, and the sputtering time is 0.3-0.5 h.

10. The method for preparing a flexible magnetron sputtering metal nanocomposite material according to claim 1, wherein in the step 3, the thickness of magnetron sputtering is 50-200 nm, and the thickness of the flexible magnetron sputtering metal nanocomposite material is 1-5 μm.

Technical Field

The invention relates to the field of metal nano composite materials, in particular to a preparation method of a flexible magnetron sputtering metal nano composite material.

Background

Transparent Conductive Electrodes (TCEs) having excellent mechanical flexibility will be important components of next-generation wearable optoelectronic devices, and applications in fields such as light emitting devices, photovoltaic cells, switching devices, and touch screen panels will be very wide. Currently, Indium Tin Oxide (ITO) has been the most widely used TCE material in both academia and industry due to its optical transparency, thermal/chemical stability, device compatibility and sophisticated fabrication processes. However, in most applications, the thickness of ITO needs to be 150 nm or more in order to ensure electrical performance, however at such thicknesses, the ITO thin film becomes brittle making it unsuitable for applications requiring large areas or flexible substrates; secondly, in order to achieve good conductivity and clarity, the ITO film needs to be annealed at high temperatures, preferably in excess of 200 ℃, and most polymer-based ITO films cannot withstand annealing temperatures for achieving high conductivity and transparency at the same time due to the relatively low softening point of the polymer. Therefore, it is necessary to design an electrode which has high toughness, does not require high-temperature treatment, and is suitable for a large-area flexible substrate.

Disclosure of Invention

The invention aims to provide a preparation method of a flexible magnetron sputtering metal nano composite material, which solves the defects of high brittleness, high annealing requirement and poor combination with a polymer substrate of an ITO film in the prior art.

The purpose of the invention is realized by adopting the following technical scheme:

the invention provides a preparation method of a flexible magnetron sputtering metal nano composite material, which comprises the following steps:

step 1, cleaning the surface of a flexible substrate to obtain a cleaned flexible substrate;

step 2, rolling the conductive polymer film on the surface of the flexible substrate to obtain a composite flexible substrate of the conductive polymer;

and 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using the gallium arsenide crystal and the gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology.

Preferably, in step 1, the flexible substrate is one of a PET substrate, a PI substrate, a PE substrate, and a TPU substrate.

Preferably, in the step 1, the surface cleaning is to sequentially place the flexible substrate in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.1-0.3 h, and then use a plasma cleaning agent for treatment for 0.1-0.2 h.

Preferably, in the step 2, the flexible substrate is pretreated for 0.2-0.4 h at the temperature of 60-80 ℃ before rolling.

Preferably, in step 2, the conductive polymer is a polymer formed by compounding chromium polynicotinate and polyaniline.

Preferably, in the step 2, the thickness of the conductive polymer film is 30-100 nm.

Preferably, the preparation method of the conductive polymer film comprises the following steps:

a. weighing chromium polynicotinate nanoparticles, adding the chromium polynicotinate nanoparticles into toluene, and uniformly mixing by ultrasonic waves to obtain a chromium polynicotinate solution; wherein the mass ratio of the chromium polynicotinate nanoparticles to the toluene is 1: 5-7;

b. adding aniline into a chromium polynicotinate solution, heating to 45-55 ℃, and stirring for 1-3 hours to obtain an aniline/chromium polynicotinate solution; wherein the mass ratio of the aniline to the chromium polynicotinate solution is 1: 6-8;

c. adding ammonium persulfate powder into the aniline/chromium polynicotinate solution, adjusting the pH value to 1-2 by using hydrochloric acid, placing the solution under the condition of ice-water bath, stirring and reacting for 5-10 hours, filtering, washing the collected solid product by using absolute ethyl alcohol for at least three times, and then placing the product in a drying oven for drying treatment to obtain a polyaniline/chromium polynicotinate coating; wherein the mass ratio of the ammonium persulfate powder to the aniline in the aniline/chromium polynicotinate solution is 2: 1-1.05;

d. placing the polyaniline/chromium polynicotinate coating in deionized water, uniformly mixing to form mixed liquid, then uniformly adsorbing the solid on filter paper by using the mixed liquid through a vacuum filtration method, and peeling the filter paper after drying to form a film to obtain a conductive polymer film; wherein the mass ratio of the polyaniline/chromium polynicotinate to the deionized water is 1: 3-6.

Preferably, the particle size of the chromium polynicotinate nano-particles is 10-20 nm.

Preferably, in step 3, the parameters of magnetron sputtering are as follows: the distance between the double targets and the flexible substrate is 100-150 mm, and the background vacuum degree is 1.5-3 multiplied by 10^-3Pa, working pressure of 0.25-0.5 Pa, working gas flow of 80-120 sccm argon gas,the sputtering power of the double targets is 150-200W, and the sputtering time is 0.3-0.5 h.

Preferably, in the step 3, the magnetron sputtering thickness of the vanadium gallium arsenide crystal and the gallium selenide crystal is 50-200 nm.

Preferably, the thickness of the flexible magnetron sputtering metal nano composite material is 1-5 μm.

The invention has the beneficial effects that:

the invention discloses a method for magnetron sputtering of a metal nano composite material on a flexible substrate, which has the advantages of simple preparation process, easy operation and better repeatability. The prepared material has good toughness, can have high specific capacity even if annealing treatment is not carried out at high temperature, and has strong bonding property between the matrix and each plating layer.

The invention takes a flexible polymer material as a substrate, and sequentially rolls a conductive polymer film and a magnetron sputtering metal composite material on the surface of the substrate to finally prepare the flexible magnetron sputtering composite material with a three-layer structure. The conductive polymer film serving as the intermediate layer improves the bonding property between the magnetron sputtering layer and the substrate layer and has better conductivity. The metal composite coating layer on the uppermost layer uses gallium vanadium crystal and gallium selenide crystal as double targets, and is different from a conventional indium tin oxide material, the co-sputtered coating under the condition of double targets can still keep certain flexibility even under a thicker condition (200nm), and the finally obtained material still has higher conductivity and transparency even without high-temperature annealing treatment based on the synergistic effect of a conductive polymer film, so that the metal composite coating layer is suitable for application requiring a large-area or flexible substrate.

The conductive polymer film material prepared by the invention is prepared by compounding chromium polynicotinate and polyaniline and then performing a vacuum-pumping film-forming method, wherein the polyaniline is coated on the surface of the chromium polynicotinate to form a coated shell-core structure based on an organic metal complex system and relatively stable attribute of the chromium polynicotinate. Polyaniline is a common conductive polymer and has excellent properties in optical and electrical directions, but the use of polyaniline is always limited due to the defect that rigid chains among molecules and interaction among chains are strong and the polyaniline is difficult to process.

Detailed Description

For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.

The magnetron sputtering coating actually utilizes the field of low-temperature plasma, and the principle is that electrons generated by a power supply accelerate to fly and impact argon atoms introduced into a cavity under the action of an electromagnetic field, so that glow discharge is generated. Argon ions and new electrons are generated at the same time and are also called secondary electrons, the argon ions with large mass bombard the target material in a high-energy state, and the generated target material atoms and molecules deposit and grow on the surface of the substrate to form a film. Meanwhile, newly generated secondary electrons are bound on the surface close to the target body under the combined action of an electromagnetic field, and continuously impact argon atoms along spiral motion to generate argon ions, and the argon ions continuously bombard the target to realize high-speed deposition of the film.

Gallium selenide (GaSe) crystal is a middle and far infrared nonlinear optical material with excellent performance, has wider transmission range and lower absorption coefficient, but has lower hardness and is easy to dissociate along a c axis₃Ga) and gallium selenide (GaSe) crystals are used as double targets to sputter the substrate together, so that the defect of low hardness of the substrate is overcome, and meanwhile, the flexibility and the ductility of the substrate are improved.

Polyaniline (PANI) is the most common conductive polymer, the main chain contains alternate benzene rings and nitrogen atoms, after the polyaniline in a semi-oxidized and semi-reduced state is doped by protonic acid, quinone rings in molecules disappear, electron clouds are redistributed, and positive charges on the nitrogen atoms are delocalized into large conjugated pi bonds, so that the polyaniline has high conductivity. The polyaniline is coated by a widely used material, but the polyaniline has poor solubility and processability, the bonding force is often insufficient after the polyaniline is combined with an inorganic material for coating, the stripping phenomenon is easy to generate, and the film forming effect of the polyaniline by using a vacuum filtration method is not good.

The invention is further described below with reference to the following examples.

Example 1

A preparation method of a flexible magnetron sputtering metal nano composite material comprises the following steps:

step 1, sequentially placing a PET matrix in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.3h, and then treating for 0.15h by using a plasma cleaning agent to obtain a cleaned flexible matrix;

step 2, after the flexible substrate is pretreated at 70 ℃ for 0.3h, the surface of the flexible substrate is rolled with a conductive polymer film with the thickness of 60nm to obtain a composite flexible substrate of a conductive polymer;

step 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using a gallium arsenide crystal and a gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology; the magnetron sputtering thickness of the gallium arsenide crystal and the gallium selenide crystal is 100nm, and the thickness of the flexible magnetron sputtering metal nano composite material is 3 mu m; the parameters of magnetron sputtering are as follows: the distance between the double target materials and the flexible substrate is 120mm, and the background vacuum degree is 2 multiplied by 10^-3Pa, the working pressure is 0.3Pa, the working gas flow is 100sccm of argon, the sputtering power of the double targets is 180W, and the sputtering time is 0.4 h.

Wherein, the conductive polymer is a polymer formed by compounding chromium polynicotinate and polyaniline, and the preparation method of the conductive polymer film comprises the following steps:

a. weighing chromium polynicotinate nanoparticles with the particle size of 10-20 nm, adding the chromium polynicotinate nanoparticles into toluene, and uniformly mixing the chromium polynicotinate nanoparticles with the toluene by ultrasonic waves to obtain a chromium polynicotinate solution; wherein the mass ratio of the chromium polynicotinate nano-particles to the toluene is 1: 6;

b. adding aniline into a chromium polynicotinate solution, heating to 45-55 ℃, and stirring for 1-3 hours to obtain an aniline/chromium polynicotinate solution; wherein the mass ratio of the aniline to the chromium polynicotinate solution is 1: 7;

c. adding ammonium persulfate powder into the aniline/chromium polynicotinate solution, adjusting the pH value to 1-2 by using hydrochloric acid, placing the solution under the condition of ice-water bath, stirring and reacting for 5-10 hours, filtering, washing the collected solid product by using absolute ethyl alcohol for at least three times, and then placing the product in a drying oven for drying treatment to obtain a polyaniline/chromium polynicotinate coating; wherein the mass ratio of the ammonium persulfate powder to the aniline in the aniline/chromium polynicotinate solution is 2: 1.02;

d. placing the polyaniline/chromium polynicotinate coating in deionized water, uniformly mixing to form mixed liquid, then uniformly adsorbing the solid on filter paper by using the mixed liquid through a vacuum filtration method, and peeling the filter paper after drying to form a film to obtain a conductive polymer film; wherein the mass ratio of the polyaniline/chromium polynicotinate to the deionized water is 1: 5.

Example 2

A preparation method of a flexible magnetron sputtering metal nano composite material comprises the following steps:

step 1, sequentially placing a PET matrix in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.1h, and then treating for 0.1h by using a plasma cleaning agent to obtain a cleaned flexible matrix;

step 2, after the flexible substrate is pretreated at 60 ℃ for 0.2h, the surface of the flexible substrate is rolled with a conductive polymer film with the thickness of 30nm to obtain a composite flexible substrate of a conductive polymer;

step 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using the gallium nitride crystal and the gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite through a vacuum magnetron sputtering coating technologyCombining materials; the magnetron sputtering thickness of the gallium arsenide crystal and the gallium selenide crystal is 50nm, and the thickness of the flexible magnetron sputtering metal nano composite material is 1 mu m; the parameters of magnetron sputtering are as follows: the distance between the double target materials and the flexible substrate is 100mm, and the background vacuum degree is 1.5 multiplied by 10^-3Pa, the working pressure is 0.25Pa, the working gas flow is 80sccm of argon, the sputtering power of the double targets is 150W, and the sputtering time is 0.3 h.

Wherein, the conductive polymer is a polymer formed by compounding chromium polynicotinate and polyaniline, and the preparation method of the conductive polymer film comprises the following steps:

a. weighing chromium polynicotinate nanoparticles with the particle size of 10-20 nm, adding the chromium polynicotinate nanoparticles into toluene, and uniformly mixing the chromium polynicotinate nanoparticles with the toluene by ultrasonic waves to obtain a chromium polynicotinate solution; wherein the mass ratio of the chromium polynicotinate nano-particles to the toluene is 1: 5;

b. adding aniline into a chromium polynicotinate solution, heating to 45-55 ℃, and stirring for 1-3 hours to obtain an aniline/chromium polynicotinate solution; wherein the mass ratio of the aniline to the chromium polynicotinate solution is 1: 6;

c. adding ammonium persulfate powder into the aniline/chromium polynicotinate solution, adjusting the pH value to 1-2 by using hydrochloric acid, placing the solution under the condition of ice-water bath, stirring and reacting for 5-10 hours, filtering, washing the collected solid product by using absolute ethyl alcohol for at least three times, and then placing the product in a drying oven for drying treatment to obtain a polyaniline/chromium polynicotinate coating; wherein the mass ratio of the ammonium persulfate powder to the aniline in the aniline/chromium polynicotinate solution is 2: 1;

d. placing the polyaniline/chromium polynicotinate coating in deionized water, uniformly mixing to form mixed liquid, then uniformly adsorbing the solid on filter paper by using the mixed liquid through a vacuum filtration method, and peeling the filter paper after drying to form a film to obtain a conductive polymer film; wherein the mass ratio of the polyaniline/chromium polynicotinate to the deionized water is 1: 3.

Example 3

A preparation method of a flexible magnetron sputtering metal nano composite material comprises the following steps:

step 1, sequentially placing a PET matrix in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.3h, and then treating for 0.2h by using a plasma cleaning agent to obtain a cleaned flexible matrix;

step 2, after the flexible substrate is pretreated at the temperature of 80 ℃ for 0.4h, rolling a conductive polymer film with the thickness of 30-100 nm on the surface of the flexible substrate to obtain a composite flexible substrate of a conductive polymer;

step 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using a gallium arsenide crystal and a gallium selenide crystal as double targets, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology; the magnetron sputtering thickness of the gallium arsenide crystal and the gallium selenide crystal is 200nm, and the thickness of the flexible magnetron sputtering metal nano composite material is 5 mu m; the parameters of magnetron sputtering are as follows: the distance between the double target materials and the flexible substrate is 150mm, and the background vacuum degree is 3 multiplied by 10^-3Pa, the working pressure is 0.5Pa, the working gas flow is 120sccm of argon, the sputtering power of the double targets is 200W, and the sputtering time is 0.5 h.

Wherein, the conductive polymer is a polymer formed by compounding chromium polynicotinate and polyaniline, and the preparation method of the conductive polymer film comprises the following steps:

a. weighing chromium polynicotinate nanoparticles with the particle size of 10-20 nm, adding the chromium polynicotinate nanoparticles into toluene, and uniformly mixing the chromium polynicotinate nanoparticles with the toluene by ultrasonic waves to obtain a chromium polynicotinate solution; wherein the mass ratio of the chromium polynicotinate nano-particles to the toluene is 1: 7;

b. adding aniline into a chromium polynicotinate solution, heating to 45-55 ℃, and stirring for 1-3 hours to obtain an aniline/chromium polynicotinate solution; wherein the mass ratio of the aniline to the chromium polynicotinate solution is 1: 8;

c. adding ammonium persulfate powder into the aniline/chromium polynicotinate solution, adjusting the pH value to 1-2 by using hydrochloric acid, placing the solution under the condition of ice-water bath, stirring and reacting for 5-10 hours, filtering, washing the collected solid product by using absolute ethyl alcohol for at least three times, and then placing the product in a drying oven for drying treatment to obtain a polyaniline/chromium polynicotinate coating; wherein the mass ratio of the ammonium persulfate powder to the aniline in the aniline/chromium polynicotinate solution is 2: 1.05;

d. placing the polyaniline/chromium polynicotinate coating in deionized water, uniformly mixing to form mixed liquid, then uniformly adsorbing the solid on filter paper by using the mixed liquid through a vacuum filtration method, and peeling the filter paper after drying to form a film to obtain a conductive polymer film; wherein the mass ratio of the polyaniline/chromium polynicotinate to the deionized water is 1: 6.

Comparative example 1

A preparation method of a flexible magnetron sputtering metal nano composite material comprises the following steps:

step 1, sequentially placing a PET matrix in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.3h, and then treating for 0.15h by using a plasma cleaning agent to obtain a cleaned flexible matrix;

step 2, after the flexible substrate is pretreated at 70 ℃ for 0.3h, rolling a polyaniline film with the thickness of 60nm on the surface of the flexible substrate to obtain a composite flexible substrate of a conductive polymer;

step 3, placing the composite flexible matrix of the electric polymer in magnetron sputtering equipment, using gallium selenide crystals as a target material, and obtaining the flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology; the magnetron sputtering thickness of the vanadium gallium crystal is 100nm, and the thickness of the flexible magnetron sputtering metal nano composite material is 3 mu m; the parameters of magnetron sputtering are as follows: the distance between the target material and the flexible substrate is 120mm, and the background vacuum degree is 2 multiplied by 10^-3Pa, the working pressure is 0.3Pa, the working gas flow is 100sccm of argon, the sputtering power of the target material is 180W, and the sputtering time is 0.4 h.

Comparative example 2

A preparation method of a flexible magnetron sputtering metal nano composite material comprises the following steps:

step 1, sequentially placing a PET matrix in acetone, absolute ethyl alcohol and deionized water for respective ultrasonic treatment for 0.3h, and then treating for 0.15h by using a plasma cleaning agent to obtain a cleaned flexible matrix;

step 2, after the flexible substrate is pretreated at 70 ℃ for 0.3h, rolling a polyaniline film with the thickness of 60nm on the surface of the flexible substrate to obtain a composite flexible substrate of a conductive polymer;

step 3, electrifyingPlacing a composite flexible matrix of the polymer in magnetron sputtering equipment, using a vanadium gallium arsenide crystal and a gallium selenide crystal as double targets, and obtaining a flexible magnetron sputtering metal nano composite material by a vacuum magnetron sputtering coating technology; the magnetron sputtering thickness of the gallium arsenide crystal and the gallium selenide crystal is 100nm, and the thickness of the flexible magnetron sputtering metal nano composite material is 3 mu m; the parameters of magnetron sputtering are as follows: the distance between the double target materials and the flexible substrate is 120mm, and the background vacuum degree is 2 multiplied by 10^-3Pa, the working pressure is 0.3Pa, the working gas flow is 100sccm of argon, the sputtering power of the double targets is 180W, and the sputtering time is 0.4 h.

In order to more clearly illustrate the present invention, the flexible magnetron sputtering metal nanocomposite materials prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were prepared into a supercapacitor under the same conditions, and the results of performance detection and comparison were shown in table 1.

TABLE 1 Properties of Flexible magnetron sputtered Metal nanocomposites

As can be seen from table 1, the flexible magnetron sputtering metal nanocomposite prepared in embodiments 1 to 3 of the present invention has a relatively high specific capacity, still has a specific capacity retention rate higher than 90% after being bent for 1000 times, and still can maintain a specific capacity retention rate higher than 90% when a constant current charge-discharge cycle stability test is performed for 5000 cycles, which indicates that the flexible magnetron sputtering metal nanocomposite is very suitable for being used as an electrode of a large-area flexible substrate.

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, 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.