CN111710473A - Preparation method of patterned flexible conductive film - Google Patents
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Abstract
The invention belongs to the field of flexible electronic devices, and discloses a preparation method of a patterned flexible conductive film, which comprises the following steps: (1) sequentially preparing a nanowire conductive thin film layer and a water-soluble polymer thin film layer on a flexible substrate; (2) directly writing micro-nano scale patterns on the surface of the water-soluble polymer film layer by using a high molecular polymer solution through an electro-hydrodynamic near-field direct writing process to etch a pattern structure; (3) chemically treating the nanowire conductive thin film layer by taking the patterned polymer thin film as a mask layer, and removing the unmasked nanowire conductive thin film; (4) and removing the residual water-soluble polymer film by using deionized water, and drying to obtain the flexible transparent conductive film. The preparation method is based on the combination of an electrofluid near-field direct writing process and a template method, and the polymer fiber obtained by the direct writing process is used as a template or a template etching agent for preparing the nanowire film, so that the preparation of the patterned flexible conductive film is realized.
Description
Technical Field
The invention belongs to the field of flexible electronic devices, and particularly relates to a preparation method of a patterned flexible conductive film.
Background
The transparent conductive film is a functional film with high conductivity and excellent optical permeability in a visible light wavelength range, is mainly used as a transparent electrode, is the most key and basic component of various electronic devices, and is indispensable in photoelectric devices such as touch screens, solar cells, LCDs, OLEDs and the like. However, the choice of materials combining high optical transparency and good electrical conductivity is limited, since high carrier concentrations usually imply strong light absorption. Indium Tin Oxide (ITO) has both of these properties and is therefore widely used. However, the use of ITO as a transparent electrode has a number of disadvantages: the indium storage capacity and the utilization rate are low; secondly, the material needs high-temperature deposition; and thirdly, the steel is hard and brittle, and has no ductility and the like.
With the rapid development of the photoelectric industry, the application field of the transparent conductive film is continuously expanded, higher requirements are further provided for the physical and chemical properties of the transparent conductive film, new challenges are provided for electrodes due to the appearance of flexible devices such as wearable equipment, flexible display and electronic skin, and the requirements are more and more difficult to meet by the traditional electrode ITO. Therefore, many materials are being sought to replace ITO for future flexible photovoltaic devices. Among the more likely alternatives include carbon-based materials such as Carbon Nanotubes (CNTs), graphene, polymeric materials such as PEDOT: PSS, metal Nanoparticles (NPS) and metal Nanowires (NWS).
In recent years, flexible electrodes represented by linear electrodes have become an important research direction. Nanowires can be classified into different types, including metal nanowires, semiconductor nanowires, and insulator nanowires. But in the field of electrode materials/conductive films, the materials that we commonly use are nanotubes, graphene, and metal nanowires. All the components can adopt a solution coating technology to realize large-area large-scale production. If the novel materials are applied to photoelectric devices on a large scale, the photoelectric properties of the novel materials must be improved. Patterning nanowire electrodes is a very effective method among many lifting approaches. Therefore, active research on photoelectric performance parameters of the nanowire network and a process for patterning the nanowires has important practical significance for accelerating the development of the flexible photoelectric industry.
The silver nanowire transparent conductive film is a unique and innovative nano silver wire technology, has the characteristics of more excellent durability, high flexibility and low resistance value compared with the traditional ITO, and has the benefit of being more than several times that of the ITO. Meanwhile, the silver nanowire transparent conductive film has good matching usability and can be suitable for the existing industrial process; the stability of the material also reduces the time required for the manufacturing process, and furthermore, the material has superior environmental reliability and related characteristics, which meet the optical and electrical characteristics required by the current industry. The industrial application range is very wide, and the ITO material is an ideal ITO substitute material in the related fields of touch panels, displays, flexible displays, solar energy and the like. According to research, a grid of finely spaced metal structures may provide high transparency with low sheet resistance, which may severely affect the optical and electrical characteristics of the grid. Therefore, the realization of better performance by preparing a micro-pattern structure on the surface of the silver nanowire film becomes a possible choice. However, the current patterning operation process for the silver nanowires mostly needs specific instruments (a photoetching machine, a PDMS mask, etc.), only limited materials can be used, the cost is high, the technical requirements are also high, and the preparation of large-area patterned silver nanowire films cannot be realized.
Disclosure of Invention
The invention aims to solve the technical defects and provides a preparation method of a patterned flexible conductive film, which combines an electrohydrodynamic near-field direct writing process with a template method, takes a direct-written polymer as a template or an etching agent, and realizes the rapid green preparation of a high-resolution large-area nano line electrode with submicron characteristic dimension, neat edge and complex pattern by regulating the concentration of a polymer solution. The technical scheme has low implementation difficulty, no pollution and wide application materials, and can realize large-area rapid preparation.
In order to achieve the above object, the present invention provides a method for preparing a flexible transparent conductive film, comprising the steps of:
(1) sequentially preparing a nanowire conductive thin film layer and a water-soluble polymer thin film layer on a flexible substrate;
(2) preparing a high molecular polymer solution with a certain concentration, adding an injection pump for standby, directly writing a micro-nano scale pattern on the surface of the water-soluble polymer film layer by using the high molecular polymer solution through an electrohydrodynamic near-field direct writing process, and etching a pattern structure to obtain a patterned polymer film;
(3) chemically treating the nanowire conductive thin film layer by taking the patterned polymer thin film as a mask layer, and removing the unmasked nanowire conductive thin film;
(4) and removing the residual water-soluble polymer film by using deionized water, and drying to obtain the flexible transparent conductive film.
Further, the flexible substrate in step (1) includes a flexible glass and a flexible polymer substrate, and the flexible substrate is a single-layer or multi-layer substrate made of one or more of polycarbonate, polyimide, polydimethylsiloxane and polyethylene terephthalate.
Further, in the step (1), the nanowire conductive thin film layer and the water-soluble polymer thin film layer are prepared by a solution film-forming method, wherein the solution film-forming method is one of spin coating, bar coating, screen printing, spray coating, blade coating, dip coating, slit coating and imprinting.
Further, in the step (1), the thickness of the nanowire conductive thin film layer is 0.1-100 micrometers, and the thickness of the polymer thin film layer is 0.1-100 micrometers.
Further, the preparation of the water-soluble polymer thin film layer is eliminated in the step (1), and the nanowire conductive thin film layer is only prepared on the flexible substrate, namely the template is changed.
Further, the high molecular polymer in the step (2) includes polyvinyl alcohol, polyoxyethylene and ethylene-vinyl alcohol copolymer.
Further, the concentration of the polymer solution configured in the step (2) should be changed with the method, when the nanowire conductive thin film layer and the water-soluble polymer thin film layer are sequentially prepared on the flexible substrate in the step (1), in order to prepare the template, the solution to be directly written contains more water to erode the water-soluble polymer layer, and the concentration of the high molecular polymer solution is 0.5-1%.
When no polymer layer exists in the step (1), the concentration of the direct-writing high-molecular polymer solution is high, so that subsequent operation is performed by taking the direct-writing spinning as a template, and when the nanowire conductive thin film layer is prepared on the flexible substrate in the step (1), the concentration of the high-molecular polymer solution is 3-4%.
Further, the electro-hydrodynamics near-field direct writing process adopted in the step (2), also known as a near-field direct writing solution electrostatic spinning technology, is characterized in that a high voltage is applied to a spray head, a collecting plate is connected with electricity, an electrostatic electric field is formed between the spray head and a collecting substrate, moving charges are gathered on the liquid surface under the action of the electric field force, the coulomb force of the charges causes the liquid surface to generate shear stress, the solution forms a Taylor cone at a spray nozzle under the action of the shear force, the electric field acting force overcomes the tension of the liquid surface along with the increase of the electric field intensity, and jet flow is generated at the top end of the Taylor cone, the jet mode is called as a cone jet flow mode, the diameter of jet liquid drops is usually 0.01-0..
Further, in the step (2), when the near-field direct writing of the electrohydrodynamics is carried out, the distance between a nozzle of the device and the flexible substrate is 0.3 mm-0.5 mm, the inner diameter of a needle tube adopted by the nozzle is related to the type of the adopted needle head, the flow rate of the solution during injection is 30 microliter/min-250 microliter/min, the flexible substrate is heated, the heating temperature is 10 ℃ to 50 ℃, and the applied voltage is 5 kilovolt-15 kilovolt.
Further, when the nanowire conductive thin film layer in the step (3) is made of a metal nanowire material, a metal oxide is generated in an unmasked area of the metal nanowire, then wet etching is performed on the substrate by using an acid etching solution, the metal oxide is subjected to chemical reaction and dissolved, and the nanowire conductive thin film which is not masked by the protective layer is etched and removed.
Further, when the nanowire conductive thin film layer in the step (3) is made of a carbon nanotube material, the carbon nanotube is etched and removed by oxygen plasma.
Further, the acid etching solution in the step (3) is acetic acid, dilute nitric acid, sulfuric acid, hydrochloric acid or any acid which reacts with metal oxide.
Compared with the prior art, the invention has the following beneficial effects:
compared with the prior art, the preparation method of the patterned flexible conductive film has the beneficial effects that:
the invention provides a preparation method of a patterned flexible conductive film, which is based on the combination of an electrofluid near-field direct writing (electrospinning) process and a template method, and adopts polymer filaments (spinning) obtained by the direct writing process as a template or a template etching agent for preparing a nanowire film, thereby realizing the preparation of the patterned flexible conductive film. And different positioning of polymer spinning is adopted to realize complementation or identity of the template pattern and the nanowire film pattern.
The invention utilizes the large-area electrohydrodynamics near-field direct-writing printing high-molecular polymer, realizes the complementary patterned preparation of the nanowire conductive film in a positive-negative mode by regulating the concentration of the polymer solution, and can realize the rapid green preparation of the high-resolution large-area nanowire electrode with submicron characteristic dimension, regular edge and complex pattern. The technical scheme has low implementation difficulty, no pollution and wide application materials, and can realize large-area rapid preparation.
Drawings
FIG. 1 is a schematic view of the overall structure after the completion of the direct-write pattern;
FIG. 2 is a schematic view of a patterned water-soluble polymer layer structure;
FIG. 3 is a schematic diagram of the structure after etching of the nanowire layer with the polymer layer template;
FIG. 4 is a schematic structural view of a final patterned nanowire layer with a water-soluble polymer film layer;
fig. 5 is a schematic structural view when only a nanowire conductive thin film layer is prepared on a flexible substrate;
FIG. 6 is a schematic diagram of the principle of an electrohydrodynamic near-field direct write process;
FIG. 7 is a schematic structural view of a final patterned nanowire layer of a water-insoluble polymer film layer;
fig. 8 is a scanning electron micrograph of the patterned nanowire layer prepared in example 1, wherein (a) is an SEM image of a drawdown-coated silver nanowire network, (b) is an SEM image of electrospun PEO on the silver nanowire network, (c) is an SEM image of a plasma oxygen-treated silver nanowire network with a masking layer, (d) is an SEM image of a patterned silver nanowire network obtained by washing and drying, (e) is an SEM image of (b) partially enlarged, (f) is an SEM image of (c) partially enlarged, and (g) is an SEM image of (d) partially enlarged.
Detailed Description
Referring to fig. 1 to 8, the present invention provides a method for preparing a patterned flexible conductive film, the method comprising the steps of:
(1) sequentially preparing a nanowire conductive thin film layer and a water-soluble polymer thin film layer on a flexible substrate;
(2) preparing a high molecular polymer solution with a certain concentration, adding an injection pump for standby, directly writing a micro-nano scale pattern on the surface of a water-soluble polymer film by an electrofluid direct writing process, as shown in figure 1, wherein figure 1 is a schematic diagram of the overall structure after the direct writing of the pattern is completed, and etching the pattern structure to obtain a patterned polymer film, as shown in figure 2;
(3) chemically processing the nanowire conductive thin film layer by taking the patterned polymer thin film as a mask layer, and removing the unmasked nanowire conductive thin film, as shown in fig. 3;
(4) and removing the residual water-soluble polymer film by using deionized water, and drying to obtain the flexible transparent conductive film, which is a final patterned nanowire layer as shown in fig. 4.
Further, the flexible substrate in step (1) includes a flexible glass and a flexible polymer substrate, and the flexible substrate is a single-layer or multi-layer substrate made of one or more of polycarbonate, polyimide, polydimethylsiloxane and polyethylene terephthalate.
Further, in the step (1), the nanowire conductive thin film layer and the water-soluble polymer thin film layer are prepared by a solution film-forming method, wherein the solution film-forming method is one of spin coating, bar coating, screen printing, spray coating, blade coating, dip coating, slit coating and imprinting.
Further, in the step (1), the nanowire conductive film layer is made of a metal nanowire material or a carbon nanotube material, the thickness of the nanowire conductive film layer is 0.1-100 micrometers, the water-soluble polymer film layer is prepared from a fibroin solution or a globin solution, and the thickness of the water-soluble polymer film layer is 0.1-100 micrometers.
Further, the preparation of the water-soluble polymer thin film layer is eliminated in the step (1), and the nanowire conductive thin film layer is only prepared on the flexible substrate, namely the template is changed.
Further, the high molecular polymer in the step (2) includes polyvinyl alcohol, polyoxyethylene and ethylene-vinyl alcohol copolymer.
Further, the concentration of the polymer solution configured in the step (2) should be changed with the method, when the nanowire conductive thin film layer and the water-soluble polymer thin film layer are sequentially prepared on the flexible substrate in the step (1), in order to prepare the template, the solution to be directly written contains more water to erode the water-soluble polymer layer, and the concentration of the high molecular polymer solution is 0.5-1%.
When no polymer layer is formed in step (1), the concentration of the direct-writing high-molecular polymer solution should be high, so that subsequent operations are performed by using the direct-writing spinning as a template, and when the nanowire conductive thin film layer is prepared on the flexible substrate in step (1), the concentration of the high-molecular polymer solution is 3-4%, as shown in fig. 5.
Further, the electro-hydrodynamic near-field direct writing process adopted in the step (2), also known as a near-field direct writing solution electrostatic spinning technology, is as shown in fig. 6, and the principle thereof is that a high voltage is applied to a spray head, a collecting plate is connected with electricity, an electrostatic electric field is formed between the spray head and a collecting substrate, under the action of the electric field force, moving charges are gathered on the liquid surface, the coulomb force of the charges causes the liquid surface to generate shear stress, under the action of the shear force, the solution forms a taylor cone at a nozzle, along with the increase of the electric field intensity, the electric field acting force overcomes the liquid surface tension, and jet flow is generated at the top end of the taylor cone, the jet mode is called as a cone jet flow mode, and the diameter of jet liquid drops is usually 0.
Further, in the step (2), when the near-field direct writing of the electrohydrodynamics is carried out, the distance between a nozzle of the device and the flexible substrate is 0.3 mm-0.5 mm, the inner diameter of a needle tube adopted by the nozzle is related to the type of the adopted needle head, the flow rate of the solution during injection is 30 microliter/min-250 microliter/min, the flexible substrate is heated, the heating temperature is 10 ℃ to 50 ℃, and the applied voltage is 5 kilovolt-15 kilovolt.
Further, in the step (3), the nanowire conductive thin film layer is made of a metal nanowire material, a metal oxide is generated in an unmasked area of the metal nanowire, then wet etching is performed on the substrate by using an acid etching solution, the metal oxide is subjected to chemical reaction and dissolved, and the nanowire conductive thin film which is not masked by the protective layer is etched and removed.
Further, the nanowire conductive thin film layer in the step (3) is made of a carbon nanotube material, and the carbon nanotube is etched and removed by oxygen plasma.
Further, the acid etching solution in the step (3) is acetic acid, dilute nitric acid, sulfuric acid, hydrochloric acid or any acid which reacts with metal oxide.
In the case where the water-soluble polymer is present in step (1), the structure of the finally obtained nanowire film is shown in fig. 4, and it can be seen from the figure that the final nanowire film pattern and the written high molecular polymer pattern are exactly complementary structures.
In the step (1), the structure of the finally obtained nanowire film is shown in fig. 7 under the condition of no water-soluble polymer, and it can be seen from the figure that the pattern of the finally obtained nanowire film is consistent with the written high molecular polymer pattern.
Specifically, deionized water is adopted in the step (4) for washing and drying, and the patterned nanowire film is obtained.
The present invention will be described in detail below with reference to specific embodiments. The scope of the invention is not limited to the specific embodiments.
Example 1
(1) In the embodiment, the flexible substrate is made of Polycarbonate (PC), the PC flexible substrate is selected and cleaned, ultrasonic cleaning is sequentially carried out for 10min by acetone, ethanol and deionized water, and then the flexible substrate is baked by an infrared lamp;
(2) and preparing the silver nanowire conductive film layer on the flexible substrate in a scraper coating mode. During the coating process, the distance between the scraper and the flexible substrate was 800 micrometers, the coating speed was 15 mm/min, the nanowire solution was dispersed in deionized water at a concentration of 10 mg/ml, and the nanowires contained therein had a diameter of about 30 nanometers and a length of about 30 micrometers. After the blade coating is finished, placing a sample on a heating table at 100 ℃, heating and sintering the silver nanowires for half an hour, and then placing the sample at room temperature to reduce the temperature to the room temperature;
(4) preparing a solution with the mass concentration of 4% by using deionized water and PEO, and adding the solution into an injector for later use;
(5) inputting the required pattern shape and adjusting various parameters of an electrofluid direct writing device (self-made), so that the distance between the nozzle and the flexible substrate is 0.5 mm, the flexible substrate is heated to 40 ℃, the voltage is 9kV, and after the parameter adjustment is finished, the electrofluid direct writing operation is carried out. Wherein, the inner diameter of the needle head is 200 μm, and the solution supply speed is 200 μ l/min;
(6) taking the sample off, placing the sample into a plasma etching machine, and carrying out oxygen plasma treatment for 300s, wherein the surface of the exposed silver nanowire area without PEO shape protection is oxidized into silver oxide without conductivity under the action of plasma oxygen, and the cross overlapping part is reserved due to the shielding protection;
(7) putting the sample subjected to oxidation treatment into an acetic acid solution with the concentration of 80%, and soaking for ten minutes;
(8) and washing the surface of the sample by using deionized water, removing residual acetic acid, washing for 3-5 minutes, and drying to obtain the patterned silver nanowire conductive film.
Example 2
(1) In the embodiment, the flexible substrate is made of polyethylene terephthalate (PET), the flexible PET substrate is selected and cleaned, ethanol and deionized water are sequentially adopted for ultrasonic cleaning for 10min during cleaning, and then the flexible PET substrate is baked by an infrared lamp;
(2) and preparing the flexible transparent conductive film layer of the carbon nano tube by adopting a wet method. Firstly, selecting single-walled carbon nanotubes with the purity of 95 percent and an anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) according to the ratio of 1: 10, then placing the carbon nano tube dispersion liquid in a water bath at 60 ℃ for heating for 10 minutes, and then respectively weighing the carbon nano tube dispersion liquid and the surfactant SDBS according to the mass ratio of 1: 2 (TXl00), slowly adding the nonionic surfactant triton X.100 into the carbon nano tube dispersion liquid, continuously stirring at a low speed for 15min, taking out the solution, and placing the solution in an ultrasonic machine for ultrasonic treatment for several minutes to prepare the carbon nano tube ink with good coating dispersibility.
(3) The carbon nanotube film was prepared by a bar coating method using a wire wound bar with a characteristic length of l mm and a coil diameter of 0.3 mm, and the thickness of the corresponding coated liquid film was about 27 μm. The Polyimide (PI) film was placed on a coating plate, an appropriate amount of the coating liquid was sucked up with a dropper and placed on PET, and then it was knife-coated once from top to bottom with an RDS coating bar, and finally dried at room temperature.
(4) After the film is dried, firstly soaking the film in deionized water for 40min to primarily remove the water-soluble SDBS and TXl00, then placing the film in a vacuum drying oven for drying for 30min at 80 ℃, taking out the film and further placing the film in deionized water for cleaning, and finishing the drying.
(5) The water-soluble polymer film layer is prepared by adopting fibroin solution. After the step (4) is finished, dropping the fibroin solution on the upper surface of the sample, and spin-coating on a spin coater to prepare a fibroin layer, wherein the set rotating speed is 600 revolutions per minute, the spin-coating time is 40 seconds, and after the step is finished, naturally drying the fibroin solution in the air;
(6) preparing a solution with the mass concentration of 1% by using deionized water and PEO, and adding the solution into an injector for later use;
(7) and (3) adjusting various parameters of the electrofluid direct writing device (self-made), setting the voltage to be 13.5kV, and performing electric atomization operation after parameter adjustment is finished. Wherein, the inner diameter of the needle is 200 μm, and the solution supply speed is 200 μ l/min.
(8) And taking the sample off, putting the sample into a plasma etching machine, and carrying out oxygen plasma treatment for 300s, wherein the exposed carbon nanotubes without the protection of the fibroin layer are etched and removed, and the carbon nanotubes at the cross and overlapped parts still have good conductivity due to the protection of the carbon nanotubes by masking.
(9) And washing the surface of the sample by using deionized water, and drying to obtain the patterned carbon nano tube flexible transparent conductive film.
Example 3
(1) In the embodiment, the flexible substrate is made of Polyimide (PI), the PI flexible substrate is selected and cleaned, ultrasonic cleaning is sequentially carried out for 10min by acetone, ethanol and deionized water, and then the PI flexible substrate is baked by an infrared lamp;
(2) and preparing the silver nanowire conductive film layer on the flexible substrate in a scraper coating mode. During the coating process, the distance between the scraper and the flexible substrate was 800 micrometers, the coating speed was 15 mm/min, the nanowire solution was dispersed in deionized water at a concentration of 10 mg/ml, and the nanowires contained therein had a diameter of about 30 nanometers and a length of about 30 micrometers. After the blade coating is finished, placing a sample on a heating table at 100 ℃, heating and sintering the silver nanowires for half an hour, and then placing the sample at room temperature to reduce the temperature to the room temperature;
(3) the water-soluble polymer film layer is prepared by adopting a globin solution. After the step (4) is finished, dripping the globin solution on the upper surface of the sample, and spin-coating on a spin coater to prepare a globin layer, wherein the set rotating speed is 800 revolutions per minute, the spin-coating time is 35 seconds, and after the completion, naturally drying the globin layer;
(4) preparing a solution with the mass concentration of 1% by using deionized water and PEO, and adding the solution into an injector for later use;
(5) and (3) adjusting various parameters of the electrofluid direct writing device (self-made), setting the voltage to be 13.5kV, and performing electric atomization operation after parameter adjustment is finished. Wherein, the inner diameter of the needle is 200 μm, and the solution supply speed is 200 μ l/min.
(6) And taking the sample off, putting the sample into a plasma etcher, and carrying out oxygen plasma treatment for 300s, wherein the bare silver nanowires protected by the non-beaded fibroin layer are etched and removed, and the silver nanowires at the crossed and overlapped parts still have good conductivity due to the shielding and protection.
(7) And washing the surface of the sample by using deionized water, and drying to obtain the patterned silver nanowire flexible transparent conductive film.
Taking example 4 as an example, SEM scanning tests were performed on the patterned nanowire layer obtained in example 1, fig. 8 is a scanning electron microscope image of the patterned nanowire layer obtained in example 1, from fig. 8(b) and 8(e), we can observe that the pattern shape obtained by directly writing PEO with higher concentration is more regular, and from fig. 8(c) and 8(f), we can observe that the unmasked silver nanowire region is broken through plasma oxygen treatment, which indicates that the region is oxidized. Finally, it can be observed from fig. 8(d) and 8(g) that the silver nanowire thin film in accordance with the direct-write pattern was obtained by the acid treatment and the deionized water rinse drying.
It should be noted that the present invention is essentially a comprehensive application of the near-field direct writing process of electrohydrodynamic, the template method and the material characteristics.
(1) In the basic method, a patterned water-soluble polymer is used as a template, so that the silver nanowires are patterned.
(2) The electrofluidic direct-write solution of a high molecular polymer can act as both an etchant and a template, the boundary between these two cases being the concentration of the direct-write solution.
(3) The pattern with a certain shape can be directly written by using the polymer solution with higher concentration, and the polymer pattern shape is kept stable by applying temperature to the substrate due to the higher concentration and less moisture in the solution, so that the polymer pattern can be used as a template.
(4) When a polymer solution with a lower concentration (taking PEO as an example) is used for directly writing a pattern, because the receiving platform is closer to the nozzle and the concentration of PEO in the solution is lower, the PEO solution drops on the water-soluble polymer film layer after reaching the volatile moisture from the nozzle, the water-soluble polymer film covered on the reconstructed nanowire film can be dissolved by the volatile moisture, the original nanowire film can show a near-field directly-written PEO spinning pattern, and then the patterned nanowire film can be prepared by taking the water-soluble polymer as a template.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A method for preparing a patterned flexible conductive film, comprising the steps of:
(1) sequentially preparing a nanowire conductive thin film layer and a water-soluble polymer thin film layer on a flexible substrate;
(2) directly writing a micro-nano scale pattern on the surface of the water-soluble polymer film layer by using a high molecular polymer solution through an electrohydrodynamic near-field direct writing process, and etching a pattern structure to obtain a patterned polymer film;
(3) chemically treating the nanowire conductive thin film layer by taking the patterned polymer thin film as a mask layer, and removing the unmasked nanowire conductive thin film;
(4) and removing the residual water-soluble polymer film by using deionized water, and drying to obtain the flexible transparent conductive film.
2. The method of claim 1, wherein the flexible substrate in step (1) comprises a flexible glass and a flexible polymer substrate, and the flexible substrate is a single-layer or multi-layer substrate made of one or more of polycarbonate, polyimide, polydimethylsiloxane and polyethylene terephthalate.
3. The method of claim 1, wherein the nanowire conductive thin film layer and the water-soluble polymer thin film layer are prepared in step (1) by a solution film-forming method, wherein the solution film-forming method is one of spin coating, bar coating, screen printing, spray coating, blade coating, dip coating, slit coating, and stamping.
4. The method for preparing the patterned flexible conductive film according to claim 1, wherein in the step (1), the nanowire conductive film layer is made of a metal nanowire material or a carbon nanotube material, the thickness of the nanowire conductive film layer is 0.1-100 micrometers, the water-soluble polymer film layer is prepared from a fibroin solution or a globin solution, and the thickness of the water-soluble polymer film layer is 0.1-100 micrometers.
5. The method for preparing a patterned flexible conductive film according to claim 1, wherein the step (1) is performed without preparing the water-soluble polymer thin film layer, and only the nanowire conductive thin film layer is prepared on the flexible substrate, i.e. the template is changed.
6. The method of claim 1, wherein the polymer in step (2) comprises one of polyvinyl alcohol, polyoxyethylene, or ethylene-vinyl alcohol copolymer.
7. The method for preparing the patterned flexible conductive film according to claims 5 and 6, wherein when the nanowire conductive film layer and the water-soluble polymer film layer are prepared on the flexible substrate in sequence in the step (1), the mass concentration of the high molecular polymer solution is 0.5-1%;
when the nanowire conductive thin film layer is prepared on the flexible substrate in the step (1), the mass concentration of the high molecular polymer solution is 3-4%.
8. The method for preparing the patterned flexible conductive film according to claim 4, wherein when the nanowire conductive thin film layer in the step (3) is made of the metal nanowire material, the unmasked region of the metal nanowire generates metal oxide, and then the substrate is subjected to wet etching by using acid etching liquid, so that the metal oxide is chemically reacted and dissolved, and the nanowire conductive thin film which is not masked by the protective layer is etched and removed.
9. The method for preparing the patterned flexible conductive film according to claim 4, wherein when the nanowire conductive thin film layer in the step (3) is made of the carbon nanotube material, the carbon nanotube is etched and removed by oxygen plasma.
10. The method for preparing the patterned flexible conductive film according to claim 8, wherein the acid etching solution in the step (3) is acetic acid, dilute nitric acid, sulfuric acid, hydrochloric acid or any acid that reacts with metal oxide.
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