CN109727706B - Flexible transparent conductive film and preparation method thereof - Google Patents
Flexible transparent conductive film and preparation method thereof Download PDFInfo
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- CN109727706B CN109727706B CN201910174410.0A CN201910174410A CN109727706B CN 109727706 B CN109727706 B CN 109727706B CN 201910174410 A CN201910174410 A CN 201910174410A CN 109727706 B CN109727706 B CN 109727706B
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Abstract
The invention discloses a flexible transparent conductive film and a preparation method thereof, and the flexible transparent conductive film comprises the following steps: (1) adding silver nanowires into absolute ethyl alcohol, ultrasonically dispersing the silver nanowires uniformly, carrying out vacuum filtration on the dispersion liquid to the surface of an organic filter membrane, and drying the filter membrane to obtain a filter membrane A with uniformly dispersed silver nanowires; (2) uniformly mixing liquid silicon rubber and a corresponding cross-linking agent, uniformly dispersing the mixture on the surface of a metal film by spin coating, and curing to obtain a film B; (3) closely attaching one side of the filter membrane A with the silver nanowires and one side of the film B with the cured silicon rubber, and transferring the silver nanowire film on the filter membrane to the surface of the silicon rubber film through pressure treatment; (4) and (4) soaking the sample obtained in the step (3) in a dilute acid solution to completely dissolve the metal film on the surface of the silicon rubber film, so as to obtain the flexible transparent conductive film. The ultrathin flexible transparent conductive film prepared by the invention has uniform conductivity and good flexibility.
Description
Technical Field
The invention belongs to the technical field of flexible conductive film materials, and particularly relates to a preparation method of a flexible transparent conductive film.
Background
With the development of electronic devices and equipment towards the direction of mobility, lightness and flexibility, novel flexible transparent conductive film materials are rapidly developed. Compared with the traditional hard conductive material, the novel flexible transparent conductive film material not only has excellent optical transparency and low surface resistance of the traditional material, but also can be used in a bending state. Among various flexible transparent conductive thin film materials, a flexible transparent conductive thin film based on silver nanowires has been a research hotspot in recent decades due to its excellent performance and low preparation cost.
Due to the development of flexible electronic skins, ultrathin, flexible, transparent, conductive films with uniform conductivity are of particular interest. For example, in the patent, a method for preparing an ultra-thin and ultra-flexible graphene conductive film (CN106158144A) proposes that a layer of graphene is first deposited on the surface of a metal foil by a chemical vapor deposition method, and then the graphene is transferred to the surface of a substrate after the metal foil is removed. Although the method can prepare the ultrathin and ultra-flexible graphene conductive film with lower surface resistance, the method also has the following problems that on one hand, the graphene is prepared by a chemical vapor deposition method, so that high requirements on equipment are provided, and the preparation efficiency is lower; on the other hand, the prepared graphene needs to be transferred to the surface of a base material, so that the efficiency is low, the graphene is easily damaged in the transfer process, and the thin film is uneven in conductivity.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of an ultrathin flexible transparent conductive film with uniform conductivity. The method has simple process equipment, and the prepared ultrathin flexible transparent conductive film has uniform conductivity and good flexibility.
The invention also aims to provide the flexible transparent conductive film of the uniformly conductive ultrathin silver nanowires prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a flexible transparent conductive film comprises the following steps:
(1) adding silver nanowires into absolute ethyl alcohol, ultrasonically dispersing the silver nanowires uniformly, carrying out vacuum filtration on the dispersion liquid to the surface of an organic filter membrane, and drying the filter membrane to obtain a filter membrane A with uniformly dispersed silver nanowires;
(2) uniformly mixing liquid silicon rubber and a corresponding cross-linking agent, uniformly dispersing the mixture on the surface of a metal film by spin coating, and curing to obtain a film B;
(3) closely attaching one side of the filter membrane A with the silver nanowires and one side of the film B with the cured silicon rubber, and transferring the silver nanowire film on the filter membrane to the surface of the silicon rubber film through pressure treatment;
(4) and (4) soaking the sample obtained in the step (3) in a dilute acid solution to completely dissolve the metal film on the surface of the silicon rubber film, so as to obtain the flexible transparent conductive film.
Preferably, the deposition amount of the silver nanowires on the surface of the filter membrane A in the step (1) is 100-500 mg/m2。
Preferably, the ratio of the cross-linking agent in the step (2) to the liquid silicone rubber is 2-10 wt%.
Preferably, the liquid silicone rubber in the step (2) is one of polydimethylsiloxane, dihydroxy polydimethylsiloxane and polymethylhydrosiloxane; the cross-linking agent is one of dibenzoyl peroxide, 2, 5-dimethyl-5-di-tert-butyl peroxy hexane, methyl vinyl dipyrrolidone silane, methyl triethoxysilane, vinyl triethoxysilane and tetramethoxy silane.
Preferably, the organic filter membrane in step (1) is any one of a polytetrafluoroethylene filter membrane, a polypropylene filter membrane, a nylon filter membrane, a polysulfone filter membrane, and a regenerated cellulose filter membrane.
Preferably, the curing temperature in the step (2) is 40-80 ℃, and the curing time is 12-24 h.
Preferably, the pressure in the step (3) is 1-5 MPa, and the pressure treatment time is 12-24 h.
Preferably, the metal film in the step (2) is any one of magnesium, aluminum, iron, copper, zinc and tin; the spin coating speed is 2000-6000 rpm.
Preferably, the diluted acid solution in the step (4) is any one of diluted hydrochloric acid, diluted sulfuric acid and diluted nitric acid, the concentration of the diluted acid solution is 1-5 mol/L, and the soaking time is 12-24 h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the preparation equipment and the preparation method are simple, the conductive layer silver nanowires and the transparent flexible substrate are respectively prepared by vacuum filtration and spin coating, and the performance of the conductive layer and the performance of the substrate can be respectively controlled, so that the prepared flexible transparent conductive film can effectively control the thickness of the conductive layer to realize ultra-thinness, and meanwhile, the film has better conductive uniformity.
The uniform-conductivity ultrathin silver nanowire flexible transparent conductive film provided by the invention can be applied to the fields of flexible electrodes, flexible sensors, flexible electronic skins and other related flexible electronic materials.
Drawings
FIG. 1 is a graph showing the relationship between the surface resistance and the bending times of the flexible test of the uniform-conductivity ultrathin silver nanowire flexible transparent conductive film prepared in the embodiments 1 to 3 of the present invention.
Fig. 2 is a test chart of the conductivity uniformity of the flexible transparent conductive film with uniformly conductive ultrathin silver nanowires prepared in embodiment 1 of the present invention.
Fig. 3 is a test chart of the conductivity uniformity of the flexible transparent conductive film with uniform conductivity and ultrathin silver nanowires prepared in embodiment 2 of the present invention.
Fig. 4 is a test chart of the conductivity uniformity of the flexible transparent conductive film with uniformly conductive ultrathin silver nanowires prepared in embodiment 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto, and the room temperature in the present invention is 25 to 30 ℃.
Example 1
(1) Adding 1mg of silver nanowires into 100ml of absolute ethyl alcohol, carrying out ultrasonic dispersion uniformly, taking 20ml of the dispersion, carrying out vacuum filtration on the dispersion to obtain a polytetrafluoroethylene filter membrane surface with the diameter of 5cm, and drying the filter membrane at room temperature for 2 hours to obtain a uniformly dispersed silver nanowire membrane, wherein the deposition amount of the silver nanowires on the membrane surface is 100mg/m2。
(2) Liquid silicon rubber dihydroxy polydimethylsiloxane and a corresponding cross-linking agent methyl triethoxysilane according to the mass ratio of 100: 2, then uniformly spin-coating and dispersing the mixture on the surface of the tin foil by a rotating speed of 2000rpm, and then curing the film for 24 hours at 40 ℃.
(3) And (3) tightly attaching one side of the sample prepared in the step (1) with the silver nanowires and one side of the sample prepared in the step (2) with the cured silicon rubber, and treating the two attached samples under the pressure of 1MPa for 24 hours to transfer the silver nanowire film on the filter membrane to the surface of the silicon rubber film.
(4) And (3) soaking the sample which is transferred to the surface of the silicon rubber film by the silver nanowire film in the step (3) in 1mol/L diluted hydrochloric acid solution for 24h, so that the metal film on the surface of the silicon rubber film is completely dissolved, and the ultrathin silver nanowire flexible transparent conductive film with uniform conductivity can be obtained.
It can be seen from table 1 that the transparency of the flexible transparent conductive film of silver nanowires prepared in this example is high, but the film resistance and thickness are higher than those of other examples due to the low concentration of the silver nanowires after suction filtration and the low spin-coating speed of the liquid silicone rubber.
Fig. 1 shows that the flexible transparent conductive film of silver nanowires prepared by the present embodiment has good flexibility.
Fig. 2 shows that the silver nanowire flexible transparent conductive film prepared by the embodiment has good conductive uniformity.
TABLE 1
| Surface resistance (omega/sq) | Transparency (%) | Thickness (μm) |
| 44.7 | 93.2 | 48 |
Example 2
(1) Adding 1mg of silver nanowires into 100ml of absolute ethyl alcohol, performing ultrasonic dispersion uniformly, taking 60ml of the dispersion, performing vacuum filtration on the dispersion to obtain the surface of a polytetrafluoroethylene filter membrane with the diameter of 5cm, and drying the filter membrane at room temperature for 4 hours to obtain a uniformly dispersed silver nanowire membrane (the deposition amount of the silver nanowires on the membrane surface is 300 mg/m)2)。
(2) Liquid silicon rubber dihydroxy polydimethylsiloxane and a corresponding cross-linking agent methyl triethoxysilane according to the mass ratio of 100: 6, then uniformly spin-coating and dispersing the mixture on the surface of the tin foil by a rotating speed of 4000rpm, and then curing the film for 18 hours at 60 ℃.
(3) And (3) tightly attaching one side of the sample prepared in the step (1) with the silver nanowires and one side of the sample prepared in the step (2) with the cured silicon rubber, and treating the two attached samples under the pressure of 3MPa for 18h to transfer the silver nanowire film on the filter membrane to the surface of the silicon rubber film.
(4) And (3) soaking the sample which is obtained by transferring the silver nanowire film to the surface of the silicon rubber film in 3mol/L diluted hydrochloric acid solution for 18h, so that the metal film on the surface of the silicon rubber film is completely dissolved, and the ultrathin silver nanowire flexible transparent conductive film with uniform conductivity can be obtained.
It can be seen from table 2 that the transparency of the silver nanowire flexible transparent conductive film prepared by the embodiment is high, and the film resistance and the thickness are reduced with the concentration of the filtered silver nanowires and the increase of the spin-coating rotation speed of the liquid silicone rubber.
Fig. 1 shows that the flexible transparent conductive film of silver nanowires prepared by the present embodiment has good flexibility.
Fig. 3 shows that the silver nanowire flexible transparent conductive film prepared by the embodiment has good conductive uniformity.
TABLE 2
| Surface resistance (omega/sq) | Transparency (%) | Thickness (μm) |
| 32.9 | 91.6 | 31 |
Example 3
(1) Adding 1mg of silver nanowires into 100ml of absolute ethyl alcohol, uniformly dispersing by ultrasonic, carrying out vacuum filtration on the dispersion to the surface of a polytetrafluoroethylene filter membrane with the diameter of 5cm, and then carrying out ultrasonic filtration on the dispersionDrying the filter membrane for 6h at room temperature to obtain the uniformly dispersed silver nanowire membrane (the deposition amount of the silver nanowires on the surface of the membrane is 500 mg/m)2)。
(2) Liquid silicon rubber dihydroxy polydimethylsiloxane and a corresponding cross-linking agent methyl triethoxysilane according to the mass ratio of 100: 10, then uniformly spin-coating and dispersing the mixture on the surface of the tin foil by rotating at 6000rpm, and then curing the film for 12 hours at 80 ℃.
(3) And (3) tightly attaching one side of the sample prepared in the step (1) with the silver nanowires and one side of the sample prepared in the step (2) with the cured silicon rubber, and treating the two attached samples under the pressure of 5MPa for 12h to transfer the silver nanowire film on the filter membrane to the surface of the silicon rubber film.
(4) And (3) soaking the sample which is transferred to the surface of the silicon rubber film by the silver nanowire film in the step (3) in 5mol/L diluted hydrochloric acid solution for 12h, so that the metal film on the surface of the silicon rubber film is completely dissolved, and the uniformly-conductive ultrathin flexible transparent conductive silver nanowire film can be obtained.
TABLE 3
| Surface resistance (omega/sq) | Transparency (%) | Thickness (μm) |
| 19.6 | 90.1 | 19 |
It can be seen from table 3 that the transparency of the flexible transparent conductive film of silver nanowires prepared in this example is high, but the film resistance and thickness are lower than those of other examples due to the high concentration of the filtered silver nanowires and the high spin-coating speed of the liquid silicone rubber.
Fig. 1 shows that the flexible transparent conductive film of silver nanowires prepared by the present embodiment has good flexibility.
Fig. 4 shows that the silver nanowire flexible transparent conductive film prepared by the embodiment has good conductive uniformity.
Claims (10)
1. A preparation method of a flexible transparent conductive film is characterized by comprising the following steps:
(1) adding silver nanowires into absolute ethyl alcohol, ultrasonically dispersing the silver nanowires uniformly, carrying out vacuum filtration on the dispersion liquid to the surface of an organic filter membrane, and drying the filter membrane to obtain a filter membrane A with uniformly dispersed silver nanowires;
(2) uniformly mixing liquid silicon rubber and a corresponding cross-linking agent, uniformly dispersing the mixture on the surface of a metal film by spin coating, and curing to obtain a film B; the spin coating speed is 2000-6000 rpm;
(3) closely attaching one side of the filter membrane A with the silver nanowires and one side of the film B with the cured silicon rubber, and transferring the silver nanowire film on the filter membrane to the surface of the silicon rubber film through pressure treatment;
(4) and (4) soaking the sample obtained in the step (3) in a dilute acid solution to completely dissolve the metal film on the surface of the silicon rubber film, so as to obtain the flexible transparent conductive film.
2. The preparation method according to claim 1, wherein the deposition amount of the silver nanowires on the surface of the filter membrane A in the step (1) is 100-500 mg/m2。
3. The method according to claim 2, wherein the ratio of the crosslinking agent to the liquid silicone rubber in the step (2) is 2 to 10 wt%.
4. The preparation method according to claim 3, wherein the liquid silicone rubber in step (2) is one of polydimethylsiloxane, dihydroxy polydimethylsiloxane and polymethylhydrosiloxane; the cross-linking agent is one of dibenzoyl peroxide, 2, 5-dimethyl-5-di-tert-butyl peroxy hexane, methyl vinyl dipyrrolidone silane, methyl triethoxysilane, vinyl triethoxysilane and tetramethoxy silane.
5. The method according to claim 4, wherein the organic filter membrane in step (1) is one of a polytetrafluoroethylene filter membrane, a polypropylene filter membrane, a nylon filter membrane, a polysulfone filter membrane, and a regenerated cellulose filter membrane.
6. The preparation method according to any one of claims 1 to 5, wherein the curing temperature in the step (2) is 40 to 80 ℃ and the curing time is 12 to 24 hours.
7. The preparation method according to claim 6, wherein the pressure in the step (3) is 1-5 MPa, and the pressure treatment time is 12-24 h.
8. The method according to claim 7, wherein the metal thin film in step (2) is any one of magnesium, aluminum, iron, copper, zinc, and tin.
9. The preparation method according to claim 8, wherein the dilute acid solution in the step (4) is any one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the concentration of the dilute acid solution is 1-5 mol/L, and the soaking time is 12-24 h.
10. A flexible transparent conductive film prepared by the method of any one of claims 1 to 9.
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| CN110993147A (en) * | 2019-12-09 | 2020-04-10 | 重庆文理学院 | Preparation method of silver nanowire transparent conductive film |
| CN113061285B (en) * | 2021-02-26 | 2021-10-22 | 中国科学院深圳先进技术研究院 | Preparation method of ultrathin porous stretchable film electrode |
| CN113953525B (en) * | 2021-10-18 | 2024-01-16 | 中国人民解放军国防科技大学 | Preparation method of nanowire silver film for packaging and interconnecting large-size power semiconductor integrated circuit |
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| CN104681645A (en) * | 2015-01-23 | 2015-06-03 | 华南师范大学 | Method for preparing composite transparent conductive electrode based on metal grid and metal nano-wire |
| CN106328260A (en) * | 2016-08-24 | 2017-01-11 | 华南师范大学 | Full-liquid phase preparation method of metal mesh transparent conductive electrode |
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