CN111986850A - Silver nanowire film and preparation method thereof - Google Patents
Silver nanowire film and preparation method thereof Download PDFInfo
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- CN111986850A CN111986850A CN202010757869.6A CN202010757869A CN111986850A CN 111986850 A CN111986850 A CN 111986850A CN 202010757869 A CN202010757869 A CN 202010757869A CN 111986850 A CN111986850 A CN 111986850A
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a silver nanowire film and a preparation method thereof. The preparation method of the silver nanowire film comprises the following steps: providing a substrate; coating the silver nanowire ink on the substrate, and performing first drying treatment to obtain an initial silver nanowire film; and (3) placing the initial silver nanowire film in mixed gas containing borane complex and water vapor for surface treatment, and then performing second drying treatment to obtain the silver nanowire film. The sheet resistance of the silver nanowire film prepared by the preparation method is remarkably reduced, the reliability is excellent, and the process of the preparation method has the characteristics of simplicity, rapidness and low cost.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a silver nanowire film and a preparation method thereof.
Background
With the development of science and technology, flexible photoelectric devices that can be bent and rolled are gradually known to the public, and are considered to have wide application prospects in the fields of consumers and industrial application. Conventional optoelectronic devices generally use a rigid glass substrate such as Indium Tin Oxide (ITO) as a transparent electrode material, and obviously cannot meet the requirement that a flexible optoelectronic device can be bent or even curled. To solve this problem, a Silver nanowire (AgNWs) transparent conductive film having high conductivity and high light transmittance is used instead of the ITO electrode.
The preparation process of the AgNWs film is simple, the transparent conductive film can be prepared by preparing ink after silver wires are synthesized by a hydrothermal method, and then carrying out blade coating and drying treatment, and complex processes or equipment such as vacuum evaporation and the like are not needed. However, the AgNWs film has the following drawbacks: (1) since the ink is formulated with a binder, it typically contains-COOH (the binder contains-COOH, or-OH is oxidized to-COOH), or-COO (CH) which can be decomposed to-COOH2)nCH3And the like. In the practical use process of the AgNWs film, under the combined action of illumination and water vapor, -COOH accelerates the ionization of AgNWs, so that the AgNWs film loses conductivity, and the device is failed, namely the reliability is poor; (2) AgNWs easily cause strong surface plasma resonance and have high haze; (3) due to the fact that interaction force between silver wires is weak, the lapping effect between AgNWs on the prepared film is poor, contact resistance is high, and therefore sheet resistance of the film is high, and further application of the film is limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a silver nanowire film and a preparation method thereof, and aims to solve the problem that the silver nanowire film prepared by the existing method is poor in reliability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a silver nanowire film, which comprises the following steps:
providing a substrate;
coating the silver nanowire ink on a substrate, and performing first drying treatment to obtain an initial silver nanowire film;
and (3) placing the initial silver nanowire film in mixed gas containing borane complex and water vapor for surface treatment, and then performing second drying treatment to obtain the silver nanowire film.
In one embodiment, the surface treatment time is 5-30min, and the temperature is 50-90 ℃.
In one embodiment, the mixed gas is obtained by heating a mixed solution of boride and water, and the mass fraction of boride in the mixed solution is 1.5-45%.
In one embodiment, the borane complex comprises at least one of dimethylamine borane, pyridine borane, tert-butylamine borane, and 2-methylpyridine borane.
In one embodiment, the temperature of the first drying treatment is 90-130 ℃; and/or the presence of a gas in the gas,
the time of the first drying treatment is 1-10 min.
In one embodiment, the temperature of the second drying treatment is 90-130 ℃; and/or the presence of a gas in the gas,
and the time of the second drying treatment is 1-10 min.
In one embodiment, the substrate is selected from any one of a PET film, a TAC film, a PEN film, a CPI film, a COP film, a PDMS film, and a glass film; and/or the presence of a gas in the gas,
the preparation method of the silver nanowires in the silver nanowire ink is selected from any one of an alcohol heating method, a hydrothermal method and a polyalcohol reduction method; and/or the presence of a gas in the gas,
the length-diameter ratio of the silver nanowires in the silver nanowire ink is 100-10000: 1.
in one embodiment, the silver nanowire ink contains a binder, and the binder comprises polysaccharide or polysaccharide derivative.
In one embodiment, the polysaccharide is selected from one or more of glycogen, starch, callose, agar, alginic acid, alginate, pectin, carrageenan, cellulose, chitin, chitosan, curdlan, dextran, levan, xanthan gum, tragacanth gum, and glucomannan; and/or the presence of a gas in the gas,
the polysaccharide derivative is selected from one or more of cellulose ester and cellulose ether; and/or the presence of a gas in the gas,
after the surface treatment, the content of carboxyl and ester groups in the adhesive is less than or equal to 0.5 percent.
The invention also provides a silver nanowire film, which is prepared by the preparation method of the silver nanowire film.
The preparation method of the silver nanowire film provided by the invention comprises the following steps of coating the silver nanowire ink on a substrate for first drying treatment, and then placing the substrate in mixed gas containing borane complex and water vapor for surface treatment, wherein in the surface treatment process: first, the-COOH and-COO (CH) on the surface of the initial silver nanowire film2)nCH3Can be reduced to-OH so as to improve the reliability of the product; secondly, an oxide layer (AgO) on the surface of AgNWs can be reduced into an Ag simple substance of a Face Centered Cubic (Face Centered Cubic) lattice with a smaller grain size, so that the surface plasma effect is well inhibited, and the haze of the product is reduced; thirdly, if the reduction reaction occurs at the lap joint of AgNWs, the welding effect can be formed, and the contact resistance of the silver wire is reduced to the maximum extent; and finally, a small amount of water vapor is filled between adjacent silver nanowires on the surface of the initial silver nanowire film, the water vapor can be evaporated in the subsequent second drying treatment process, and the acting force between the adjacent silver nanowires can be obviously increased along with the evaporation of the water vapor liquid on the surface of the initial silver nanowire film, so that the mutual overlapping of the silver nanowires can be further promoted, and the silver nanowire film with good reliability, low haze and low sheet resistance is finally prepared. Thereby enlarging the application range of the silver nanowire film, and the preparation method has the characteristics of simple and quick process and low cost.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a silver nanowire film according to an embodiment of the present invention;
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On one hand, an embodiment of the present invention provides a method for preparing a silver nanowire thin film, as shown in fig. 1, including the following steps:
s01: providing a substrate;
s02: coating the silver nanowire ink on a substrate, and performing first drying treatment to obtain an initial silver nanowire film;
s03: and (3) placing the initial silver nanowire film in mixed gas containing borane complex and water vapor for surface treatment, and then performing second drying treatment to obtain the silver nanowire film.
The preparation method of the silver nanowire film provided by the embodiment of the invention comprises the following steps of coating the silver nanowire ink on a substrate, carrying out first drying treatment, and then carrying out surface treatment in mixed gas containing borane complex and water vapor, wherein in the surface treatment process: (1) first, the-COOH and-COO (CH) on the surface of the initial silver nanowire film is reacted by the borane complex2)nCH3Can be reduced to-OH so as to improve the reliability of the product; (2) secondly, an oxide layer (AgO) on the AgNWs surface can be reduced into a simple substance Ag of a face-centered cubic lattice with a smaller grain size, so that the surface plasma effect is better inhibited, and the haze of the product is reduced; (3) thirdly, if the reduction reaction occurs at the lap joint of AgNWs, the welding effect can be formed, and the contact resistance of the silver wire is reduced to the maximum extent; (4) finally, a small amount of water vapor is filled between adjacent silver nanowires on the surface of the initial silver nanowire film, then the water vapor is evaporated in the second drying treatment process, and the water vapor liquid on the surface of the initial silver nanowire film is evaporated to act between the adjacent silver nanowiresThe force is obviously increased, so that mutual lapping among the silver nanowires can be further promoted, and finally the silver nanowire film with good reliability, low haze and low sheet resistance is prepared. Thereby enlarging the application range of the silver nanowire film, and the preparation method has the characteristics of simple and quick process and low cost.
The silver nanowire film prepared by the embodiment of the invention is a transparent conductive film. The synthesis conditions of the silver nanowires are mild, and specifically, the preparation method of the silver nanowires in the silver nanowire ink is selected from any one of an alcoholic thermal method, a hydrothermal method and a polyalcohol reduction method. The surface treatment is carried out in the mixed gas containing the borane complex and the water vapor, the method is simple, convenient and cheap, and the advantages enable the silver nanowire film obtained by the preparation method of the silver nanowire film to be applied to the large scale in the fields of foldable, crimpable and wearable devices.
In one embodiment, the silver nanowire ink contains a binder, and the binder comprises polysaccharide or polysaccharide derivative. Specifically, the polysaccharide is selected from one or more of glycogen, starch, callose, agar, alginic acid, alginate, pectin, carrageenan, cellulose, chitin, chitosan, curdlan, dextran, levan, xanthan gum, tragacanth gum and glucomannan; the polysaccharide derivative is selected from one or more of cellulose ester and cellulose ether; the adhesive can be used for better preparing the silver nanowire ink, and simultaneously, the surface treatment is carried out through mixed gas containing borane complex and water vapor, so that-COOH and-COO (CH) on the surface of the initial silver nanowire film obtained by the silver nanowire ink2)nCH3Reduced to-OH.
Furthermore, after the surface treatment, the content of carboxyl and ester groups in the adhesive is less than or equal to 0.5 percent, thereby remarkably improving the reliability of the product.
In one embodiment, the substrate in the step S01 is any one of PET (Polyethylene Terephthalate), TAC (Triacetyl Cellulose), PEN (Polyethylene Naphthalate), PDMS (Polydimethylsiloxane), CPI (Colorless transparent Polyimide), COP (Cyclo-Olefin polymer), and a glass film.
In an embodiment, in the step S02, any one of an alcohol heating method, a hydrothermal method and a polyol reduction method is selected as a method for preparing the silver nanowires of the silver nanowire ink, and an aspect ratio of the obtained silver nanowires is 100 to 10000: 1. in one embodiment, the silver nanowire ink is coated on the surface of a PET film, then first drying treatment is carried out, and the initial silver nanowire film can be obtained after a solvent is volatilized. Specifically, the temperature of the first drying treatment is 90-130 ℃; the time of the first drying treatment is 1-10 min. If the treatment temperature is too low, the ink solvent is difficult to volatilize, and the film forming property is influenced; if the drying temperature is too high, the silver nanowire film can be excessively oxidized, and the quality of the product is influenced. The drying time is matched with the temperature, and the drying time is not too long or too short.
In one embodiment, in step S03, the initial silver nanowire thin film is subjected to a surface treatment in a mixed gas containing a borane complex and water vapor for 5 to 30min at a temperature of 50 to 90 ℃. Within the time and temperature range, water vapor can be fully filled between the silver nanowires on the surface of the initial silver nanowire film, so that the acting force between the silver nanowires can be better improved, and meanwhile, the borane complex can be used for better reducing-COOH on the surface of the initial silver nanowire film into-OH.
For the surface treatment, the initial silver nanowire film can be placed in a mixed gas containing borane complex and water vapor for standing. Specifically, the initial silver nanowire film is placed in a mixed gas containing a borane complex and water vapor at the temperature of 50-90 ℃ and stands for 5-30 min. If the temperature is too low, the steam quantity is too small, the reaction is slow, and the effect is not ideal; if the temperature is too high, the amount of steam is too large, and the reaction will run away. The drying time is matched with the temperature, and the drying time is not too long or too short.
Specifically, the mixed gas containing the borane complex and the water vapor is obtained by heating a mixed solution of boride and water, wherein the mass fraction of boride in the mixed solution is 1.5-45%. The mixed gas obtained from the mixed solution has better effect on the surface treatment of the silver nanowire film.
Further, the borane complex comprises at least one of dimethylamine borane, pyridine borane, tert-butylamine borane, and 2-methylpyridine borane.
Further, the temperature of the second drying treatment is 90-130 ℃; the time of the second drying treatment is 1-10 min. If the treatment temperature is too low, the water is not volatilized and dried, and the film forming property is influenced; if the drying temperature is too high, the silver nanowire film can be excessively oxidized, and the quality of the product is influenced. The drying time is matched with the temperature, and the drying time is not too long or too short.
On the other hand, the embodiment of the invention also provides a silver nanowire film, and the silver nanowire film is prepared by the preparation method of the silver nanowire film.
The silver nanowire film provided by the embodiment of the invention is obtained by the special preparation method, so that the silver nanowire film is obtained with good reliability, low haze and low sheet resistance, and the application range of the silver nanowire film is expanded.
Specifically, the silver nanowire film is composed of a part or all of fused nano silver wire networks, wherein the contained binder is hydroxylated binder, such as hydroxylated polysaccharide or polysaccharide derivative.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of a silver nanowire film comprises the following steps:
s11: providing a PET film;
s12: coating the silver nanowire ink on a PET film, and drying for 1min at 130 ℃ to obtain an initial silver nanowire film;
s13: placing the initial silver nanowire film in mixed gas at the temperature of 50 ℃ for surface treatment for 30min, wherein the mixed gas is obtained by heating mixed solution of dimethylamine borane and water, the mass fraction of the dimethylamine borane in the mixed solution is 45%, and the balance of the dimethylamine borane in the mixed solution is water;
s14: and then drying for 10min at the temperature of 90 ℃ to obtain the silver nanowire film.
Example 2
A preparation method of a silver nanowire film comprises the following steps:
s11: providing a PET film;
s12: coating the silver nanowire ink on a PET film, and drying for 2min at the temperature of 100 ℃ to obtain an initial silver nanowire film;
s13: placing the initial silver nanowire film in mixed gas at the temperature of 90 ℃ for surface treatment for 30min, wherein the mixed gas is obtained by heating mixed solution of tert-butylamine borane and water, the mass fraction of the tert-butylamine borane in the mixed solution is 1.5%, and the balance of water;
s14: and then drying for 2min at the temperature of 100 ℃ to obtain the silver nanowire film.
Example 3
A preparation method of a silver nanowire film comprises the following steps:
s11: providing a PET film;
s12: coating the silver nanowire ink on a PET film, and drying for 5min at the temperature of 110 ℃ to obtain an initial silver nanowire film;
s13: placing the initial silver nanowire film in mixed gas at the temperature of 60 ℃ for surface treatment for 20min, wherein the mixed gas is obtained by heating mixed solution of dimethylamine borane, pyridine borane and water, and the mass fraction of the dimethylamine borane in the mixed solution is 5%, the mass fraction of the pyridine borane in the mixed solution is 3%, and the balance is water;
s14: and then drying for 1min at the temperature of 130 ℃ to obtain the silver nanowire film.
Example 4
A preparation method of a silver nanowire film comprises the following steps:
s11: providing a PET film;
s12: coating the silver nanowire ink on a PET film, and drying for 10min at 90 ℃ to obtain an initial silver nanowire film;
s13: placing the initial silver nanowire film in mixed gas at the temperature of 75 ℃ for surface treatment for 20min, wherein the mixed gas is obtained by heating mixed solution of tert-butylamine borane, 2-methylpyridine borane and water, the mass fraction of the tert-butylamine borane in the mixed solution is 15%, the mass fraction of the 2-methylpyridine borane in the mixed solution is 5%, and the balance is water;
s14: and then drying the film for 5min at the temperature of 110 ℃ to obtain the silver nanowire film.
Comparative example 1
A preparation method of a silver nanowire film comprises the following steps:
e01: providing a PET film;
e02: and (3) coating the silver nanowire ink on a PET film, and drying for 5min at the temperature of 110 ℃ to obtain the silver nanowire film.
Comparative example 2
A preparation method of a silver nanowire film comprises the following steps:
e01: providing a PET film;
e02: and (3) coating the silver nanowire ink on a PET film, and drying for 10min at the temperature of 90 ℃ to obtain the silver nanowire film.
E03: placing the initial silver nanowire film in water vapor at the temperature of 75 ℃ for surface treatment for 20min, wherein the water vapor is obtained by adding water;
e04: and then drying for 2min at the temperature of 100 ℃ to obtain the silver nanowire film.
Performance testing
(1) Square resistance: the test was performed using a hand-held four-finger probe (model M3, suzhou crystal lattice electronics ltd) at 30 random points and averaged.
(2) Haze: the haze value was measured by a haze meter (model SGW-810, Shanghai apparatus electric analyzer Co., Ltd.), and 10 points were randomly measured and averaged.
(3) High temperature and high humidity resistance change rate: the prepared silver nanowire transparent conductive film is matched with Suzhou fibrate high polymer material strandSF-2772X laser conductive silver paste produced by the company Limited is processed by silver paste printing, laser printing, attaching, FPC connecting and other processes to prepare a testing device. The device has multiple independent channels, and can test the resistance value of each channel to obtain the channel resistance change rate after aging treatment, namely (R)t-R0)/R0，R0Is an initial channel resistance, RtIs the channel resistance after processing. The average value of the resistance change rate of each channel is recorded as the resistance change rate of the device, and when the resistance change rate exceeds 50 percent of the Rt of the channel in the device>2M omega, the device is judged to be NG. The treatment conditions were 85 ℃ and 85% relative humidity.
The final data are shown in table 1 below.
TABLE 1
As can be seen from the data in table 1, the silver nanowire film obtained in the embodiment of the present invention through the specific surface treatment has the characteristics of reduced sheet resistance, reduced haze, and good reliability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the silver nanowire film is characterized by comprising the following steps:
providing a substrate;
coating the silver nanowire ink on the substrate, and performing first drying treatment to obtain an initial silver nanowire film;
and (3) placing the initial silver nanowire film in mixed gas containing borane complex and water vapor for surface treatment, and then performing second drying treatment to obtain the silver nanowire film.
2. The method for preparing the silver nanowire film as claimed in claim 1, wherein the surface treatment time is 5-30min and the temperature is 50-90 ℃.
3. The method for preparing a silver nanowire film as claimed in claim 1, wherein the mixed gas is obtained by heating a mixed solution of boride and water, and the mass fraction of boride in the mixed solution is 1.5% to 45%.
4. The method of preparing a silver nanowire film of claim 1, wherein the borane complex comprises at least one of dimethylamine borane, pyridine borane, tert-butylamine borane, and 2-methyl pyridine borane.
5. The method for preparing the silver nanowire film according to claim 1, wherein the temperature of the first drying treatment is 90 to 130 ℃; and/or the presence of a gas in the gas,
the time of the first drying treatment is 1-10 min.
6. The method for preparing the silver nanowire film according to claim 1, wherein the temperature of the second drying treatment is 90 to 130 ℃; and/or the presence of a gas in the gas,
and the time of the second drying treatment is 1-10 min.
7. The method for preparing a silver nanowire film according to any one of claims 1 to 6, wherein the substrate is any one selected from a PET film, a TAC film, a PEN film, a CPI film, a COP film, a PDMS film and a glass film; and/or the presence of a gas in the gas,
the preparation method of the silver nanowires in the silver nanowire ink is selected from any one of an alcohol heating method, a hydrothermal method and a polyalcohol reduction method; and/or the presence of a gas in the gas,
the length-diameter ratio of the silver nanowires in the silver nanowire ink is 100-10000: 1.
8. the method for preparing the silver nanowire film as claimed in any one of claims 1 to 6, wherein the silver nanowire ink contains a binder, and the binder comprises a polysaccharide or a polysaccharide derivative.
9. The method of preparing a silver nanowire film of claim 8, wherein the polysaccharide is selected from one or more of glycogen, starch, callose, agar, alginic acid, alginate, pectin, carrageenan, cellulose, chitin, chitosan, curdlan, dextran, levan, xanthan gum, tragacanth gum and glucomannan; and/or the presence of a gas in the gas,
the polysaccharide derivative is selected from one or more of cellulose ester and cellulose ether; and/or the presence of a gas in the gas,
after the surface treatment, the content of carboxyl and ester groups in the adhesive is less than or equal to 0.5 percent.
10. A silver nanowire thin film, which is prepared by the method for preparing a silver nanowire thin film according to any one of claims 1 to 9.
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