CN115148418A - Method for preparing laminated silver nanowire flexible conductive film in large area and application - Google Patents
Method for preparing laminated silver nanowire flexible conductive film in large area and application Download PDFInfo
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- 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
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- 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
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Abstract
The invention provides a method for preparing a laminated silver nanowire flexible conductive film in a large area and application thereof.A silver nanowire dispersion liquid is injected to the surface of water along a container wall at a constant speed by using an injection pump, so that the silver nanowires form a uniform and transparent single-layer film; and continuously passing the flexible substrate through a plurality of containers to continuously transfer the silver nanowire film on the water surface to the flexible substrate to realize ordered lamination of single-layer silver nanowires, treating the laminated silver nanowire flexible transparent conductive film by using a sodium chloride aqueous solution, respectively cleaning the laminated silver nanowire flexible transparent conductive film by using water and ethanol, and finally drying the laminated silver nanowire flexible transparent conductive film. The invention not only overcomes the defects of large surface roughness and poor photoelectric property caused by the random disordered arrangement of the nanowires in the preparation of the silver nanowire flexible transparent conductive film by using a Meyer bar method, a spraying method, a printing method and other methods, but also can prepare the high-performance silver nanowire flexible transparent conductive film in a large area in a simple, high-efficiency and low-cost mode, thereby meeting the application of various flexible photoelectron products.
Description
Technical Field
The invention relates to the technical field of semiconductor devices, in particular to a method for preparing a laminated silver nanowire flexible conductive film in a large area and application thereof.
Background
With the growing trend of the flexible electronic industry, the flexible transparent conductive film with flexibility resistance, high light transmittance and high conductivity has become a strategic material of flexible optoelectronic products. The transparent conductive thin film material on the market is mainly metal oxide, especially Indium Tin Oxide (ITO). However, ITO is not suitable for flexible electronic applications due to its large brittleness. Therefore, the development of other transparent conductive materials with excellent performance to replace ITO (indium tin oxide), the preparation of a high-performance flexible transparent conductive film with low cost and large area becomes one of the primary tasks for developing novel flexible optoelectronic devices, and the development and the updating of the optoelectronic devices are of great significance.
To date, a variety of materials have been tried to replace ITO, such as carbon nanotubes, graphene, conductive polymers, metal grids, and metal (silver, copper, and gold) nanowires. Among them, silver nanowires have been the most likely electrode material to replace ITO due to their excellent light transmittance, conductivity, and flexibility, and low cost. At present, the flexible transparent conductive film of silver nanowires is prepared by methods such as a spin coating method, a vacuum filtration method, a drop coating method, a meyer bar method, a spraying method, a printing method and the like, the nanowires are randomly and disorderly lapped, and the surface appearance is fluctuated greatly, so that the surface roughness of the film is large; the application of the thin film is affected extremely by the excessive surface roughness, and when the thin film is applied to electronic devices such as organic solar cells and organic light emitting diodes, short circuit is easily caused. The contact between the silver nanowires randomly and disorderly arranged is insufficient, so that the photoelectric property of the film is not ideal enough. In contrast, the stacked ordered arrangement of the silver nanowire network has been shown to enhance the electrical conductivity, light transmission and surface planarity of the film. Although researchers have prepared the silver nanowire transparent conductive film with ordered lamination by using the LB self-assembly method, LB equipment is complex and expensive, and generally a toxic solvent chloroform is also used; more importantly, it is not suitable for large-area production of flexible transparent conductive thin films of silver nanowires. Therefore, how to simply and efficiently arrange the silver nanowire stacks in order to realize large-area preparation of the high-performance flexible transparent conductive film is still a challenging task.
Disclosure of Invention
The invention aims to solve the problem of cheapness of silver nanowire laminated ordered arrangement, provides a method for preparing a laminated silver nanowire flexible conductive film in a large area and application thereof, the whole preparation process is continuous and can be suitable for industrial production requirements, and the flexible film with low square resistance and high light transmittance can be obtained by changing the number of layers of the laminated silver nanowires in an adjustable manner.
The invention provides a method for preparing a laminated silver nanowire flexible conductive film in a large area, which comprises the following steps:
s1, hydrophilic treatment of a flexible substrate: carrying out hydrophilic treatment on the flexible substrate to obtain a flexible hydrophilic substrate;
s2, obtaining a silver nano film: filling water in a silver nano-film preparation container, and injecting the silver nano-wire dispersion liquid into the water surface along the container wall at a constant speed by using an injection pump to obtain a silver nano-wire film;
s3, obtaining a large-area conductive film: extending the flexible hydrophilic substrate from one end of the silver nano film preparation container to be below the water surface in the silver nano film preparation container, and then extending the flexible hydrophilic substrate from the other end of the silver nano film preparation container to transfer the silver nano wire film on the water surface to the flexible hydrophilic substrate to obtain a conductive film;
s4, fusing the silver nanowires: putting the conductive film into a fusion container containing a fusion solution to separate polyvinylpyrrolidone wrapped on the surfaces of the silver nanowires, and depositing silver ions on the surfaces of the silver nanowires and the joints again through autocatalytic reduction to fuse the silver nanowires, so as to obtain a large-area laminated flexible transparent conductive film of the silver nanowires;
s5, cleaning: and sequentially putting the large-area laminated silver nanowire flexible transparent conductive film into a first cleaning container containing water and a second cleaning solvent containing a cleaning agent, cleaning and drying, and finishing the preparation of the large-area laminated silver nanowire flexible transparent conductive film.
According to the method for preparing the laminated silver nanowire flexible conductive film in a large area, as a preferred mode, in the step S2, the number of the silver nano film preparation containers is at least two, the silver nano film preparation containers are sequentially arranged, and rollers are arranged on the left side and the right side of the outer part and the left side and the right side of the inner part of each silver nano film preparation container;
in the step S3, the flexible hydrophilic substrate sequentially enters each silver nano-film preparation container along the rollers, so that the silver nanowires are transferred onto the flexible hydrophilic substrate in a stacked manner;
in step S4, the fusion container, the first cleaning container and the second cleaning container are sequentially disposed at one side of the silver nano-film preparation container and are both provided with rollers, and the flexible hydrophilic substrate continuously moves among the silver nano-film preparation container, the first cleaning container and the second cleaning container in sequence.
According to the method for preparing the laminated silver nanowire flexible conductive film in a large area, as a preferred mode, in the step S1, the hydrophilic treatment method is plasma hydrophilic treatment;
the flexible substrate material is transparent, and the flexible substrate material is any one of the following materials: polyethylene terephthalate, polyimide, polydimethylsiloxane, polyurethane, polyvinyl alcohol, polymethyl methacrylate, polyethylene, polyether ether ketone, polycarbonate, polypropylene, polystyrene, and polyvinyl chloride.
As a preferred mode, in the step S2, the diameter of the silver nanowire in the silver nanowire dispersion liquid is 10-300 nm, the length of the silver nanowire dispersion liquid is 10-500 mu m, the concentration of the silver nanowire dispersion liquid is 0.001-2 mg/mL, the dispersion solvent of the silver nanowire dispersion liquid is one or more of methanol, ethanol or isopropanol, and the silver nanowire film is a uniform and transparent film.
As an optimal mode, in the step S2, the silver nanowire film is in a single-layer ordered structure.
As a preferred mode, in the step S4, the fusion solution is an aqueous solution of sodium chloride,
the chlorine ions in the sodium chloride aqueous solution obtained by autocatalytic reduction are used as a catalyst to reduce the oxidized silver ions again and deposit the silver ions on the surface and the connection part of the silver nanowire, the concentration of the sodium chloride aqueous solution is 0.1-5 mol/L, and the treatment time of the step S4 is 5-300S.
According to the method for preparing the laminated silver nanowire flexible conductive film in a large area, as a preferred mode, in the step S5, ethanol is used as a cleaning agent.
As a preferred mode, in the step S2, the number of the silver nano film preparation containers is 2-20, and the silver nano wire layers are orderly stacked and transferred onto the flexible hydrophilic substrate.
According to the method for preparing the laminated silver nanowire flexible conductive film in a large area, as an optimal mode, the angle formed by the intersection of the silver nanowires of the adjacent upper layer and the adjacent lower layer is 0 ° To 180 ° Any angle of (1).
The invention provides an application of a large-area preparation laminated silver nanowire flexible conductive film, which is applied to any of the following fields: wearable electronics, solar cells, touch screens, flexible displays, thin film transistors, organic light emitting diodes, and heaters.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a laminated silver nanowire flexible transparent conductive film in a large area comprises the following steps:
injecting silver nanowire dispersion liquid to the surface of water along a container wall at a constant speed by using an injection pump to form a uniform and transparent film by using silver nanowires;
continuously passing the flexible substrate through a plurality of containers to continuously transfer the silver nanowire film on the water surface to the flexible substrate, so as to realize the ordered lamination of the silver nanowires and obtain a large-area laminated silver nanowire flexible transparent conductive film;
and step three, after the laminated silver nanowire flexible transparent conductive film is treated by using a sodium chloride aqueous solution, respectively cleaning the laminated silver nanowire flexible transparent conductive film by using water and ethanol, and finally drying the laminated silver nanowire flexible transparent conductive film.
Preferably, in the preparation method of the present invention, the silver nanowire dispersion used in the first step has a diameter of 10 to 300nm, a length of 10 to 500 μm, a concentration of 0.001 to 2mg/mL, and the dispersion solvent is one or more of methanol, ethanol or isopropanol. The most preferred silver nanowires are 20nm in diameter, 50 μm in length, 0.5mg/mL concentration, ethanol as solvent.
Preferably, the silver nanowire film self-assembled on the water surface in the step one is of a single-layer ordered structure, and electrostatic repulsion is generated due to negative charge of the silver nanowires.
Preferably, in the preparation method of the present invention, the flexible substrate material used in step two is transparent, and includes polyethylene terephthalate, polyimide, polydimethylsiloxane, polyurethane, polyvinyl alcohol, polymethyl methacrylate, polyethylene, polyetheretherketone, polycarbonate, polypropylene, polystyrene, polyvinyl chloride, and the like. And the flexible base material is subjected to hydrophilic treatment by plasma. The Plasma hydrophilic treatment (Plasma hydrophilic treatment) means that active particles in Plasma react with the surface of a material to generate hydrophilic groups, thereby making the surface of the material hydrophilic. The most preferred flexible substrate is a hydrophilically treated transparent polyethylene terephthalate.
Preferably, in the second step, the single silver nanowire film is orderly stacked, the stacking times are 2-20 times, and the angle formed by the intersection of the adjacent upper and lower silver nanowires is 0 ° To 180 ° Any angle of (1).
Preferably, in the preparation method of the present invention, the concentration of the sodium chloride aqueous solution in the step three is 0.1 to 5mol/L, and the chemical treatment time is 5 to 300s. The most preferred concentration of the aqueous sodium chloride solution is 2mol/L and the chemical treatment time is 60s.
When the sodium chloride solution is treated, on one hand, due to strong interaction between chloride ions and silver, polyvinylpyrrolidone coated on the surface of the silver nanowire can be separated, and the polyvinylpyrrolidone is a residue in the process of preparing the silver nanowire; on the other hand, due to the existence of oxygen and chloride ions in the solution, silver undergoes an oxidation reduction reaction to generate silver ions, wherein the chloride ions are used as a catalyst, and then the silver ions can be re-deposited on the surfaces and the joints of the nanowires through autocatalytic reduction, so that the nanowires are fused.
The invention can obtain the flexible film with low square resistance and high light transmittance by changing the adjustable layer number of the laminated silver nanowires, and the whole preparation process is continuous and can meet the requirements of industrial production.
The flexible transparent conductive film prepared by the method is applied to the fields of wearable electronic equipment, solar cells, touch screens, flexible displays, thin film transistors, organic light emitting diodes, heaters and the like.
The invention has the following advantages:
the invention can orderly laminate the single-layer silver nanowire film in a simple, efficient and controllable way, realizes the large-area preparation of the silver nanowire flexible transparent conductive film with a flat and uniform surface, solves the defects of large surface roughness and poor photoelectric property caused by the random disordered arrangement of the nanowires in the silver nanowire flexible transparent conductive film prepared by the methods such as the Meyer rod method, the spraying method, the printing method and the like at present, and obtains the high-performance flexible transparent conductive film which can be compared with ITO. The method has the characteristics of simple equipment, strong operability, low cost, high preparation efficiency, environmental friendliness and the like, and is suitable for industrial production. The invention is beneficial to the application of the flexible transparent conductive film of the silver nanowires in flexible optoelectronic devices such as wearable electronic equipment, solar cells, touch screens, flexible displays, transistors, organic light emitting diodes, heaters and the like, and has great commercial value.
Drawings
FIG. 1 is a schematic diagram of an experimental apparatus and an experimental method for preparing a laminated silver nanowire flexible conductive film in a large area;
FIG. 2a is a surface topography of a single-layer silver nanowire flexible transparent conductive film prepared by a method for preparing a laminated silver nanowire flexible conductive film in a large area;
FIG. 2b is a surface topography of a double-layer silver nanowire flexible transparent conductive film prepared by a method for preparing a laminated silver nanowire flexible conductive film in a large area;
FIG. 3a is a scanning electron microscope topography of a silver nanowire flexible transparent conductive film with 2 stacked layers according to a method for preparing a stacked silver nanowire flexible conductive film in a large area;
FIG. 3b is a scanning electron microscope topography of a silver nanowire flexible transparent conductive film with 3 stacked layers according to a method for preparing a stacked silver nanowire flexible conductive film in a large area;
FIG. 3c is a Scanning Electron Microscope (SEM) morphology of a flexible transparent conductive film of silver nanowires with the number of laminated layers of 4 by a method for preparing a flexible conductive film of laminated silver nanowires in a large area;
FIG. 3d is a scanning electron microscope topography of a silver nanowire flexible transparent conductive film with 5 stacked layers according to a method for preparing a stacked silver nanowire flexible conductive film in a large area;
FIG. 3e is a scanning electron microscope topography of a flexible transparent conductive thin film of silver nanowires with 6 layers stacked by a method for preparing a flexible conductive thin film of stacked silver nanowires in a large area;
FIG. 3f is a scanning electron microscope topography of a silver nanowire flexible transparent conductive film with 7 stacked layers according to a method for preparing a stacked silver nanowire flexible conductive film in a large area;
FIG. 3g is a scanning electron microscope topography of a silver nanowire flexible transparent conductive film with 8 laminated layers according to a method for preparing a laminated silver nanowire flexible conductive film in a large area;
FIG. 4a is a schematic diagram of a method for preparing a laminated silver nanowire flexible conductive film in a large area before silver nanowires are welded by sodium chloride and a corresponding scanning electron microscope topography;
FIG. 4b is a schematic diagram of a method for preparing a laminated silver nanowire flexible conductive film in a large area after silver nanowires are welded by sodium chloride and a corresponding scanning electron microscope topography;
fig. 5a is a graph of the resistance result of the flexible transparent conductive film of silver nanowires, which is a method for preparing a laminated flexible conductive film of silver nanowires in a large area.
Fig. 5b is a graph of transparency results of a silver nanowire flexible transparent conductive film prepared by a method of preparing a laminated silver nanowire flexible conductive film in a large area.
Fig. 5c is a charge state performance result diagram of the silver nanowire flexible transparent conductive film prepared by the method for preparing the laminated silver nanowire flexible conductive film in a large area.
Fig. 5d is a thermoelectric figure of merit performance result diagram of the silver nanowire flexible transparent conductive film in a method for preparing a laminated silver nanowire flexible conductive film in a large area.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
As shown in fig. 1, a method for preparing a laminated silver nanowire flexible conductive film in a large area includes the following steps:
s1, hydrophilic treatment of a flexible substrate: carrying out hydrophilic treatment on the flexible substrate to obtain a flexible hydrophilic substrate;
the hydrophilic treatment method is plasma hydrophilic treatment, and the treatment time is 5 minutes;
the flexible substrate material is transparent, and the flexible substrate material is any one of the following materials: polyethylene terephthalate, polyimide, polydimethylsiloxane, polyurethane, polyvinyl alcohol, polymethyl methacrylate, polyethylene, polyether ether ketone, polycarbonate, polypropylene, polystyrene, and polyvinyl chloride.
S2, obtaining a silver nano film: filling water in a silver nano-film preparation container, and injecting the silver nano-wire dispersion liquid into the water surface along the container wall at a constant speed by using an injection pump to obtain a silver nano-wire film;
the number of the silver nano-film preparation containers is at least two, the silver nano-film preparation containers are sequentially arranged, and rollers are arranged on the left side and the right side of the outer part and the left side and the right side of the inner part of each silver nano-film preparation container;
the diameter of the silver nanowire in the silver nanowire dispersion liquid is 10-300 nm, the length of the silver nanowire dispersion liquid is 10-500 mu m, and the concentration of the silver nanowire dispersion liquid is 0.001-2 mg/mL, the dispersion solvent of the silver nanowire dispersion liquid is one or more of methanol, ethanol or isopropanol, and the silver nanowire film is a uniform and transparent film;
the silver nanowire film is of a single-layer ordered structure;
the number of the silver nano-film preparation containers is 2-20, and the silver nano-wire layers are orderly stacked and transferred to the flexible hydrophilic substrate;
s3, obtaining a large-area conductive film: extending the flexible hydrophilic substrate from one end of the silver nano film preparation container to be below the water surface in the silver nano film preparation container, and then extending the flexible hydrophilic substrate from the other end of the silver nano film preparation container to transfer the silver nano wire film on the water surface to the flexible hydrophilic substrate to obtain a conductive film;
the flexible hydrophilic substrate sequentially enters each silver nano-film preparation container along the rollers, so that the silver nanowires are transferred onto the flexible hydrophilic substrate in a stacked manner;
the angle formed by the intersection of the silver nanowires of the adjacent upper and lower layers is 0 ° To 180 ° Any angle of (1);
s4, fusing the silver nanowires: putting the conductive film into a fusion container containing a fusion solution, separating polyvinylpyrrolidone wrapped on the surfaces of the silver nanowires, and depositing silver ions on the surfaces of the silver nanowires and the joints again through autocatalytic reduction to fuse the silver nanowires to obtain a large-area laminated flexible transparent conductive film of the silver nanowires;
the fusion container, the first cleaning container and the second cleaning container are sequentially arranged on one side of the silver nano-film preparation container and are respectively provided with a roller, and the flexible hydrophilic substrate continuously moves among the silver nano-film preparation container, the first cleaning container and the second cleaning container in sequence;
the fusion solution is a sodium chloride water solution,
the chlorine ions in the sodium chloride aqueous solution obtained by autocatalytic reduction are used as a catalyst to ensure that oxidized silver ions are reduced again and deposited on the surface and the connection part of the silver nanowire, the concentration of the sodium chloride aqueous solution is 0.1-5 mol/L, and the treatment time is 5-300 s;
s5, cleaning: and sequentially putting the large-area laminated silver nanowire flexible transparent conductive film into a first cleaning container containing water and a second cleaning solvent containing a cleaning agent, cleaning and drying, wherein the cleaning agent is ethanol, and the preparation of the large-area laminated silver nanowire flexible transparent conductive film is completed.
Example 2
(1) According to the schematic diagram of the experimental device shown in the attached figure 1, taking silver nanowire ethanol dispersion with the diameter of 25nm, the length of 25 microns and the concentration of 0.5mg/mL, injecting the silver nanowire ethanol dispersion into the water surface along the wall of a glass container at the speed of 5mL/h by using a syringe pump, and enabling the silver nanowires to form a layer of uniform and transparent film on the water surface;
(2) Inserting the coiled hydrophilic-treated transparent polyethylene terephthalate flexible substrate into water from one side of the container, extracting the substrate from the other side of the container, and transferring the single-layer silver nanowire film on the surface of the water onto the flexible substrate;
(3) In order to realize the ordered lamination of the silver nanowires, the flexible substrate transferred with the single-layer silver nanowire film in the step (2) is inserted into water from one side of the container with the single-layer silver nanowire film on the water surface, and is extracted from the other side, and the single-layer silver nanowire film on the water surface is transferred to the flexible substrate with the single-layer silver nanowire film to obtain a double-lamination silver nanowire flexible transparent conductive film, as shown in attached figures 2a and 2 b;
(4) Repeating the processes to obtain the silver nanowire flexible transparent conductive film with the required number of lamination layers, wherein the appearance graphs of the silver nanowire flexible transparent conductive film with the number of lamination layers of 2-8 are shown in attached figures 3 a-3 g;
(5) And (3) immersing the flexible transparent conductive film of the laminated silver nanowires into 2mol/L sodium chloride aqueous solution for treatment for 60s, wherein polyvinylpyrrolidone wrapped on the surfaces of the silver nanowires is removed after the sodium chloride treatment, and the crossed silver nanowires are tightly welded together, as shown in attached figures 4 a-4 b.
(6) And continuously passing the laminated silver nanowire flexible transparent conductive film treated by the sodium chloride through a water tank and an ethanol tank to clean the film, and finally drying.
(7) The sheet resistance and the light transmittance at 550nm of the flexible transparent conductive film of silver nanowires were measured using a four-probe system and an ultraviolet-visible spectrophotometer, and the results are shown in fig. 5a to 5 d.
Example 3
(1) According to the schematic diagram of the experimental device shown in the attached figure 1, taking a silver nanowire ethanol dispersion with the diameter of 20nm, the length of 50 microns and the concentration of 1mg/mL, and injecting the silver nanowire ethanol dispersion into the water surface at the speed of 10mL/h along the wall of a glass container by using a syringe pump to form a layer of uniform and transparent film on the water surface by using the silver nanowires;
(2) Inserting the coiled hydrophilic-treated transparent polyethylene terephthalate flexible substrate into water from one side of the container, extracting the substrate from the other side of the container, and transferring the single-layer silver nanowire film on the surface of the water onto the flexible substrate;
(3) In order to realize the ordered lamination of the silver nanowires, the flexible substrate transferred with the single-layer silver nanowire film in the step (2) is inserted into water from one side of the container with the single-layer silver nanowire film on the water surface, and is extracted from the other side of the container, and the single-layer silver nanowire film on the water surface is transferred to the flexible substrate with the single-layer silver nanowire film, so that the double-lamination silver nanowire flexible transparent conductive film is obtained;
(4) Repeating the processes to obtain the silver nanowire flexible transparent conductive film with the required number of lamination layers;
(5) And (3) immersing the laminated silver nanowire flexible transparent conductive film into a 1mol/L sodium chloride aqueous solution for treatment for 30s, continuously cleaning the film through a water tank and an ethanol tank, and finally drying.
(6) The square resistance and the light transmittance at 550nm of the silver nanowire flexible transparent conductive film were tested by using a four-probe system and an ultraviolet-visible spectrophotometer.
Example 4
(1) According to the schematic diagram of the experimental device shown in the attached figure 1, taking a silver nanowire ethanol dispersion with the diameter of 30nm, the length of 20 microns and the concentration of 2mg/mL, and injecting the silver nanowire ethanol dispersion into the water surface at the speed of 20mL/h along the wall of a glass container by using a syringe pump to form a layer of uniform and transparent film on the water surface by using the silver nanowires;
(2) Inserting the coiled hydrophilic-treated transparent polyethylene terephthalate flexible substrate into water from one side of the container, extracting the substrate from the other side of the container, and transferring the single-layer silver nanowire film on the surface of the water onto the flexible substrate;
(3) In order to realize the ordered lamination of the silver nanowires, the flexible substrate transferred with the single-layer silver nanowire film in the step (2) is inserted into water from one side of the container with the single-layer silver nanowire film on the water surface, is extracted from the other side of the container, and is transferred to the flexible substrate with the single-layer silver nanowire film on the water surface to obtain a double-lamination silver nanowire flexible transparent conductive film;
(4) Repeating the processes to obtain the silver nanowire flexible transparent conductive film with the required number of lamination layers;
(5) And (3) immersing the laminated silver nanowire flexible transparent conductive film into 0.5mol/L sodium chloride aqueous solution for treatment for 90s, continuously cleaning the film through a water tank and an ethanol tank, and finally drying.
(6) The square resistance and the light transmittance at 550nm of the silver nanowire flexible transparent conductive film were tested by using a four-probe system and an ultraviolet-visible spectrophotometer.
Examples 1, 3 and 4 can achieve the effect of example 2.
Example 5
An application of a large-area preparation laminated silver nanowire flexible conductive film is disclosed, wherein the large-area laminated silver nanowire flexible transparent conductive film is applied to any of the following fields: wearable electronics, solar cells, touch screens, flexible displays, thin film transistors, organic light emitting diodes, and heaters.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A method for preparing a laminated silver nanowire flexible conductive film in a large area is characterized by comprising the following steps: the method comprises the following steps:
s1, hydrophilic treatment of a flexible substrate: carrying out hydrophilic treatment on the flexible substrate to obtain a flexible hydrophilic substrate;
s2, obtaining a silver nano film: filling water in a silver nano film preparation container, and injecting a silver nano wire dispersion liquid into the water surface along the container wall at a constant speed by using an injection pump to obtain a silver nano wire film;
s3, obtaining a large-area conductive film: extending the flexible hydrophilic substrate from one end of the silver nano film preparation container to a position below the water surface in the silver nano film preparation container, and then extending the flexible hydrophilic substrate from the other end of the silver nano film preparation container to transfer the silver nano wire film on the water surface to the flexible hydrophilic substrate to obtain a conductive film;
s4, fusing the silver nanowires: putting the conductive film into a fusion container containing a fusion solution to separate polyvinylpyrrolidone wrapped on the surface of the silver nanowires, and depositing silver ions on the surface of the silver nanowires and the joints again through autocatalytic reduction to fuse the silver nanowires, so as to obtain a large-area laminated flexible transparent conductive film of the silver nanowires;
s5, cleaning: and sequentially putting the large-area laminated silver nanowire flexible transparent conductive film into a first cleaning container containing water and a second cleaning solvent containing a cleaning agent, cleaning and drying, and finishing the preparation of the large-area laminated silver nanowire flexible transparent conductive film.
2. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, characterized in that: in the step S2, the number of the silver nano-film preparation containers is at least two, the silver nano-film preparation containers are sequentially arranged, and rollers are arranged on the left side and the right side of the outer part and the left side and the right side of the inner part of each silver nano-film preparation container;
in the step S3, the flexible hydrophilic substrate sequentially enters each silver nano-film preparation container along a roller, so that the silver nanowires are transferred onto the flexible hydrophilic substrate in a laminated manner;
in step S4, the fusion container, the first cleaning container, and the second cleaning container are sequentially disposed on one side of the silver nano-film preparation container and are both provided with rollers, and the flexible hydrophilic substrate continuously moves among the silver nano-film preparation container, the first cleaning container, and the second cleaning container in sequence.
3. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, wherein the method comprises the following steps: in the step S1, the hydrophilic treatment method is plasma hydrophilic treatment;
the flexible substrate material is transparent, and the flexible substrate material is any one of the following materials: polyethylene terephthalate, polyimide, polydimethylsiloxane, polyurethane, polyvinyl alcohol, polymethyl methacrylate, polyethylene, polyether ether ketone, polycarbonate, polypropylene, polystyrene, and polyvinyl chloride.
4. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, wherein the method comprises the following steps: in the step S2, the diameter of the silver nanowires in the silver nanowire dispersion liquid is 10-300 nm, the length of the silver nanowires is 10-500 microns, and the concentration of the silver nanowires is 0.001-2 mg/mL, the dispersion solvent of the silver nanowire dispersion liquid is one or more of methanol, ethanol or isopropanol, and the silver nanowire film is a uniform and transparent film.
5. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, wherein the method comprises the following steps: in the step S2, the silver nanowire film is of a single-layer ordered structure.
6. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, wherein the method comprises the following steps: in the step S4, the fusion solution is a sodium chloride aqueous solution, chloride ions in the sodium chloride aqueous solution obtained by autocatalysis reduction are used as a catalyst to reduce oxidized silver ions again and deposit the oxidized silver ions on the surface and the connection part of the silver nanowire, the concentration of the sodium chloride aqueous solution is 0.1-5 mol/L, and the treatment time in the step S4 is 5-300S.
7. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 1, characterized in that: in step S5, the cleaning agent is ethanol.
8. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 2, wherein the method comprises the following steps: in the step S2, the number of the silver nano-film preparation containers is 2-20, and the silver nano-wire layer is orderly stacked and transferred to the flexible hydrophilic substrate.
9. The method for preparing the laminated silver nanowire flexible conductive film in a large area according to claim 8, wherein the method comprises the following steps: the angle formed by the intersection of the silver nanowires of the adjacent upper layer and the adjacent lower layer is any angle from 0 degree to 180 degrees.
10. The use of any one of claims 1 to 9 for preparing a flexible conductive film of laminated silver nanowires in large area, wherein: the large-area laminated silver nanowire flexible transparent conductive film is applied to any of the following fields: wearable electronics, solar cells, touch screens, flexible displays, thin film transistors, organic light emitting diodes, and heaters.
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| CN110797140A (en) * | 2019-11-13 | 2020-02-14 | 东南大学 | Silver nanowire and graphene composite flexible transparent conductive film and preparation method thereof |
| CN111489864A (en) * | 2020-02-07 | 2020-08-04 | 浙江工业大学 | Cross-ordered silver nanowire thin film and patterning method thereof |
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