CN111681806A - Bending-resistant transparent conductive composite film and manufacturing method thereof - Google Patents
Bending-resistant transparent conductive composite film and manufacturing method thereof Download PDFInfo
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- CN111681806A CN111681806A CN202010752092.4A CN202010752092A CN111681806A CN 111681806 A CN111681806 A CN 111681806A CN 202010752092 A CN202010752092 A CN 202010752092A CN 111681806 A CN111681806 A CN 111681806A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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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
Abstract
The invention discloses a bending-resistant transparent conductive composite film and a manufacturing method thereof, wherein the bending-resistant transparent conductive composite film comprises a transparent conductive film and a high polymer layer which are arranged on a flexible support film, and the transparent conductive film is a transparent conductive oxide film plated on the flexible support film; the transparent conductive film comprises a film substrate and a plurality of mound-shaped bulges uniformly distributed on the film substrate; the polymer layer is arranged on the transparent conductive film, the polymer layer comprises a large number of polymer chains, and at least part of the polymer chains surround the hillock-shaped bulges to form a binding structure of the hillock-shaped bulges. The transparent conductive composite film has good bending resistance, and can keep good transparency, conductivity and uniformity.
Description
Technical Field
The invention relates to a transparent conductive composite film, in particular to a bending-resistant transparent conductive composite film and a manufacturing method thereof.
Background
Transparent conductive films are generally used as transparent electrodes in touch displays (e.g., touch screens and displays).
In recent years, with the development of curved or flexible electronic products, touch displays are expected to be flexible, and thus a transparent conductive film as a transparent electrode thereof is required to have bending resistance.
Most of the conventional transparent conductive thin films are transparent conductive oxide thin films such as Indium Tin Oxide (ITO) and Aluminum Zinc Oxide (AZO), which have good transparency, conductivity and uniformity and can meet the requirements of a common touch display.
Therefore, non-transparent conductive oxide thin films such as Metal Mesh (Metal Mesh) and nano silver wire films are proposed as the bending-resistant transparent conductive films, which generally have good bending resistance, however, the transparency, conductivity or uniformity of the non-transparent conductive oxide thin films are generally poor, and when the non-transparent conductive oxide thin films are applied to a touch display, the performance of the touch display is often reduced.
Disclosure of Invention
The invention aims to provide a bending-resistant transparent conductive composite film and a manufacturing method thereof, wherein the transparent conductive composite film has good bending resistance and can maintain good transparency, conductivity and uniformity.
In order to solve the technical problems, the technical scheme is as follows:
the utility model provides a resistant crooked transparent conductive composite film, is including setting up the transparent conductive film on flexible support membrane, and transparent conductive film is for plating the transparent conductive oxide film of system on flexible support membrane, its characterized in that: further comprising a polymer layer; the transparent conductive film comprises a film substrate and a plurality of hilly bulges uniformly distributed on the film substrate; the polymer layer is arranged on the transparent conductive film, the polymer layer comprises a large number of polymer chains, and at least part of the polymer chains surround the hillock-shaped bulges to form a binding structure of the hillock-shaped bulges.
In the transparent conductive composite film, a large number of hillock-shaped bulges are uniformly distributed on a film substrate, and are surrounded by a large number of macromolecular chains to form a binding structure of the hillock-shaped bulges; adopt this kind of structure to make transparent conductive composite film when the atress is crooked, the bellied constraint structure of mound can play the effect that the support was tightened up, and is taut with transparent conductive composite film, avoids transparent conductive composite film to appear breaking, effectively keeps transparent conductive composite film's electric conductivity.
The flexible support film is generally a glass thin plate, a plastic film, a polyimide plastic film, or a colorless polyimide plastic film. The glass thin plate is usually a thin plate with the thickness of less than 0.2mm, the polyimide plastic film has good high temperature resistance (high temperature is convenient for forming and crystallizing the transparent conductive film), and the colorless polyimide plastic film can ensure the transparency. The transparent conductive film is a thin film made of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), Indium Gallium Zinc Oxide (IGZO), or other transparent conductive oxides. The thickness of the transparent conductive film is 10-100 nm, and in the specific scheme, the thickness of the transparent conductive film is 20-60 nm. The transparent conductive film with the thickness can reduce the stress generated in the film when the film is subjected to bending action under the condition of ensuring the conductive performance of the film.
In a preferable scheme, the hillock-shaped bulges are naturally generated on the surface of the transparent conductive film through controlling the coating parameters during coating.
In a further preferred embodiment, the mound-like protrusion is an outward extending portion of a columnar crystal embedded in the film substrate, and specifically, a magnetron sputtering deposition process may be used to form the transparent conductive film, based on a film formation mechanism of magnetron sputtering island-like crystal growth, the transparent conductive film is finally a polycrystalline structure formed by the columnar crystal, and the sputtering power is increased to reduce the uniformity of the growth speed of each columnar crystal, so that the mound-like protrusion is formed on the surface of the transparent conductive film by the part of the columnar crystal with higher final growth speed. The hillock-shaped protrusion is a columnar crystal which is embedded in the film matrix and extends outwards, namely, the hillock-shaped protrusion is provided with a root part which is embedded in the film matrix, the bonding between the hillock-shaped protrusion and the film matrix is tighter, and when the hillock-shaped protrusion is surrounded and bound by the macromolecular chains, the acting force of the macromolecular chains can be effectively transmitted into the film matrix, so that the transparent conductive composite film is tougher.
In another preferred embodiment, the hillock-shaped protrusion is formed by roughening the transparent conductive film by a process after the transparent conductive film is formed.
In a further preferred embodiment, the hillock-shaped protrusion is formed by etching the surface of the transparent conductive film with an etching solution after the transparent conductive film is manufactured. Since the crystallinity of different regions (e.g., the center and the edge of a crystal grain constituting the polycrystalline thin film) of the transparent conductive film is not uniform, the etching rate is also not uniform, and a hillock is formed at a position where the etching is slow (e.g., the center of a crystal grain), in general, such a hillock formed by etching can also form a structure in which the root portion is buried in the thin film substrate. The etching solution may be diluted aqua regia or the like.
In the specific scheme, the height of the hilly protrusions is 20% -50% of the transparent conductive film substrate. The height of the hilly bumps can be controlled by adjusting the process (such as coating power and etching time), and the height of the hilly bumps is 20% -50% of the transparent conductive film substrate, so that the polymer chains can effectively surround the hilly bumps to form a binding structure.
In a preferred embodiment, the polymer layer is a polymer coating, and the polymer layer is formed by polymerizing or crosslinking monomer molecules on the surface of the transparent conductive film. Firstly, the polymer coating is made of materials with better elasticity and toughness (such as polyethylene, polypropylene, polyamide, polyimide and the like), and generally contains a large number of polymer chains; secondly, when the polymer layer is formed, monomer molecules for forming the polymer chain can be arranged on the surface of the transparent conductive film through modes of vapor deposition, solution coating and the like, then the polymerization reaction of the monomer molecules is initiated to form the polymer layer, the monomer molecules have good permeability and can easily permeate into gaps among the hillock-shaped bulges, and then the polymerization is carried out, so that the polymer chain surrounding and bounding the hillock-shaped bulges can be effectively formed.
In a further preferred embodiment, the polymer layer has a predetermined tensile stress. The polymer layer keeps certain taut state between the mound arch for when the complex film received crooked effect, the polymer layer can adapt to the crooked change of complex film more fast, with the toughness of keeping the complex film in crooked process, avoids transparent conducting film to appear breaking.
In a further preferred embodiment, the polymer chains are formed by photo-induced polymerization or cross-linking, which generally places the formed polymer chains in a strained state, and finally forms a predetermined tensile stress in the polymer layer. In a specific embodiment, the polymer layer is a polyacrylic acid film formed by photo-initiated polymerization or cross-linking reaction. Polyacrylic films are capable of developing significant tensile stresses.
In still further preferred embodiment, in the process of forming the polymer layer, the length of the polymer chains of the polymer layer is increased by optimizing the composition and/or the polymerization process, so that in the polymer layer, at least a part of the polymer chains jointly form a binding structure around two adjacent hilly protrusions. Preferably, when the polymer chains together form a constrained structure around two adjacent hilly protrusions, the polymer chains together form an "8" -shaped constrained structure around two adjacent hilly protrusions. The structure can bind the adjacent hill-shaped bulges, thereby improving the overall toughness of the composite film and further increasing the bending resistance of the composite film. The thickness of the polymer layer is only required to be made to be equivalent to the height of the hilly protrusion, so that the toughness and the bending resistance of the transparent conductive composite film can be improved. For easier fabrication, the polymer layer can be made thicker, such as a 1 μm-10 μm thick coating, and the bottom portion of the coating in contact with the transparent conductive film also has the structure of the polymer chain forming a bond around the hilly-shaped bump.
A method for manufacturing a bending-resistant transparent conductive composite film, characterized by comprising the steps of:
step (1), arranging a transparent conductive oxide film on a flexible support film, and distributing a large number of hill-shaped bulges on the surface of the transparent conductive oxide film;
and (2) arranging a polymer layer on the transparent conductive oxide film, and enabling at least part of polymer chains of the polymer layer to surround the hilly bulges to form a bound structure.
Preferably, in the step (1), the mound-like protrusion is an outward extending portion of a columnar crystal embedded in the film substrate, specifically, a magnetron sputtering deposition process may be adopted to form the transparent conductive film, based on a film formation mechanism of magnetron sputtering island-like crystal growth, the transparent conductive film is finally a polycrystalline structure formed by the columnar crystal, and the sputtering power is increased to reduce the uniformity of the growth speed of each columnar crystal, so that the mound-like protrusion is formed on the surface of the transparent conductive film by the part of the columnar crystal with the higher final growth speed.
Preferably, in the step (1), the hillock-shaped protrusion is formed by etching the surface of the transparent conductive film with an etching solution after the transparent conductive film is formed. The etching solution can adopt diluted queen bee water.
In a preferable embodiment, in the step (2), the polymer chain around the hillock-shaped protrusions is formed by using polymerization or crosslinking reaction of monomer molecules on the surface of the transparent conductive film initiated by light.
The invention has the beneficial effects that: a large number of hilly bulges are arranged on the surface of a transparent conductive oxide film of a transparent conductive film, and a macromolecule layer is arranged on the transparent conductive film, so that a macromolecule chain of the macromolecule layer surrounds the hilly bulges to form a binding structure, thereby forming a transparent conductive composite film; when the transparent conductive composite film is subjected to bending action, the macromolecular chains bound on the hill-shaped protrusions can strain the transparent conductive film, so that the transparent conductive film is prevented from cracking, and the conductivity of the transparent conductive film is effectively maintained. Therefore, the transparent conductive composite film not only has good bending resistance, but also has good transparency, conductivity and uniformity of a common transparent conductive oxide film, and the conductive layer of the transparent conductive composite film is a transparent conductive oxide film.
Drawings
FIG. 1 is a cross-sectional view of a transparent conductive composite film in example 1 of the present invention;
fig. 2 is a schematic view of a transparent conductive film and a polymer layer of the transparent conductive composite film in embodiment 1 of the present invention.
Detailed Description
The invention will be further described with reference to the following drawings and specific examples:
example 1
The bending-resistant transparent conductive composite film as shown in fig. 1-2 comprises a transparent conductive film 2 and a polymer layer 3 which are arranged on a flexible support film 1, wherein the transparent conductive film 2 is a transparent conductive oxide thin film plated on the flexible support film 1; the transparent conductive film 2 comprises a film base 201 and a plurality of mound-shaped protrusions 202 uniformly distributed on the film base 201; the polymer layer 3 is disposed on the transparent conductive film 2, the polymer layer 3 includes a plurality of polymer chains 301, and a part of the polymer chains 301 surround the hillock 202 to form a bound structure of the hillock 202.
The thickness of the transparent conductive film 2 was 10 nm. The height of the hillock 202 is 20% of the transparent conductive film base 201. The macromolecular layer 3 is a polymer coating.
The specific manufacturing method of the bending-resistant transparent conductive composite film comprises the following steps:
step (1), arranging a transparent conductive oxide film on a flexible support film 1, and distributing a large number of hill-shaped bulges 202 on the surface of the transparent conductive oxide film;
step (2), arranging a polymer layer 3 on the transparent conductive oxide film, and enabling part of polymer chains 301 of the polymer layer 3 to surround the hill-shaped protrusion 202 to form a single-ring bound structure 302; part of the polymer chains 301 together form a surrounding binding structure 303 around two adjacent hilly protrusions 202; portions of the polymer chains 301 collectively form a "8" -shaped bound structure 304 around two adjacent hilly protrusions 202.
In the step (1), the mound 202 is an outward extending portion of the columnar crystal 203 embedded in the film substrate 201, and specifically, the transparent conductive film 2 is formed by a magnetron sputtering deposition process, based on a film forming mechanism of magnetron sputtering island-shaped crystal growth, the transparent conductive film 2 is finally a polycrystalline structure formed by the columnar crystal 203, and the sputtering power is increased to reduce the uniformity of the growth speed of each columnar crystal 203, so that the mound 202 is formed on the surface of the transparent conductive film 2 by the portion of the columnar crystal 203 with higher final growth speed.
In the step (2), the polymer chain 301 surrounding the hilly protrusions 202 is formed by photo-induced polymerization or cross-linking of monomer molecules on the surface of the transparent conductive film 2.
Example 2
In the present embodiment, in the case where the other portions are the same as those in embodiment 1, the difference is that: and after the transparent conductive film is manufactured, etching the surface of the transparent conductive film by using etching liquid to form the hillock-shaped protrusion. Since the crystallinity of different regions (such as the center and the edge of crystal grains constituting the polycrystalline film) of the transparent conductive film is not uniform, the etching speed is also not uniform, and hillock is formed at a position where the etching is slow (such as the center of the crystal grains), and such hillock formed by etching can also form a structure in which the root is embedded in the film base. The etching solution may be diluted aqua regia or the like.
Example 3
In the present embodiment, in the case where the other portions are the same as those in embodiment 1, the difference is that: the thickness of the transparent conductive film was 100 nm.
Example 4
In the present embodiment, in the case where the other portions are the same as those in embodiment 1, the difference is that: the height of the hilly bumps is 50% of the transparent conductive film substrate.
Claims (10)
1. The utility model provides a resistant crooked transparent conductive composite film, is including setting up the transparent conductive film on flexible support membrane, and transparent conductive film is for plating the transparent conductive oxide film of system on flexible support membrane, its characterized in that: further comprising a polymer layer; the transparent conductive film comprises a film substrate and a plurality of hilly bulges uniformly distributed on the film substrate; the polymer layer is arranged on the transparent conductive film, the polymer layer comprises a large number of polymer chains, and at least part of the polymer chains surround the hillock-shaped bulges to form a binding structure of the hillock-shaped bulges.
2. A bend resistant transparent conductive composite film according to claim 1 wherein: when the hilly protrusions are used for coating, the hilly protrusions are naturally generated on the surface of the transparent conductive film through the control of coating parameters.
3. A bend resistant transparent conductive composite film according to claim 2 wherein: the hillock-shaped protrusion is an outward extending part of a columnar crystal embedded in the film substrate, a magnetron sputtering deposition process can be specifically adopted to form the transparent conductive film, the transparent conductive film is finally of a polycrystalline structure formed by the columnar crystal based on a film forming mechanism of magnetron sputtering island-shaped crystal growth, the uniformity of the growth speed of each columnar crystal is reduced by increasing sputtering power, and the hillock-shaped protrusion is formed on the surface of the transparent conductive film by the part of the columnar crystal with higher final growth speed.
4. A bend resistant transparent conductive composite film according to claim 1 wherein: the hilly bumps are formed by coarsening the transparent conductive film after the film is formed.
5. A bend resistant transparent conductive composite film according to claim 4 wherein: and after the transparent conductive film is manufactured, etching the surface of the transparent conductive film by using etching liquid to form the hillock-shaped protrusion.
6. A bend resistant transparent conductive composite film according to claim 1 wherein: the polymer layer is a polymer coating and is formed by polymerizing or crosslinking monomer molecules on the surface of the transparent conductive film.
7. A bend resistant transparent conductive composite film according to claim 6 wherein: the polymer layer has a predetermined tensile stress.
8. A bend resistant transparent conductive composite film according to claim 7 wherein: the polymer chains are formed by photo-initiated polymerization or cross-linking reactions, which generally keep the formed polymer chains in a strained state and finally form a predetermined tensile stress in the polymer layer.
9. A bend resistant transparent conductive composite film according to claim 8 wherein: in the process of forming the macromolecule layer, the length of the macromolecule chain of the macromolecule layer is enlarged through optimization of components and/or a polymerization process, so that in the macromolecule layer, at least part of the macromolecule chain jointly forms a binding structure around two adjacent hilly bulges.
10. A method for manufacturing a bending-resistant transparent conductive composite film, characterized by comprising the steps of:
step (1), arranging a transparent conductive oxide film on a flexible support film, and distributing a large number of hill-shaped bulges on the surface of the transparent conductive oxide film;
and (2) arranging a polymer layer on the transparent conductive oxide film, and enabling at least part of polymer chains of the polymer layer to surround the hilly bulges to form a bound structure.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2020/000179 WO2022020975A1 (en) | 2020-05-25 | 2020-08-10 | Bending-resistant transparent conductive composite film and manufacturing method therefor |
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| CN202010449502 | 2020-05-25 | ||
| CN2020104495028 | 2020-05-25 |
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2020
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- 2020-08-10 WO PCT/CN2020/000179 patent/WO2022020975A1/en active Application Filing
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| CN111681806B (en) | 2021-11-12 |
| WO2022020975A1 (en) | 2022-02-03 |
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