CN112309611A - Transparent conductive film, preparation method and application thereof, and photoelectric device comprising transparent conductive film - Google Patents
Transparent conductive film, preparation method and application thereof, and photoelectric device comprising transparent conductive film Download PDFInfo
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- CN112309611A CN112309611A CN201910712419.2A CN201910712419A CN112309611A CN 112309611 A CN112309611 A CN 112309611A CN 201910712419 A CN201910712419 A CN 201910712419A CN 112309611 A CN112309611 A CN 112309611A
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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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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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
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- H—ELECTRICITY
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- 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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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
Abstract
The invention discloses a transparent conductive film, a preparation method and application thereof, and a photoelectric device containing the transparent conductive film. The transparent conductive film sequentially comprises a first conductive film layer, a transparent substrate layer and a second conductive film layer which are mutually overlapped, wherein a plurality of through holes are formed in the transparent substrate, and the aperture of each through hole is 0.5-100 mu m; when being equipped with two or more than two through-holes that run through on the transparent substrate, the interval between two arbitrary adjacent through-hole central points is 0.1 ~ 100mm, the through-hole accounts for transparent substrate's volume ratio is 0.001 ~ 25 permillage, it has conductive medium to fill in the through-hole. The transparent conductive film can realize bulk phase conductivity on the basis of not influencing the light transmission of the material, has uniform conductivity, can generate more signals, realizes the diversification of photoelectric products, can control the erasable range of the conductive liquid crystal panel, has simple preparation process, and is beneficial to realizing industrial large-scale production.
Description
Technical Field
The invention relates to the field of photoelectric products, in particular to a transparent conductive film, a preparation method and application thereof, and a photoelectric device containing the transparent conductive film.
Background
Photoelectric products all need light penetration and electric conduction, so that the transparent conductive film is the basis of the photoelectric products, and the photoelectric products such as a conductive liquid crystal panel, a flat panel display, a touch panel, a solar cell, electronic paper, OLED (organic light emitting diode) lighting and the like all need to use the transparent conductive film.
In a conventional transparent conductive film, an ITO (indium tin oxide) layer is generally magnetron sputtered on a surface of a transparent film material such as PET (polyethylene terephthalate), PC (polycarbonate), PI (polyimide), or the like, thereby achieving a surface conductive effect. However, such a transparent conductive film can actually realize single-sided (two-dimensional) conduction, and cannot achieve bulk-phase (three-dimensional) conduction.
In a conventional method, a transparent conductive film is connected to an external Circuit through a Flexible Printed Circuit (FPC), so that a position signal sensed by the transparent conductive film is transmitted to a processor for recognition and determination of a touch position. In photoelectric products, a single-side conductive transparent conductive film generates few signals, and diversification of the photoelectric products is limited.
Two conductive films are commercially available at present, one is a polymer film filled with carbon black, carbon nanotubes and graphene, and the polymer film has the characteristic of bulk phase conductivity but does not have transparency; the second is a conductive film prepared by coating silver nanowires, magnetron sputtering ITO, and electroplating a metal grid on a polymer film, which has transparency but does not have bulk (three-dimensional) conductive effect.
Patent CN 103295670a reports a transparent conductive film with three-dimensional conductive effect, which includes a transparent substrate, a conductive line, a first conductive layer and a second conductive layer. The first conductive layer and the second conductive layer are electrically connected by a lead electrode. The first conductive layer and the second conductive layer of the conductive film are both composed of a plurality of electrodes arranged at intervals, so that the adjacent two electrodes are insulated from each other, and the electrode constituting the first conductive layer and the electrode constituting the second conductive layer are arranged in a crossed manner in space to form mutual inductance capacitance, so that longitudinal (vertical) transmission of current cannot be formed.
Therefore, how to obtain a transparent conductive film for realizing bulk (three-dimensional) conduction by longitudinal (perpendicular) transmission of current is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the technical problem that the conductive film in the prior art is opaque or is difficult to be applied to photoelectric products; or only plane (two-dimensional) conduction or three-dimensional mutual inductance capacitance can be realized, and the defect of longitudinal (vertical) transmission of current is difficult to form, so that the transparent conductive film, the preparation method and the application thereof, and the photoelectric device containing the transparent conductive film are provided. The transparent conductive film can realize bulk phase conduction (forming longitudinal (vertical to the film) transmission of current) on the basis of not influencing the light transmission of the material, has uniform conductive performance, can generate more signals, and realizes the diversification of photoelectric products, such as the functions of electrochromism and the like through a composite liquid crystal material; and the preparation process is simple, and is beneficial to realizing industrial large-scale production.
The invention provides a transparent conductive film, which sequentially comprises a first conductive film layer, a transparent substrate layer and a second conductive film layer which are mutually overlapped, wherein a plurality of through holes are formed in the transparent substrate, and the aperture of each through hole is 0.5-100 mu m; when being equipped with two or more than two through-holes that run through on the transparent substrate, the interval between two arbitrary adjacent through-hole central points is 0.1 ~ 100mm, the through-hole accounts for transparent substrate's volume ratio is 0.001 ~ 25 permillage, it has conductive medium to fill in the through-hole.
In the present invention, the transparent substrate may be a transparent substrate that is conventional in the art, such as a PE (polyethylene) film, a PS (polystyrene) film, a PU (polyurethane) film, a PET (polyethylene terephthalate) film, a PC (polycarbonate) film, a PI (polyimide) film, a PEN (polyethylene naphthalate) film, or a PVC (polyvinyl chloride) film.
In the present invention, the aperture of the through hole is preferably 0.5 to 80 μm, for example, 0.5 μm, 1.0 μm, 5 μm, 20 μm or 80 μm.
In the invention, the distance between the center points of any two adjacent through holes is preferably 1-50 mm, such as 1mm, 5mm, 10mm, 15mm or 50 mm.
In the present invention, the volume ratio of the through holes to the transparent substrate is preferably 0.0013 to 0.25%, for example, 0.0013%, 0.0016%, 0.011%, 0.016%, or 0.25%.
In the invention, preferably, the aperture of each through hole is 0.5-80 μm, the distance between the central points of any two adjacent through holes is 1-50 mm, and the volume ratio of the through holes to the transparent substrate is 0.0013-0.25 per mill.
In the invention, preferably, the aperture of the through hole is 1 μm, the distance between the central points of any two adjacent through holes is 5mm, and the volume ratio of the through holes in the transparent substrate is 0.0013 per thousand.
In the present invention, preferably, the aperture of the through hole is 0.5 μm, the distance between the center points of any two adjacent through holes is 1mm, and the volume ratio of the through hole to the transparent substrate is 0.016 ‰.
In the invention, preferably, the aperture of the through hole is 80 μm, the distance between the central points of any two adjacent through holes is 50mm, and the volume ratio of the through holes in the transparent substrate is 0.25 per thousand.
In the invention, preferably, the aperture of the through hole is 5 μm, the distance between the central points of any two adjacent through holes is 10mm, and the volume ratio of the through holes in the transparent substrate is 0.0016 per thousand.
In the invention, preferably, the aperture of the through hole is 20 μm, the distance between the central points of any two adjacent through holes is 15mm, and the volume ratio of the through holes in the transparent substrate is 0.011 per thousand.
In the present invention, the conductive medium may be one or more of conductive media conventional in the art, such as metal, metal oxide, conductive carbon material, and conductive polymer.
Wherein the metal may be a metal conventional in the art, such as one or more of gold, silver, copper, iron, tin, aluminum, and platinum, further such as silver and/or copper.
Wherein the metal oxide may be a metal oxide conventional In the art, such as ITO (In)2O3Sn, indium tin oxide), ATO (Sn)2Sb, antimony tin oxide), AZO (ZnO: Al) and FTO (SnO)2F), for example AZO.
The conductive carbon material may be a conductive carbon material conventional in the art, such as conductive carbon black and/or graphite, and further such as conductive carbon black.
The conductive polymer may be one or more of polyaniline, polypyrrole and polythiophene, such as polypyrrole, which are conventional in the art.
In the present invention, the material of the first conductive film may be a conductive material conventional in the art, such as one or more of a metal, a metal oxide, a conductive carbon material, and a conductive polymer, and further such as a metal and/or a metal oxide.
Wherein the metal may be a metal conventional in the art, such as one or more of gold, silver, copper, iron, tin, aluminum and platinum, such as one or more of silver, copper and gold, and such as silver, copper or gold.
Wherein the metal oxide may be a metal oxide conventional In the art, such as ITO (In)2O3Sn, indium tin oxide), ATO (Sn)2Sb, antimony tin oxide), AZO (ZnO: Al) and FTO (SnO)2F), for example AZO.
The conductive carbon material may be a conductive carbon material conventional in the art, such as carbon nanotubes and/or graphene.
The conductive polymer may be one or more of polyaniline, polypyrrole, and polythiophene, which are conventional in the art.
In the present invention, the first conductive film can be formed by a method conventional in the art, such as magnetron sputtering, coating, imprinting or plasma etching.
When the material of the first conductive film is metal, the first conductive film can be prepared by a coating method, such as one or more of a silver nanowire film, a copper nanowire film, an aluminum nanowire film and a gold nanowire film; the first conductive film may also be formed by coating, imprinting or plasma etching, such as one or more of a gold conductive mesh film, a silver conductive mesh film, a copper conductive mesh film, an iron conductive mesh film, a tin conductive mesh film, an aluminum conductive mesh film, and a platinum conductive mesh film.
When the first conductive film is made of metal oxide, the first conductive film can be prepared by adopting a magnetron sputtering method; the first conductive film may also be made by coating, imprinting or plasma etching, such as one or more of an ITO conductive mesh film, an ATO conductive mesh film, an AZO conductive mesh film, and an FTO conductive mesh film.
When the material of the first conductive film is a conductive carbon material and/or a conductive polymer, the first conductive film can be prepared by a coating method.
In the invention, the first conductive film can be an ITO film, an ATO film, an AZO film or an FTO film which are subjected to magnetron sputtering; or a coated silver nanowire film, copper nanowire film, aluminum nanowire film, gold nanowire film, carbon nanotube film, graphene film, polyaniline film, polypyrrole film, or polythiophene film; it may also be a coated, embossed or plasma etched gold conductive mesh film, silver conductive mesh film, copper conductive mesh film, iron conductive mesh film, tin conductive mesh film, aluminum conductive mesh film, platinum conductive mesh film, ITO conductive mesh film, ATO conductive mesh film, AZO conductive mesh film or FTO conductive mesh film.
In the present invention, the material of the second conductive film may be a conductive material conventional in the art, such as one or more of a metal, a metal oxide, a conductive carbon material, and a conductive polymer, and further such as a metal and/or a metal oxide.
Wherein the metal may be a metal conventional in the art, such as one or more of gold, silver, copper, iron, tin, aluminum and platinum, such as one or more of silver, copper and gold, and such as silver, copper or gold.
Wherein the metal oxide may be a metal oxide conventional In the art, such as ITO (In)2O3Sn, indium tin oxide), ATO (Sn)2Sb, antimony tin oxide), AZO (ZnO: Al) and FTO (SnO)2F), for example AZO.
The conductive carbon material may be a conductive carbon material conventional in the art, such as carbon nanotubes and/or graphene.
The conductive polymer may be one or more of polyaniline, polypyrrole, and polythiophene, which are conventional in the art.
The second conductive film can be formed by a method conventional in the art, such as magnetron sputtering, coating, imprinting or plasma etching.
When the material of the second conductive film is ITO (In)2O3:Sn)、ATO(Sn2Sb, AZO (ZnO: Al) and FTO (SnO)2F), the second conductive film can be prepared by adopting a magnetron sputtering method.
When the material of the second conductive film is metal, the second conductive film can be prepared by a coating method, such as one or more of a silver nanowire film, a copper nanowire film, an aluminum nanowire film and a gold nanowire film; the second conductive film may also be formed by coating, imprinting or plasma etching, such as one or more of a gold conductive mesh film, a silver conductive mesh film, a copper conductive mesh film, an iron conductive mesh film, a tin conductive mesh film, an aluminum conductive mesh film, and a platinum conductive mesh film.
When the material of the second conductive film is metal oxide, the first conductive film can be prepared by adopting a magnetron sputtering method; the second conductive film may also be formed by coating, imprinting or plasma etching, such as one or more of an ITO conductive mesh film, an ATO conductive mesh film, an AZO conductive mesh film, and an FTO conductive mesh film.
When the material of the second conductive film is a conductive carbon material and/or a conductive polymer, the second conductive film can be prepared by a coating method.
In the invention, the second conductive film can be an ITO film, an ATO film, an AZO film or an FTO film which are subjected to magnetron sputtering; or a coated silver nanowire film, copper nanowire film, aluminum nanowire film, gold nanowire film, carbon nanotube film, graphene film, polyaniline film, polypyrrole film, or polythiophene film; it may also be a coated, embossed or plasma etched gold conductive mesh film, silver conductive mesh film, copper conductive mesh film, iron conductive mesh film, tin conductive mesh film, aluminum conductive mesh film, platinum conductive mesh film, ITO conductive mesh film, ATO conductive mesh film, AZO conductive mesh film or FTO conductive mesh film.
In the present invention, preferably, the first conductive film and the second conductive film are both a silver nanowire film, an AZO film, or a gold conductive mesh film.
In the invention, preferably, the first conductive film is a copper nanowire film, and the second conductive film is an AZO film; or, the first conductive film is an AZO film, and the second conductive film is a copper nanowire film.
In the present invention, the surface of the first conductive film and/or the second conductive film may further include a hardened layer to prevent the first conductive film layer and/or the second conductive film layer from being peeled off or oxidized.
Wherein, the surface of the first conductive film and/or the second conductive film is a side not directly contacting with the transparent substrate, as known by those skilled in the art.
The material of the hardened layer may be a material that can prevent the conductive film layer from falling off, such as acrylate and/or polyurethane, which are conventional in the art.
Wherein the hardened layer can be prepared by a method conventional in the art, such as coating.
In the present invention, the through holes can be obtained by a method conventional in the art, such as punching the transparent substrate, and then pressing through the transparent substrate by using the conductive medium.
The perforation process may be any perforation process known in the art, such as laser perforation or chemical etching perforation.
Wherein the conductive medium is generally harder than the transparent substrate when pressed through the transparent substrate with the conductive medium. The conductive medium may be a metal.
In the present invention, preferably, the through hole is perpendicular to the transparent substrate.
In the present invention, the cross-sectional shape of the through-hole may be circular, square or triangular.
The invention also provides a preparation method of the transparent conductive film, which comprises the following steps of carrying out magnetron sputtering, coating, imprinting or plasma etching treatment on the material of the first conductive film and the material of the second conductive film to enable the materials to be respectively attached to the two side surfaces of the transparent substrate;
when the transparent conducting film further comprises the hardening layer, the material of the hardening layer is coated on the surface of the first conducting film layer and/or the second conducting film layer.
The invention also provides an application of the transparent conductive film as a conductive element in a photoelectric device.
The photoelectric device can be one or more of a conductive liquid crystal panel, a touch panel, a solar cell, electronic paper, an electrochromic film and an OLED lighting lamp, such as the conductive liquid crystal panel.
The conductive liquid crystal panel may be a conductive liquid crystal panel conventional in the art, such as an electronic blackboard, an electronic whiteboard, a writing pad, or a writing liquid crystal panel.
The invention also provides a photoelectric device which comprises the transparent conductive film.
The photoelectric device can be one or more of a conductive liquid crystal panel, a touch panel, a solar cell, electronic paper, an electrochromic film and an OLED lighting lamp.
The conductive liquid crystal panel may be a conductive liquid crystal panel conventional in the art, such as an electronic blackboard, an electronic whiteboard, a writing pad, or a writing liquid crystal panel.
When the photoelectric device is a conductive liquid crystal panel, the photoelectric device sequentially comprises the transparent conductive film layer, the display layer and the conductive layer which are mutually overlapped.
Wherein, the material of the display layer can be liquid crystal polymer.
Wherein the erasing process of the conductive liquid crystal panel can be as follows: the transparent conductive film layer is tightly attached to an erasing component; the erasing component is connected with a first electrode, and the conducting layer is connected with a second electrode; the first electrode and the second electrode form an electric loop through a driving circuit, and an erasing pulse signal is generated through the driving circuit.
The wiping member may be a metal sheet.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the transparent conductive film can realize bulk phase conduction (forming longitudinal (vertical to the film) transmission of current) on the basis of not influencing the light transmission of the material, has uniform conductive performance, can generate more signals and realizes the diversification of photoelectric products; and the preparation process is simple, and is beneficial to realizing industrial large-scale production.
(2) The photoelectric device in the invention has diversified functions, for example, the composite liquid crystal material can realize the functions of electrochromism and the like; and can control the erasable range of the conductive liquid crystal panel, and the minimum erasable area can reach 2.3mm2。
Drawings
Fig. 1 is a schematic cross-sectional view of the transparent conductive film produced in example 1.
Fig. 2 is a circuit diagram illustrating an erasing process of the conductive liquid crystal panel according to embodiment 2.
The drawings illustrate the following:
10: a transparent substrate layer;
20: a through hole;
301: a first conductive film layer;
302: a second conductive film layer;
401: a first hardened layer;
402: a second hardened layer;
1: an electrode;
2: a drive circuit;
3: an electrode;
110: an erasing member metal piece;
111: a transparent conductive film layer;
112: a liquid crystal polymer layer;
113: a conductive film layer.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Fig. 1 is a schematic cross-sectional view of a transparent conductive film in embodiment 1. The transparent conductive film comprises, in order: a first hardened layer 401, a first conductive film 301, a transparent substrate layer 10, a second conductive film 302 and a second hardened layer 401, wherein through holes 20 are distributed on the transparent substrate layer 10.
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, stamping silver metal on the surface of a transparent PVC film 10, pressing through the PVC film to form silver metal conductive channels 20 with the diameter of 1 mu m, controlling the distance between the central points of two adjacent silver metal conductive channels to be 5mm, and controlling the volume ratio of the silver metal conductive channels to the transparent PVC film to be 0.0013 per mill;
(2) then coating silver nanowires on the surfaces of both sides of the PVC film to prepare transparent conductive layers 301 and 302;
(3) and finally, coating acrylic acid on the surface of the silver nanowire layer to obtain a first hardened layer 401 and a second hardened layer 402 so as to prevent the silver nanowire from being stripped or oxidized.
Example 2
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, preparing through holes with the aperture of 0.5 mu m on the surface of a transparent PC film by using a laser drilling instrument, controlling the distance between two adjacent holes and the center point of the hole to be 1mm, and controlling the volume ratio of the through holes to the transparent PC film to be 0.016 thousandth;
(2) then filling polypyrrole in the hole;
(3) and finally, carrying out magnetron sputtering AZO on the surfaces of the two sides of the transparent PC film to prepare the transparent conducting layer.
Example 3
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, stamping copper metal on the surface of a transparent PI film, pressing through the PI film to form a copper metal conductive channel with the diameter of 80 mu m, controlling the distance between the central points of two adjacent copper metal conductive channels to be 50mm, and controlling the volume ratio of the copper metal conductive channel to the transparent PI film to be 0.25 per mill;
(2) then coating a copper nanowire on the surface of one side of the PI film to prepare a transparent conducting layer, and carrying out magnetron sputtering AZO on the surface of the other side of the PI film to prepare the transparent conducting layer;
(3) and finally, coating a polyurethane hardening layer on the surface of the copper nanowire to prevent the copper nanowire from being stripped or oxidized.
Example 4
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, preparing through holes with the aperture of 5 microns on the surface of a transparent PET film through chemical etching, controlling the distance between two adjacent holes and the center point of the hole to be 10mm, and controlling the volume ratio of the through holes to the transparent PET film to be 0.0016 per mill;
(2) then filling conductive carbon black in the holes;
(3) and finally, etching the gold conductive grids on the two side surfaces of the transparent PET film by using plasma to obtain the transparent conductive layer.
Example 5
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, preparing through holes with the aperture of 20 microns on the surface of a transparent PET film through chemical etching, controlling the distance between two adjacent holes and the center point of the hole to be 15mm, and controlling the volume ratio of the through holes to the transparent PET film to be 0.011 per thousand;
(2) then filling conductive carbon black in the holes;
(3) and finally, etching the gold conductive grids on the two side surfaces of the transparent PET film by using plasma to obtain the transparent conductive layer.
Comparative example 1
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, stamping silver metal on the surface of a transparent PVC film, pressing through the PVC film to form silver metal conductive channels with the diameter of 200 mu m, controlling the distance between the central points of two adjacent silver metal conductive channels to be 5mm, and controlling the volume ratio of the silver metal conductive channels to the transparent PVC film to be 1.6 per mill;
(2) then coating silver nanowires on the surfaces of both sides of the PVC film to prepare a transparent conducting layer;
(3) and finally, coating an acrylic acid hardened layer on the surface of the silver nanowire to prevent the silver nanowire from being stripped or oxidized.
Comparative example 2
The preparation method of the transparent conductive film comprises the following steps:
(1) firstly, stamping silver metal on the surface of a transparent PVC film, pressing through the PVC film to form silver metal conductive channels with the diameter of 1 mu m, controlling the distance between the central points of two adjacent silver metal conductive channels to be 10mm, and controlling the volume ratio of the silver metal conductive channels to the transparent PVC film to be 0.0007 per mill;
(2) then coating silver nanowires on the surfaces of both sides of the PVC film to prepare a transparent conducting layer;
(3) and finally, coating an acrylic acid hardened layer on the surface of the silver nanowire to prevent the silver nanowire from being stripped or oxidized.
Effect example 1
The transparent conductive films obtained in examples 1 to 5 and comparative examples 1 to 2 were subjected to light transmittance, haze and conductivity tests.
The test method refers to GB/T2410-.
Specific results are shown in table 1 below.
TABLE 1
As can be seen from Table 1:
(1) the transparent conductive film prepared in the embodiments 1-5 has excellent performance, the bulk resistance is less than or equal to 1200 omega, the visible light transmittance at 550nm is more than or equal to 70 percent, and the haze is less than or equal to 3 percent;
(2) the aperture size, the via pitch, and the via volume of the transparent conductive film prepared in comparative examples 1 to 2 were out of the range of the present application, and it was apparently difficult to achieve the performance of the transparent conductive film of the present application.
Effect example 2
The transparent conductive films obtained in examples 1 to 5 and comparative examples 1 to 2 were applied to a conductive liquid crystal panel, and the erasure properties thereof were examined.
The structure of the conductive liquid crystal panel is shown in fig. 2: the liquid crystal display panel sequentially comprises a transparent conductive film layer 111, a liquid crystal polymer layer 112 (display layer) and a conductive layer 113 which are mutually overlapped, wherein under the action of pressure, the arrangement of liquid crystal molecules of the liquid crystal polymer is changed so as to display color, namely display information; under the action of a voltage electric field, the arrangement of liquid crystal molecules is changed along with the electric field so as to be transparent, namely, information is erased.
The erase procedure is as follows: the driving circuit 2 generates an erasing pulse signal with the voltage range of 5-30V; the metal sheet 110 of the erasing part is tightly attached to the transparent conductive film 111 prepared in the examples 1-5 and the comparative examples 1-2, the electrode 1 is led out from the metal sheet 110 of the erasing part, the electrode 3 is led out from the conductive film 113, the electrodes 1 and 3 are connected with the driving circuit 2 and form an electric circuit with the liquid crystal display part, and the local content can be accurately erased under the action of micro-current erasing pulses.
The area of the metal sheet of the erasing part is 10mm2The selected erase region is the region of the liquid crystal polymer layer where the liquid crystal molecules change with the electric field. Condition that the areas covered by the metal sheet of the erasing part are all the target erasing areasNext, the one-time erasable areas of the conductive liquid crystal panels produced from the transparent conductive films of examples 1 to 5 and comparative examples 1 to 2 are shown in table 2 below.
TABLE 2
As shown in Table 2, the erasable area of the transparent conductive film can be controlled in the erasable range of the conductive liquid crystal panel, and the erasable area can be 2.3mm at the lowest under the conditions that the resistance of the transparent conductive film is not more than 1200 omega, the visible light transmittance at 550nm is not less than 70% and the haze is not more than 3%2And the erasing precision is high.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. A transparent conductive film is characterized by sequentially comprising a first conductive film layer, a transparent substrate layer and a second conductive film layer which are mutually overlapped, wherein a plurality of through holes are formed in the transparent substrate, and the aperture of each through hole is 0.5-100 mu m; when being equipped with two or more than two through-holes that run through on the transparent substrate, the interval between two arbitrary adjacent through-hole central points is 0.1 ~ 100mm, the through-hole accounts for transparent substrate's volume ratio is 0.001 ~ 25 permillage, it has conductive medium to fill in the through-hole.
2. The transparent conductive film according to claim 1, wherein the transparent substrate is a PE film, a PS film, a PU film, a PET film, a PC film, a PI film, a PEN film, or a PVC film;
and/or the aperture of the through hole is 0.5-80 μm, preferably 0.5 μm, 1.0 μm, 5 μm, 20 μm or 80 μm;
and/or the distance between the center points of any two adjacent through holes is 1-50 mm, preferably 1mm, 5mm, 10mm, 15mm or 50 mm;
and/or the through holes account for 0.0013-25 per thousand, preferably 0.0013 per thousand, 0.0016 per thousand, 0.011 per thousand, 0.016 per thousand or 0.25 per thousand of the volume ratio of the transparent substrate.
3. The transparent conductive film according to claim 1, wherein the aperture of the through holes is 0.5 to 80 μm, the distance between the center points of any two adjacent through holes is 1 to 50mm, and the volume ratio of the through holes to the transparent substrate is 0.0013 to 0.25%.
4. The transparent conductive film of claim 1, wherein the conductive medium is one or more of a metal, a metal oxide, a conductive carbon material, and a conductive polymer;
the metal is preferably one or more of gold, silver, copper, iron, tin, aluminium and platinum, more preferably silver and/or copper;
the metal oxide is preferably one or more of ITO, ATO, AZO and FTO, and more preferably AZO;
the conductive carbon material is preferably conductive carbon black and/or graphite, more preferably conductive carbon black;
the conductive polymer is preferably one or more of polyaniline, polypyrrole, and polythiophene, and more preferably polypyrrole.
5. The transparent conductive film according to any one of claims 1 to 4, wherein the material of the first conductive film is one or more of a metal, a metal oxide, a conductive carbon material and a conductive polymer, preferably a metal and/or a metal oxide; the metal is preferably one or more of gold, silver, copper, iron, tin, aluminum and platinum, more preferably one or more of silver, copper and gold; the metal oxide is preferably one or more of ITO, ATO, AZO and FTO, and more preferably AZO; the conductive carbon material is preferably carbon nano tube and/or graphene; the conductive polymer is preferably one or more of polyaniline, polypyrrole and polythiophene;
and/or the material of the second conductive film is one or more of metal, metal oxide, conductive carbon material and conductive polymer, preferably metal and/or metal oxide; the metal is preferably one or more of gold, silver, copper, iron, tin, aluminum and platinum, more preferably one or more of silver, copper and gold; the metal oxide is preferably one or more of ITO, ATO, AZO and FTO, and more preferably AZO; the conductive carbon material is preferably carbon nano tube and/or graphene; the conductive polymer is preferably one or more of polyaniline, polypyrrole and polythiophene;
and/or the first conductive film and/or the second conductive film are/is prepared by magnetron sputtering, coating, imprinting or plasma etching.
6. The transparent conductive film of claim 5, wherein the first conductive film and the second conductive film are both a silver nanowire film, an AZO film, or a gold conductive mesh film;
or the first conductive film is a copper nanowire film, and the second conductive film is an AZO film;
or, the first conductive film is an AZO film, and the second conductive film is a copper nanowire film.
7. The transparent conductive film according to any one of claims 1 to 4, wherein the surface of the first conductive film and/or the second conductive film further comprises a hardened layer; the material of the hardening layer is preferably acrylate and/or polyurethane;
and/or the through hole is obtained by adopting the following method: perforating the transparent substrate; or, pressing through the transparent substrate by using the conductive medium; wherein, the punching treatment is preferably laser punching or chemical etching punching;
and/or the through hole is perpendicular to the transparent substrate;
and/or the cross section of the through hole is in a circular, square or triangular shape.
8. The method according to any one of claims 1 to 7, comprising the steps of subjecting the material of the first conductive film and the material of the second conductive film to magnetron sputtering, coating, imprinting or plasma etching treatment so as to be respectively attached to both side surfaces of the transparent substrate;
when the transparent conducting film further comprises the hardening layer, the material of the hardening layer is coated on the surface of the first conducting film layer and/or the second conducting film layer.
9. Use of a transparent conductive film according to any one of claims 1 to 7 as a conductive element in an optoelectronic device;
the optoelectronic device is preferably one or more of a conductive liquid crystal panel, a touch panel, a solar cell, electronic paper, an electrochromic film and an OLED lighting.
10. An optoelectronic device comprising the transparent conductive film according to any one of claims 1 to 7;
the photoelectric device is preferably one or more of a conductive liquid crystal panel, a touch panel, a solar cell, electronic paper, an electrochromic film and an OLED illuminating lamp;
when the photoelectric device is a conductive liquid crystal panel, the photoelectric device sequentially comprises the transparent conductive film layer, the display layer and the conductive layer which are mutually overlapped; the material of the display layer is preferably a liquid crystal polymer.
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| CN201910712419.2A CN112309611A (en) | 2019-08-02 | 2019-08-02 | Transparent conductive film, preparation method and application thereof, and photoelectric device comprising transparent conductive film |
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| CN201910712419.2A CN112309611A (en) | 2019-08-02 | 2019-08-02 | Transparent conductive film, preparation method and application thereof, and photoelectric device comprising transparent conductive film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773717A (en) * | 2022-06-15 | 2022-07-22 | 周久胖 | Antistatic and high-transparency polyethylene film for packaging and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773717A (en) * | 2022-06-15 | 2022-07-22 | 周久胖 | Antistatic and high-transparency polyethylene film for packaging and preparation method thereof |
| CN114773717B (en) * | 2022-06-15 | 2023-12-08 | 哈尔滨鹏程新材料科技股份有限公司 | Antistatic high-transparency polyethylene film for packaging and preparation method thereof |
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