CN112908517A - Transparent conductive film and preparation method thereof - Google Patents
Transparent conductive film and preparation method thereof Download PDFInfo
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- 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
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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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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Abstract
The invention provides a transparent conductive film and a preparation method thereof, wherein the transparent conductive film sequentially comprises a transparent substrate, a first conductive layer, a second conductive layer and a third conductive layer from bottom to top, the first conductive layer and the third conductive layer respectively and independently contain conductive oxides, the second conductive layer contains metal or carbon materials, the thickness of the first conductive layer is 25-100 nm, the thickness of the second conductive layer is 50-150 nm, and the thickness of the third conductive layer is 5-50 nm. The transparent conductive film prepared by the preparation method has low sheet resistance and high light transmittance, is less prone to cracking or warping, and has better performance.
Description
Technical Field
The invention relates to the technical field of conductive films, in particular to a transparent conductive film and a preparation method thereof.
Background
The transparent conductive film is a film which can conduct electricity and has high light transmittance in a visible light range, and is widely applied to the fields of optical devices, display devices, touch screens, film photovoltaic modules and the like.
The transparent conductive film is mainly a Transparent Conductive Oxide (TCO) conductive film, a substrate of the Transparent Conductive Oxide (TCO) conductive film is usually polyethylene terephthalate (PET), and a conductive layer of the Transparent Conductive Oxide (TCO) conductive film is usually Indium Tin Oxide (ITO), and the transparent conductive film has good flexibility, but the resistance performance and the transmittance performance of the transparent conductive film are still to be improved.
In the prior art, a transparent conductive film compounded by a metal grid and a conductive oxide is prepared by obtaining a layer of transparent oxide film on the surface of the metal grid by using a vacuum magnetron sputtering method, and the conductive film sequentially comprises a PET substrate, a metal grid layer and a conductive oxide layer from bottom to top and has lower sheet resistance and higher light transmittance. The inventors have found that, in the process of preparing the composite transparent conductive film, the conductive oxide layer needs to be annealed to improve the crystallinity thereof, so as to improve the conductivity of the conductive oxide layer, but due to the material difference between the metal grid layer and the conductive oxide layer interface, the stress distribution is not uniform in the annealing process, so that the conductive oxide layer is cracked or warped, and the performance of the transparent conductive film is affected.
Disclosure of Invention
The invention aims to provide a transparent conductive film and a preparation method thereof, which are used for further reducing the sheet resistance of the transparent conductive film and solving the problem of cracking or warping of a conductive oxide layer caused by uneven stress distribution during annealing of the transparent conductive film. The specific technical scheme is as follows:
the first aspect of the invention provides a transparent conductive film, which sequentially comprises a transparent substrate, a first conductive layer, a second conductive layer and a third conductive layer from bottom to top, wherein the first conductive layer and the third conductive layer respectively and independently contain conductive oxides, the second conductive layer contains metal or carbon materials, the thickness of the first conductive layer is 25-100 nm, preferably 30-50 nm, the thickness of the second conductive layer is 50-150 nm, preferably 60-100 nm, and the thickness of the third conductive layer is 5-50 nm, preferably 10-25 nm.
In one embodiment of the present invention, the conductive oxide in the first conductive layer and the third conductive layer is each independently selected from any one of FTO, ITO, IWO, AZO, zinc oxide, and tin dioxide.
In one embodiment of the present invention, the metal is selected from any one of aluminum, silver, copper, nanogold or nanosilver, and the carbon material is selected from graphene.
In one embodiment of the invention, the transparent substrate is selected from any one of glass, PET, PEN and PI, and the thickness of the glass transparent substrate is 0.3-5 mm; the thickness of the PET, PEN or PI transparent base material is 0.025-0.3 mm.
In one embodiment of the present invention, the second conductive layer is a conductive layer containing a continuous line-like pattern or a conductive layer containing a continuous grid-like pattern.
In one embodiment of the present invention, in the second conductive layer, the area of the line-shaped conductive material accounts for 0.01% to 5% of the surface area of the plane of the transparent conductive film.
In one embodiment of the invention, the transparent conductive film has a light transmittance of 85-90%, a haze of 0.9-1.2%, and a sheet resistance of 0.1-10 Ω/sq.
A second aspect of the present invention provides a method for preparing the transparent conductive film according to the first aspect, including:
preparing a first conductive layer on the surface of a transparent substrate:
depositing a layer of conductive oxide on the surface of the transparent substrate, and then annealing to obtain the first conductive layer, wherein the annealing temperature is 120-170 ℃, and the annealing time is 20-40 min;
preparing a second conductive layer on the surface of the first conductive layer:
coating, depositing or printing a conductive material on the surface of the first conductive layer to form the second conductive layer containing a pattern;
preparing a third conductive layer on the surface of the second conductive layer:
and depositing a layer of conductive oxide on the surface of the second conductive layer to form the third conductive layer.
In one embodiment of the present invention, a method for forming the first conductive layer and the third conductive layer includes: magnetron sputtering, chemical vapor deposition, plasma chemical vapor deposition, reactive plasma deposition or atomic layer deposition.
In one embodiment of the present invention, the second conductive layer is prepared by:
coating the nano metal wire slurry on the surface of the first conductive layer through a slit coating die, and forming a second conductive layer after curing; wherein the curing temperature is 100-140 ℃, the curing time is 8-15 min, the concentration of the nano metal wire slurry is 5-10 mg/ml, the length of the nano metal wire is 10-25 mu m, the diameter is 20-40 nm, and the nano metal wire is selected from a nano silver wire or a nano gold wire;
or printing ink containing a conductive material on the surface of the first conductive layer, and drying to form a conductive material line; wherein the solid content of the ink is 10% -20%, and the line width of the conductive material line is 1-100 μm;
or sputtering a layer of metal film on the surface of the first conducting layer by a magnetron sputtering method, and then chemically etching to obtain a metal line; wherein the line width of the metal lines is 10-100 μm.
The invention has the beneficial effects that:
according to the transparent conductive film and the preparation method thereof, the first conductive layer containing conductive oxide is prepared on the surface of the transparent substrate and annealed, so that the annealed first conductive layer has lower sheet resistance, and the second conductive layer is not formed on the surface of the first conductive layer before annealing, so that cracking or warping of the first conductive layer caused by material difference between the interface of the second conductive layer and the first conductive layer in the annealing process is avoided; and preparing a second conductive layer on the surface of the annealed first conductive layer, and then preparing a third conductive layer containing conductive oxide on the surface of the second conductive layer, wherein the first conductive layer has lower sheet resistance, so that the transparent conductive film can have lower sheet resistance without annealing the third conductive layer. In addition, the third conducting layer is covered on the surface of the second conducting layer, so that the effect of preventing the conducting material in the second conducting layer from being oxidized can be achieved, and the stability of the transparent conducting film is improved. In conclusion, the transparent conductive film prepared by the preparation method has low sheet resistance and high light transmittance, is less prone to cracking or warping, and has better performance. Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
FIG. 1 is a schematic structural diagram of a transparent conductive film according to an embodiment of the present invention;
fig. 2 is a schematic structural view of a metal grid according to an embodiment of the present invention.
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. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a transparent conductive film, as shown in figure 1, which sequentially comprises a transparent substrate 1, a first conductive layer 2, a second conductive layer 3 and a third conductive layer 4 from bottom to top, wherein the first conductive layer 2 and the third conductive layer 4 respectively and independently contain conductive oxides, the second conductive layer 3 contains metal or carbon materials, and the thickness of the first conductive layer 2 is 25-100 nm; the thickness of the second conductive layer 3 is 50-150 nm; the thickness of the third conductive layer 4 is 5 to 50 nm. By controlling the thicknesses of the first conductive layer, the second conductive layer, and the third conductive layer within the above ranges, a transparent conductive film having excellent conductivity, light transmittance, and mechanical properties can be obtained.
According to the invention, the first conductive layer, the second conductive layer and the third conductive layer are sequentially arranged from bottom to top, and the thicknesses of the first conductive layer, the second conductive layer and the third conductive layer are controlled within the thickness range, so that the conductivity of the transparent conductive film can be effectively improved. The oxide conductive layer generally plays a role of conducting electricity, and the inventors have also surprisingly found that covering a thinner third conductive layer on the surface of the second conductive layer can play a role of preventing the conductive material in the second conductive layer from being oxidized, and improve the stability of the transparent conductive film.
The material of the transparent substrate is not particularly limited in the present invention as long as the object of the present invention can be achieved, and the transparent substrate is selected from any one of glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and Polyimide (PI).
The metal in the second conductive layer of the present invention may be selected from any one of aluminum, silver, copper, nanogold, or nanosilver, and the carbon material in the second conductive layer is selected from graphene. The above metal or carbon material may be added to the second conductive layer, thereby improving the conductive performance of the second conductive layer.
In one embodiment of the present invention, when the transparent substrate is made of glass, the thickness of the glass transparent substrate is 0.3 to 5mm, preferably 0.4 to 1 mm. When the transparent substrate is PET, PEN or PI material, the thickness of the PET, PEN or PI transparent substrate is 0.025-0.3 mm, preferably 0.05-0.2 mm. The function of the transparent substrate is to provide a base material for the transparent conductive film.
The conductive oxide in the first conductive layer and the third conductive layer is not particularly limited in the present invention, and may be, for example, each independently selected from fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), tungsten-doped indium oxide (IWO), aluminum-doped zinc oxide (AZO), zinc oxide, and tin dioxide (SnO)2) Any one of the above.
In one embodiment of the present invention, the second conductive layer is a conductive layer with a continuous line-shaped pattern or a conductive layer with a continuous grid-shaped pattern, and the conductive performance of the second conductive layer can be further improved by the continuous line-shaped pattern or the continuous grid-shaped pattern. Illustratively, the pattern may include, but is not limited to: a floral pattern, a regular hexagonal pattern, etc.
In one embodiment of the present invention, the line width of the continuous line pattern or the continuous grid pattern is 0.01 to 0.5mm, preferably 0.02 to 0.1 mm. Without being limited to any theory, when the line width is too narrow, the conductivity of the second conductive layer is not improved, and when the line width is too wide, the transmittance of the conductive film is affected. By controlling the line width of the continuous line-shaped pattern or the continuous grid-shaped pattern within the above range, the second conductive layer can have excellent conductive properties, and the transparent conductive film can also have excellent light transmittance.
Fig. 2 is a schematic structural diagram (top view) of a metal grid in the second conductive layer according to an embodiment of the present application, wherein the line width b of the metal grid is about 20 μm (i.e., 0.02 mm).
In one embodiment of the present invention, the area of the line-shaped conductive material in the second conductive layer accounts for 0.01% to 5% of the surface area of the plane of the transparent conductive film. Without being limited to any theory, when the area of the line-shaped conductive material in the second conductive layer occupies too small surface area of the transparent conductive film plane, the improvement of the conductive performance of the second conductive layer is affected; when the area of the line-shaped conductive material in the second conductive layer occupies too large surface area of the transparent conductive film plane, the light transmittance of the conductive film is affected.
In the invention, the ratio of the area of the linear conductive material in the second conductive layer to the surface area of the transparent conductive film plane may be calculated as follows:
and (3) taking a picture of the second conductive layer, and calculating the surface area S1 of the linear conductive material in the unit area S2, wherein the percentage a of the area of the linear conductive material in the second conductive layer in the surface area of the plane of the transparent conductive film is as follows: and a is S1/S2 multiplied by 100%.
In one embodiment of the invention, the transparent conductive film has a light transmittance of 85% to 90%, a haze of 0.9% to 1.2%, and a sheet resistance of 0.1 to 10 Ω/sq. Therefore, the transparent conductive film has the characteristics of high light transmittance, low haze and low sheet resistance, and has excellent performance.
The invention also provides a preparation method of the transparent conductive film, which comprises the following steps:
preparing a first conductive layer on the surface of a transparent substrate:
depositing a layer of conductive oxide on the surface of the transparent substrate, and then annealing to obtain a first conductive layer, wherein the annealing temperature is 120-170 ℃, and the annealing time is 20-40 min;
preparing a second conductive layer on the surface of the first conductive layer:
coating, depositing or printing a conductive material on the surface of the first conductive layer to form a second conductive layer containing a pattern;
preparing a third conductive layer on the surface of the second conductive layer:
and depositing a layer of conductive oxide on the surface of the second conductive layer to form a third conductive layer.
According to the invention, the first conducting layer containing the conducting oxide is prepared on the surface of the transparent substrate and is annealed, so that the annealed first conducting layer has lower sheet resistance. Because the second conducting layer is not formed on the surface of the first conducting layer before annealing, the cracking or warping of the first conducting layer caused by the material difference between the second conducting layer and the conducting oxide layer in the annealing process is avoided.
When the first conductive layer is annealed, the annealing temperature is 120-170 ℃, the annealing temperature is preferably 130-160 ℃, the annealing time is preferably 140-150 ℃, the annealing time is 20-40 min, the annealing time is preferably 25-35 min, and the annealing time is preferably 30-35 min, so that the conductive performance of the first conductive layer is improved.
After the second conductive layer is prepared, the third conductive layer containing the conductive oxide is prepared on the surface of the second conductive layer, and the first conductive layer has lower sheet resistance, so that the transparent conductive film can have lower sheet resistance without annealing the third conductive layer. The conductive layer containing a conductive oxide generally functions to improve the conductivity of the transparent conductive film. The inventor surprisingly finds that the third conducting layer which is slightly thinner is prepared on the surface of the second conducting layer, so that the whole conducting performance of the transparent conducting film is hardly influenced, the effect of preventing the conducting material in the second conducting layer from being oxidized can be achieved, and the stability of the transparent conducting film is improved.
The method for forming the first conductive layer and the third conductive layer is not particularly limited as long as the object of the present invention can be achieved, and for example, a magnetron sputtering method, a chemical vapor deposition method, a plasma chemical vapor deposition method (PECVD), a Reactive Plasma Deposition (RPD), or an atomic layer deposition method can be used.
In one embodiment of the present invention, the second conductive layer is prepared by:
coating the nano metal wire slurry on the surface of the first conductive layer through a slit coating die, and forming a second conductive layer after curing; wherein the curing temperature is 100-140 ℃, and preferably 110-120 ℃; the curing time is 8-15 min, preferably 10-12 min, and the concentration of the nano metal wire slurry is 5-10 mg/ml, preferably 7-8 mg/ml; the length of the nano metal wire is 10-25 μm, preferably 15-20 μm; the diameter is 20-35 nm, preferably 30-35 nm; the nano metal wire is selected from a nano silver wire or a nano gold wire.
In one embodiment of the present invention, the nano metal wires are distributed in the second conductive layer in an interlaced manner, and the pattern formed by the second conductive layer is in an interlaced and continuous grid shape. The nano silver wire and the nano gold wire have the advantages of excellent conductivity and low resistance, so that the second conductive layer has high conductivity.
The present invention is not particularly limited as long as the object of the present invention can be achieved. In one embodiment of the present invention, the method for preparing the nano metal wire slurry may be:
and mixing and dispersing the nano metal wire and absolute ethyl alcohol uniformly to obtain nano metal wire slurry with the concentration of 5-10 mg/ml.
In one embodiment of the present invention, the second conductive layer may be prepared by:
printing ink containing a conductive material on the surface of the first conductive layer, and drying to form a conductive material line; wherein, the solid content of the ink is 10 to 20 percent, and preferably 15 to 18 percent; the line width of the conductive material line is 10-100 μm.
In one embodiment of the present invention, the conductive material may be selected from one of aluminum powder, silver powder, copper powder, or graphene. In the second conductive layer, the conductive material forms a continuous line pattern.
In one embodiment of the present invention, the second conductive layer may be prepared by:
and sputtering a layer of metal film on the surface of the first conducting layer by a magnetron sputtering method, and then chemically etching to obtain a metal line.
In one embodiment of the present invention, the line width of the metal lines is 10 to 100 μm, preferably 30 to 70 μm, and more preferably 40 to 60 μm. The second conductive layer is formed such that the conductive material forms a continuous grid pattern.
Of course, the preparation process of the second conductive layer may further include: vacuum sputtering, thermal evaporation, electron beam evaporation, screen printing, dimple coating, extrusion coating, blade coating, or nanoimprinting, as long as the conductive layer containing a continuous line-like pattern or the second conductive layer containing a continuous grid-like pattern can be formed.
In the present invention, when the third conductive layer is formed by the RPD method, the RPD device has a similar principle to the magnetron sputtering device as long as the object of the present invention can be achieved, and the present invention is not particularly limited thereto.
According to the transparent conductive film and the preparation method thereof, the first conductive layer containing conductive oxide is prepared on the surface of the transparent substrate and annealed, so that the annealed first conductive layer has lower sheet resistance, and the second conductive layer is not formed on the surface of the first conductive layer before annealing, so that cracking or warping of the first conductive layer caused by material difference between the interface of the second conductive layer and the first conductive layer in the annealing process is avoided; and preparing a second conductive layer on the surface of the annealed first conductive layer, and then preparing a third conductive layer containing conductive oxide on the surface of the second conductive layer, wherein the first conductive layer has lower sheet resistance, so that the transparent conductive film can have lower sheet resistance without annealing the third conductive layer. In addition, the third conducting layer is covered on the surface of the second conducting layer, so that the effect of preventing the conducting material in the second conducting layer from being oxidized can be achieved, and the stability of the transparent conducting film is improved. In conclusion, the transparent conductive film prepared by the preparation method has low sheet resistance and high light transmittance, is less prone to cracking or warping, and has better performance.
Hereinafter, embodiments of the present invention will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on weight.
Test method：
Measurement of the total thickness of the transparent conductive film:
and testing the thickness of the transparent conductive film by using a step instrument or a scanning electron microscope.
Testing the light transmittance of the transparent conductive film:
and testing the light transmittance of the conductive film by using an ultraviolet-visible light spectrophotometer.
Haze test of transparent conductive film:
the haze of the transparent conductive film was measured using a haze meter.
Testing the sheet resistance of the transparent conductive film:
and testing the sheet resistance of the transparent conductive film by using a sheet resistance tester.
And (3) testing the cracking or warping condition of the conductive oxide layer:
for the transparent conductive films obtained in each of the examples and comparative examples, 10 sheets of the transparent conductive films were selected for each of which the conductive oxide layer was observed under an electron microscope to have cracks or warps.
The step meter, the scanning electron microscope, the ultraviolet-visible light spectrophotometer, the haze meter and the sheet resistance meter can all adopt testing equipment commonly used in the field, and the invention is not described herein again.
Examples
Example 1
< preparation of first conductive layer >
Preparing an ITO first conductive layer on the surface of a PEN transparent substrate with the thickness of 125 mu m by a vacuum magnetron sputtering method, and then annealing at the annealing temperature of 120 ℃ for 40 min. The thickness of the first conductive layer was 100 nm.
< preparation of second conductive layer >
And mixing and dispersing the nano silver wire and the absolute ethyl alcohol uniformly to obtain nano metal wire slurry with the concentration of 8 mg/ml. The length of the nano metal wire is 20 μm, and the diameter is 30 nm.
Coating the nano metal wire slurry on the surface of the first conductive layer through a slit coating die, and forming a second conductive layer after curing; wherein the curing temperature is 100 ℃ and the curing time is 15 min. The thickness of the second conductive layer is 80nm, namely the thickness of the nano silver wire layer, the line width of the nano silver wire is 20 μm, and the line spacing is 500 μm.
< preparation of third conductive layer >
And preparing an IWO coating on the surface of the second conductive layer by adopting Reactive Plasma Deposition (RPD) to form a third conductive layer. By controlling the RPD deposition time, a third conductive layer with a thickness of 50nm is obtained.
Example 2
Except that in < preparation of first conductive layer >, the annealing temperature of the first conductive layer was 140 ℃, the annealing time was 35min, and the thickness of the first conductive layer was 50 nm; in the preparation of the second conductive layer, the concentration of the nano metal wire slurry is 8mg/ml, the curing temperature is 110 ℃, the curing time is 12min, and the thickness of the second conductive layer is 120 nm; the third conductive layer was formed in the same manner as in example 1, except that the RPD deposition time was controlled so that the thickness of the third conductive layer was 40 nm.
Example 3
Except that in < preparation of first conductive layer >, the annealing temperature of the first conductive layer was 145 ℃, the annealing time was 32min, and the thickness of the first conductive layer was 70 nm; in the preparation of the second conductive layer, the concentration of the nano metal wire slurry is 8mg/ml, the curing temperature is 115 ℃, the curing time is 11min, and the thickness of the second conductive layer is 50 nm; the third conductive layer was formed in the same manner as in example 1, except that the RPD deposition time was controlled so that the thickness of the third conductive layer was 30 nm.
Example 4
Except that in < preparation of first conductive layer >, the annealing temperature of the first conductive layer was 150 ℃, the annealing time was 30min, and the thickness of the first conductive layer was 80 nm; in the preparation of the second conductive layer, the concentration of the nano metal wire slurry is 8mg/ml, the curing temperature is 120 ℃, the curing time is 10min, and the thickness of the second conductive layer is 100 nm; the third conductive layer was formed in the same manner as in example 1, except that the RPD deposition time was controlled so that the thickness of the third conductive layer was 20 nm.
Example 5
Except that in < preparation of first conductive layer >, the annealing temperature of the first conductive layer was 170 ℃, the annealing time was 20min, and the thickness of the first conductive layer was 25 nm; in the preparation of the second conductive layer, the concentration of the nano metal wire slurry is 8mg/ml, the curing temperature is 140 ℃, the curing time is 8min, and the thickness of the second conductive layer is 150 nm; the same procedure as in example 1 was repeated, except that the RPD deposition time was controlled so that the thickness of the third conductive layer was 5 nm.
Example 6
Except that in < preparation of first conductive layer >, the material of the first conductive layer is IWO; in < preparation of third conductive layer >, the material of the third conductive layer was ITO, and the rest was the same as example 4.
Example 7
Except that in < preparation of first conductive layer >, the material of the first conductive layer is AZO; in < preparation of third conductive layer >, the material of the third conductive layer was AZO, and the same was used as in example 4.
Example 8
The same procedure as in example 4 was repeated, except that in < preparation of first conductive layer >, PET was used as the transparent base material.
Example 9
The same as example 4 was repeated, except that in < preparation of first conductive layer >, glass was used for the transparent substrate, and the thickness of the transparent substrate was 200 μm.
Example 10
The same as in example 4 was performed except that < preparation of second conductive layer > was different.
< preparation of second conductive layer >
And performing vacuum sputtering on the surface of the first conducting layer to obtain a Cu surface layer with the thickness of 100nm, and performing chemical etching to obtain metal lines to form a linear grid structure. The line width of the metal lines is 20 μm, and the line spacing is 500 μm.
Example 11
The same as in example 4 was performed except that < preparation of second conductive layer > was different.
< preparation of second conductive layer >
The silver paste ink was printed onto the surface of the first conductive layer by means of an inkjet printing apparatus using a commercially available finished silver paste ink (herriella Heraeus, germany, model SOL590) to form a second conductive layer having a line-like grid structure with a thickness of 100 nm. Wherein the line width of the lines is 10 μm, and the line spacing is 500 μm.
Comparative example 1
A Cu surface layer with the thickness of 100nm is obtained on the surface of a PEN transparent substrate with the thickness of 125 mu m through a vacuum magnetron sputtering method, and a metal line is obtained after chemical etching, so that a conductive metal layer with the thickness of 100nm is formed. The line width of the metal lines is 20 μm, and the line spacing is 500 μm.
Preparing an ITO conductive oxide layer on the conductive metal layer by a vacuum magnetron sputtering method, and then annealing at the annealing temperature of 150 ℃ for 30 min. The thickness of the ITO conductive oxide layer was 200 nm.
Comparative example 2
And mixing and dispersing the nano silver wire and the absolute ethyl alcohol uniformly to obtain nano metal wire slurry with the concentration of 8 mg/ml. The length of the nano metal wire is 20 μm, and the diameter is 30 nm.
And coating the nano metal wire slurry on the surface of a 125-micron PEN transparent base material through a slit coating die, and curing to form a conductive metal layer, wherein the curing temperature is 120 ℃ and the curing time is 10 min. The thickness of the conductive metal layer was 100 nm.
And coating the PH1000 slurry on the surface of the conductive metal layer through a slit coating die to form a conductive oxide layer. Wherein the curing temperature is 120 ℃, and the curing time is 10 min. The thickness of the conductive oxide layer was 100 nm. The pH1000 slurry is commercially available (Heraeus, Germany).
Comparative example 3
The same as in comparative example 1 was used except that 0.2mm of glass was used as the transparent substrate.
The preparation and performance parameters for the examples are shown in Table 1 and the preparation and performance parameters for the comparative examples are shown in Table 2.
As can be seen from examples 1 to 8, 10 to 11 and comparative examples 1 to 2, the transparent conductive film has higher light transmittance, lower haze and lower sheet resistance, and has better performance.
As can be seen from examples 1 to 11 and comparative examples 1 and 3, the transparent conductive film of the present invention can effectively prevent the conductive oxide layer from cracking or warping during annealing.
It can be seen from example 9 and comparative example 3 that, when the transparent substrate material is glass, the transparent conductive film of the present invention has higher light transmittance, lower haze and lower sheet resistance, and has better performance.
As can be seen from example 10 and comparative example 1, the transparent conductive thin film of the present invention has a lower thickness and better performance when the conductive oxide layer is subjected to a vacuum sputtering process.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A transparent conductive film sequentially comprises a transparent substrate, a first conductive layer, a second conductive layer and a third conductive layer from bottom to top, wherein the first conductive layer and the third conductive layer respectively and independently contain conductive oxides, the second conductive layer contains metal or carbon materials, the thickness of the first conductive layer is 25-100 nm, the thickness of the second conductive layer is 50-150 nm, and the thickness of the third conductive layer is 5-50 nm.
2. The transparent conductive film according to claim 1, wherein the conductive oxide in the first conductive layer and the third conductive layer is each independently selected from any one of FTO, ITO, IWO, AZO, zinc oxide, and tin dioxide.
3. The transparent conductive film according to claim 1, wherein the metal is selected from any one of aluminum, silver, copper, nanogold, or nanosilver, and the carbon material is selected from graphene.
4. The transparent conductive film according to claim 1, wherein the transparent substrate is selected from any one of glass, PET, PEN and PI, and the thickness of the glass transparent substrate is 0.3-5 mm; the thickness of the PET, PEN or PI transparent base material is 0.025-0.3 mm.
5. The transparent conductive film according to claim 1, wherein the second conductive layer is a conductive layer containing a continuous line-like pattern or a conductive layer containing a continuous grid-like pattern.
6. The transparent conductive film according to claim 5, wherein the area of the conductive material in the form of a line in the second conductive layer is 0.01 to 5% of the surface area of the plane of the transparent conductive film.
7. The transparent conductive film according to claim 1, wherein the transparent conductive film has a light transmittance of 85 to 90%, a haze of 0.9 to 1.2%, and a sheet resistance of 0.1 to 10 Ω/sq.
8. A method for producing the transparent conductive film according to any one of claims 1 to 7, comprising:
preparing a first conductive layer on the surface of a transparent substrate:
depositing a layer of conductive oxide on the surface of the transparent substrate, and then annealing to obtain the first conductive layer, wherein the annealing temperature is 120-170 ℃, and the annealing time is 20-40 min;
preparing a second conductive layer on the surface of the first conductive layer:
coating, depositing or printing a conductive material on the surface of the first conductive layer to form the second conductive layer containing a pattern;
preparing a third conductive layer on the surface of the second conductive layer:
and depositing a layer of conductive oxide on the surface of the second conductive layer to form the third conductive layer.
9. The method for producing a transparent conductive film according to claim 8, wherein the method for forming the first conductive layer and the third conductive layer comprises: magnetron sputtering, chemical vapor deposition, plasma chemical vapor deposition, reactive plasma deposition or atomic layer deposition.
10. The method of manufacturing a transparent conductive film according to claim 8, wherein the second conductive layer is manufactured by:
coating the nano metal wire slurry on the surface of the first conductive layer through a slit coating die, and forming a second conductive layer after curing; wherein the curing temperature is 100-140 ℃, the curing time is 8-15 min, the concentration of the nano metal wire slurry is 5-10 mg/ml, the length of the nano metal wire is 10-25 mu m, the diameter is 20-40 nm, and the nano metal wire is selected from a nano silver wire or a nano gold wire;
or printing ink containing a conductive material on the surface of the first conductive layer, and drying to form a conductive material line; wherein the solid content of the ink is 10% -20%, and the line width of the conductive material line is 1-100 μm;
or sputtering a layer of metal film on the surface of the first conducting layer by a magnetron sputtering method, and then chemically etching to obtain a metal line; wherein the line width of the metal lines is 10-100 μm.
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Denomination of invention: A transparent conductive thin film and its preparation method Granted publication date: 20220805 Pledgee: Bank of China Limited Zhenjiang Runzhou Branch Pledgor: Dazheng (Jiangsu) micro nano technology Co.,Ltd. Registration number: Y2024980006540 |