CN111883287A - Low-sheet-resistance transparent conductive film - Google Patents
Low-sheet-resistance transparent conductive film Download PDFInfo
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- CN111883287A CN111883287A CN202010880225.6A CN202010880225A CN111883287A CN 111883287 A CN111883287 A CN 111883287A CN 202010880225 A CN202010880225 A CN 202010880225A CN 111883287 A CN111883287 A CN 111883287A
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention discloses a low-sheet resistance transparent conductive film, which comprises a transparent base material, a refractive index matching layer, a transition layer, a metal alloy layer and a transparent conductive layer which are stacked from bottom to top, wherein a water-oxygen barrier layer at the base material side, which is formed by combining the refractive index matching layer and the transition layer together, is additionally arranged between the transparent base material and the metal alloy layer, the transition layer aims to provide a compact continuous conductive layer substrate for the upper metal alloy layer, the island-shaped discontinuous phenomenon of thin-layer metal is reduced, and after the water-oxygen barrier layer at the base material side is combined together with the refractive index matching layer made of a high-refractive-index material, the metal alloy layer is effectively prevented from being degraded in the using process, so that the reliability and the weather resistance of the whole conductive film are greatly improved.
Description
Technical Field
The invention relates to the field of conductive films, in particular to a low-sheet-resistance transparent conductive film.
Background
In recent years, with the rapid development of semiconductor manufacturing technology and photovoltaic technology, technologies such as flat panel displays, touch panels, window films, polymer dispersed liquid crystals, solar cells, and the like have been rapidly developed and perfected, and these new technologies all require the use of a transparent conductive film as an electrode, a light receiving surface, or an electromagnetic pulse shielding film. Taking a touch screen as an example, several types commonly used in touch screens, such as a resistive touch screen, a surface capacitive touch screen, and an inductive capacitive touch screen, all need to use a transparent conductive film as an electrode material.
Transparent conductive films are generally recognized as being transparent in the visible range and have a relatively low resistivity. Currently, ITO (a mixture of tin oxide and indium oxide), AZO (aluminum-doped zinc oxide), aluminum oxide, and the like are commonly used as transparent conductive films.
It was found from the literature search that M.Bender and W.Seelig et al in 1998 written "Dependence of film composition and thickness on optical and chemical properties of ITO-metal-ITO multilayers" (relationship between the photoelectric properties of ITO-metal-ITO multilayer films and their film thicknesses and compositions) "67-71 in Thin solid films, 326(1998) in which the ITO/AG/ITO (I/M/I) multilayer film replaces a single ITO film, in an attempt to obtain better conductivity and lower cost. However, the photoelectric properties of such a sandwich structure do not meet the expectations of people. One topic group of shanghai transportation later proposed a dielectric layer/metal layer/dielectric layer sandwich structure with good conductivity and low resistance. However, the film with the structure still has a thicker thickness, is easy to fall off on a flexible base material PET, has poor adhesion, is exposed in air, has unstable tissue, poor oxidation resistance and poor weather resistance test for 500h, and has poor data.
For example, taking the conductive film having a sheet resistance of about 15 ohms manufactured by ITO which is currently developed in the industry as an example, the thickness of ITO is about 130nm or more, and the flexibility is deteriorated due to the thickness, so that the flexible substrate cannot be used basically.
For example, taking the conductive film having a sheet resistance of about 15 ohms manufactured by ITO which is currently developed in the industry as an example, the thickness of ITO is about 130nm or more, and the flexibility is deteriorated due to the thickness, so that the flexible substrate cannot be used basically. The silver laminated conductive film successfully solves the problem and has a reduction in cost. The disadvantage is that the silver laminated conductive film is slightly inferior to ITO in weather resistance and transmittance.
Disclosure of Invention
The invention aims to: the low-sheet resistance transparent conductive film with better weather resistance and transmittance is provided to make up for the defects of the prior art.
The technical scheme of the invention is realized as follows:
the invention discloses a low-sheet resistance transparent conductive film, which comprises a transparent base material, a refractive index matching layer, a transition layer, a metal alloy layer and a transparent conductive layer which are stacked from bottom to top,
wherein the refractive index matching layer is a zinc sulfide layer, a niobium pentoxide layer, a titanium dioxide layer, a zinc oxide layer or a zinc oxide mixed layer, the thickness is 15-50 nm,
the transition layer is a zinc oxide mixed layer formed by mixing zinc oxide with at least one of magnesium oxide, gallium oxide and aluminum oxide, and the thickness of the transition layer is 3-15 nm.
In certain embodiments, the index matching layer is a niobium pentoxide layer having a thickness of 35 nm.
In certain embodiments, the transition layer is a zinc magnesium oxide layer, a zinc gallium oxide layer, or a zinc aluminum oxide layer.
In certain embodiments, the transition layer is a zinc magnesium oxide layer having a thickness of 6 nm.
In some embodiments, the transparent substrate layer is made of one of PI, PET, PC, COP and glass, has a thickness of 0.005 to 1 μm, and has upper and lower surfaces hardened when the material is PET or PC.
In certain embodiments, the material of the transparent substrate layer is PET and has a thickness of 0.125 μm.
In certain embodiments, the metal alloy layer is a silver alloy layer or a copper alloy layer, and the remaining alloy component in the silver alloy is at least one of palladium, gold, copper, platinum, rhodium, the proportion of silver being greater than 95%; the other alloy components in the copper alloy are at least one of palladium, gold, silver, platinum and rhodium, and the proportion of copper is more than 95 percent; the thickness of the metal alloy layer is 4-20 nm, and the sheet resistance is 5-30 omega.
In certain embodiments, the remaining alloy in the silver alloy layer is palladium and copper, the silver alloy layer has a thickness of 6.5nm and a sheet resistance of 16 Ω.
In some embodiments, the transparent conductive layer is a tin oxide layer or an indium tin oxide layer with a thickness of 20 to 80 nm.
In some embodiments, the transparent conductive layer is an indium tin oxide layer having a thickness of 52 nm.
In certain embodiments, the transition layer has a proportion of zinc oxide in the mixed material of greater than 80%.
The invention has the advantages that:
the invention provides a low sheet resistance transparent conductive film, wherein a substrate-side water oxygen barrier layer formed by combining a refractive index matching layer and a transition layer is additionally arranged between a transparent substrate and a metal alloy layer, the transition layer aims to provide a compact continuous conductive layer substrate for the upper metal alloy layer and reduce island-shaped discontinuity of thin-layer metal, and after the transition layer and the refractive index matching layer made of high-refractive-index materials are combined into the substrate-side water oxygen barrier layer, the metal alloy layer is effectively prevented from being degraded in the using process, so that the reliability and the weather resistance of the whole conductive film are greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Example (b): the laminated structure of the low sheet resistance transparent conductive film is shown in fig. 1, and the transparent conductive film comprises a transparent substrate 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are laminated from bottom to top, and various different embodiments can be formed by selecting different materials, composition contents or thicknesses of the layers. We now describe our products and their properties by way of six examples:
example 1
A low-sheet-resistance transparent conductive film is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of the layers are respectively PET, niobium pentoxide, zinc magnesium oxide, silver alloy (the rest alloy in the silver alloy is palladium and copper, the proportion of silver is more than 95%, the sheet resistance is 16 omega) and indium tin oxide (the indium tin ratio is 90:10), and the thicknesses of the layers are respectively 0.125 mu m, 35nm, 6nm, 6.5nm and 52 nm. The transparent conductive film has better properties (including weather resistance, transparency, adhesion, etc.).
The manufacturing process can adopt a conventional roll-to-roll magnetron sputtering deposition method, and the roll-to-roll magnetron sputtering deposition method has the advantages of sputtering various materials, high vacuum degree, strong adhesive force, compact film material and capability of coating on a flexible substrate.
As in the present embodiment, the material is deposited on the flexible transparent substrate by a magnetron sputtering process sequentially through a niobium pentoxide target, a zinc magnesium oxide target, a silver-palladium-copper alloy target, and an indium tin oxide target.
When the material is PET or PC, the upper and lower surfaces are hardened by applying a coating process, such as HC hardening, which is a conventional technique and will not be described herein.
Of course, the transparent conductive film may also be formed by other processes, such as chemical vapor deposition or physical vapor deposition, and the process and process parameters thereof may refer to the prior art and are not described herein again.
Tables 1 and 2 show the results of the tests on the product of example 1
TABLE 1
| Square resistance omega | VLT(％) | Adhesion force |
| 16Ω | 85％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 2
TABLE 2
Example 2
A low-sheet-resistance transparent conductive film is composed of a transparent base 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of each layer are respectively PC, zinc sulfide, zinc gallium oxide, copper alloy (wherein the rest alloy in the copper alloy is palladium and gold, the proportion of copper is more than 95%, the sheet resistance is 18 omega) and tin oxide, and the thicknesses of each layer are respectively 0.100 mu m, 40nm, 7nm, 5.5nm and 55 nm.
Tables 3 and 4 show the results of the tests on the product of example 2
TABLE 3
| Square resistance omega | VLT(％) | Adhesion force |
| 18Ω | 84％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 4
TABLE 4
Example 3
A low-sheet-resistance transparent conductive film is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of the layers are PI, titanium dioxide, zinc aluminum oxide, silver alloy (the rest alloy in the silver alloy is platinum and rhodium, the proportion of silver is more than 95 percent, the sheet resistance is 12 omega) and indium tin oxide (the indium tin ratio is 90:10), and the thicknesses of the layers are 0.150 mu m, 30nm, 5nm, 7nm and 60nm respectively.
Tables 5 and 6 show the results of the tests on the product of example 3
TABLE 5
| Square resistance omega | VLT(％) | Adhesion force |
| 16.6Ω | 82％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 6
TABLE 6
Example 4
A low sheet resistance transparent conductive film is composed of a transparent substrate 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of each layer are respectively COP, zinc oxide, zinc aluminum oxide, copper alloy (wherein the rest alloy in the copper alloy is palladium and platinum, the proportion of copper is more than 95%, the sheet resistance is 17 omega) and tin oxide, and the thicknesses of each layer are respectively 0.120 mu m, 40nm, 5nm, 6nm and 45 nm.
Tables 7 and 8 show the results of the tests on the product of example 4
TABLE 7
| Square resistance omega | VLT(％) | Adhesion force |
| 17Ω | 81％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 8
TABLE 8
Example 5
A low-sheet-resistance transparent conductive film is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of the layers are respectively glass, zinc oxide, zinc magnesium oxide, silver alloy (the rest alloy in the copper alloy is gold and platinum, the proportion of copper is more than 95 percent, the sheet resistance is 12 omega) and indium tin oxide (the indium tin ratio is 90:10), and the thicknesses of the layers are respectively 0.085 mu m, 45nm, 10nm, 7nm and 60 nm.
Tables 9 and 10 show the results of the tests on the product of example 5
TABLE 9
| Square resistance omega | VLT(％) | Adhesion force |
| 12Ω | 81％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 10
Example 6
A low-sheet-resistance transparent conductive film is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13 and a transparent conductive layer 14 which are stacked from bottom to top, wherein the materials of the layers are respectively PET, titanium dioxide, zinc gallium oxide, copper alloy (the rest alloy in the copper alloy is gold and rhodium, the proportion of copper is more than 95 percent, the sheet resistance is 10 omega) and indium tin oxide (the indium tin ratio is 90:10), and the thicknesses of the layers are respectively 0.135 mu m, 30nm, 9nm, 11nm and 54 nm.
Tables 11 and 12 show the results of the tests on the product of example 6
TABLE 11
| Square resistance omega | VLT(％) | Adhesion force |
| 10Ω | 82％ | 5B |
Weather resistance test conditions: high temperature and humidity 85 deg.C, 85% RH, high temperature storage 80 deg.C, low temperature storage-40 deg.C, cold and heat shock-40 deg.C (60min) to 80 deg.C (60min),20cycles, the results are shown in Table 12
TABLE 12
It should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.
Claims (9)
1. A low sheet resistance transparent conductive film is characterized in that: comprises a transparent substrate, a refractive index matching layer, a transition layer, a metal alloy layer and a transparent conducting layer which are stacked from bottom to top,
wherein the refractive index matching layer is a zinc sulfide layer, a niobium pentoxide layer, a titanium dioxide layer, a zinc oxide layer or a zinc oxide mixed layer, the thickness is 15-50 nm,
the transition layer is a zinc oxide mixed layer formed by mixing zinc oxide with at least one of magnesium oxide, gallium oxide and aluminum oxide, and the thickness of the transition layer is 3-15 nm.
2. The transparent conductive film of claim 1, wherein: the refractive index matching layer is a niobium pentoxide layer and has a thickness of 35 nm.
3. The transparent conductive film of claim 1, wherein: the transition layer is a zinc magnesium oxide layer and is 6nm thick.
4. The transparent conductive film of claim 1, wherein: the transparent substrate layer is made of one of PI, PET, PC, COP and glass, the thickness of the transparent substrate layer is 0.005-1 mu m, and when the transparent substrate layer is made of PET or PC, the upper surface and the lower surface of the transparent substrate layer are hardened.
5. The transparent conductive film with low sheet resistance according to claim 4, wherein: the transparent substrate layer is made of PET and has a thickness of 0.125 μm.
6. The transparent conductive film of claim 1, wherein: the metal alloy layer is a silver alloy layer or a copper alloy layer, the rest alloy components in the silver alloy are at least one of palladium, gold, copper, platinum and rhodium, and the proportion of silver is more than 95%; the other alloy components in the copper alloy are at least one of palladium, gold, silver, platinum and rhodium, and the proportion of copper is more than 95 percent; the thickness of the metal alloy layer is 4-20 nm, and the sheet resistance is 5-30 omega.
7. The transparent conductive film with low sheet resistance according to claim 6, wherein: the rest alloy in the silver alloy layer is palladium and copper, the thickness of the silver alloy layer is 6.5nm, and the sheet resistance is 16 omega.
8. The transparent conductive film of claim 1, wherein: the transparent conducting layer is a tin oxide layer or an indium tin oxide layer, and the thickness of the transparent conducting layer is 20-80 nm.
9. The transparent conductive film of claim 8, wherein: the transparent conducting layer is an indium tin oxide layer, and the thickness is 52 nm.
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