CN111916252A - Transparent conductive film with low sheet resistance - Google Patents
Transparent conductive film with low sheet resistance Download PDFInfo
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- CN111916252A CN111916252A CN202010880261.2A CN202010880261A CN111916252A CN 111916252 A CN111916252 A CN 111916252A CN 202010880261 A CN202010880261 A CN 202010880261A CN 111916252 A CN111916252 A CN 111916252A
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Abstract
The invention discloses a transparent conductive film with low sheet resistance, which comprises a transparent base material, a refractive index matching layer, a transition layer, a metal alloy layer, a first transparent conductive layer, a medium barrier layer and a second 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 added 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 and reduce the island-shaped discontinuous phenomenon of thin-layer metal, and after the water oxygen barrier layer at the base material side is combined with the refractive index matching layer together, the metal alloy layer is effectively prevented from being degraded in the using process, the integral reliability and weather resistance are greatly improved, the medium barrier layer and the inner transparent conductive layer are added at the air side of the metal alloy layer, and the water oxygen is effectively isolated from the metal through the outermost transparent conductive layer at the air side in the processing and transportation processes Water-oxygen attack of the alloy layer.
Description
Technical Field
The invention relates to the field of conductive films, in particular to a transparent conductive film with low sheet resistance.
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 electrical properties of ITO-metal-ITO multilayers (relationship of the photoelectric properties of ITO-metal-ITO multilayer films to the film thickness and composition)" 67-71 in Thin solid films, 326(1998) in which ITO/AG/ITO (I/M/I) multilayer films replace 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. 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 transparent conductive film with low sheet resistance and 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 provides a transparent conductive film with low sheet resistance, which comprises a transparent substrate, a refractive index matching layer, a transition layer, a metal alloy layer, a first transparent conductive layer, a medium barrier layer and a second 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 at least one of magnesium oxide, gallium oxide and aluminum oxide with zinc oxide, the thickness is 3-15 nm,
the dielectric barrier layer is a zinc oxide layer, a silicon dioxide layer, an aluminum oxide layer or a silicon nitride layer, or a zinc oxide mixed layer formed by mixing one of magnesium oxide, gallium oxide and aluminum oxide with zinc oxide, or a silicon dioxide mixed layer formed by mixing one of silicon nitride and aluminum oxide with silicon dioxide.
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 dielectric barrier layer is a silicon dioxide layer having a thickness of 10 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 some embodiments, the metal alloy layer is a silver alloy layer or a copper alloy layer, the remaining alloy component in the silver alloy layer is at least one of palladium, gold, copper, platinum and rhodium, and the proportion of silver is greater than 95%; the rest alloy components in the copper alloy layer 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 first transparent conductive layer is a tin oxide layer, or a zinc oxide layer, or an indium tin oxide layer, or a zinc oxide mixed layer of zinc oxide mixed with one of magnesium oxide, gallium oxide and aluminum oxide, and the thickness is 5nm to 40 nm.
In some embodiments, the second transparent conductive layer is a tin oxide layer or an indium tin oxide layer with a thickness of 20 to 80 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:
(1) 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.
(2) Meanwhile, the invention adds a medium barrier layer with compact molecular structure and a transparent conducting layer at the inner side at the air side of the metal alloy layer, thereby effectively isolating the water-oxygen erosion of the metal alloy layer by water-oxygen passing through the transparent conducting layer at the outermost side of the air side in the processing and transportation processes, and greatly improving the ring detection resistance.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Example (b): the laminated structure of the transparent conductive film with low sheet resistance is shown in fig. 1, and the transparent conductive film has a transparent substrate 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a dielectric barrier layer 15 and a second transparent conductive layer 16 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 transparent conductive film with low sheet resistance comprises a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a dielectric barrier layer 15 and a second transparent conductive layer 16 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%, and the sheet resistance is 16 omega), indium tin oxide (indium tin ratio is 90:10), silicon dioxide and indium tin oxide (indium tin ratio is 90:10), and the thicknesses of the layers are respectively 0.125 mu m, 35nm, 6nm, 6.5nm, 20nm, 10nm and 20 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 this embodiment, the flexible transparent substrate is deposited by a magnetron sputtering process sequentially using a niobium pentoxide target, a zinc magnesium oxide target, a silver-palladium-copper alloy target, an indium tin oxide target, a silicon dioxide 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 |
| 16 | 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 transparent conductive film with low sheet resistance is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a medium barrier layer 15 and a second transparent conductive layer 16 which are stacked from bottom to top, wherein the materials of the layers are respectively PC, zinc sulfide, zinc gallium oxide, copper alloy (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), zinc oxide, zinc magnesium oxide and tin oxide, and the thicknesses of the layers are respectively 0.100 mu m, 40nm, 7nm, 5.5nm, 16nm, 10nm and 22 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 |
| 18 | 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 4
TABLE 4
Example 3
A transparent conductive film with low sheet resistance is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a medium blocking layer 15 and a second transparent conductive layer 16 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%, the sheet resistance is 13 omega), tin oxide, aluminum oxide 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, 18nm, 10nm and 25nm respectively.
Tables 5 and 6 show the results of the tests on the product of example 3
TABLE 5
| Square resistance omega | VLT(％) | |
| 13 | 83.5 | 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 transparent conductive film with low sheet resistance is composed of a transparent substrate 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a dielectric barrier layer 15 and a second transparent conductive layer 16 which are stacked from bottom to top, wherein the materials of the layers are COP, zinc oxide, zinc aluminum oxide, zinc gallium 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 18 omega), zinc magnesium oxide, zinc aluminum oxide and tin oxide, and the thicknesses of the layers are respectively 0.120 mu m, 40nm, 5nm, 6nm, 18nm, 10nm and 30 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 |
| 18 | 83 | 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 transparent conductive film with low sheet resistance is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a medium blocking layer 15 and a second transparent conductive layer 16 which are stacked from bottom to top, wherein the materials of the layers are respectively glass, zinc oxide, zinc aluminum oxide, silver alloy (the rest alloy in the copper alloy is gold and platinum, the proportion of copper is more than 95%, the sheet resistance is 13 omega), tin oxide, silicon nitride 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, 35nm, 10nm and 25 m.
Tables 9 and 10 show the results of the tests on the product of example 5
TABLE 9
| Square resistance omega | VLT(％) | |
| 13 | 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 10
Example 6
A transparent conductive film with low sheet resistance is composed of a transparent base material 10, a refractive index matching layer 11, a transition layer 12, a metal alloy layer 13, a first transparent conductive layer 14, a medium blocking layer 15 and a second transparent conductive layer 16 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 95 percent, and the sheet resistance is 10 omega), zinc aluminum oxide, silicon dioxide 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, 25nm, 10nm and 32 m.
Tables 11 and 12 show the results of the tests on the product of example 6
TABLE 11
| Square resistance omega | VLT(％) | |
| 10 | 79 | 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
The invention can adopt a roll-to-roll magnetron sputtering deposition method to prepare the layers on the flexible transparent substrate in sequence. The roll-to-roll magnetron sputtering deposition method is adopted to sputter various materials, has high vacuum degree, strong adhesive force and compact film material, and can be used for coating films on flexible substrates.
Of course, the transparent conductive film with low sheet resistance provided by the present invention may also be performed by other process methods, 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.
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 (10)
1. A transparent conductive film with low sheet resistance is characterized in that: comprises a transparent substrate, a refractive index matching layer, a transition layer, a metal alloy layer, a first transparent conductive layer, a medium barrier layer and a second 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, the thickness of the zinc oxide mixed layer is 3-15 nm,
the dielectric barrier layer is a zinc oxide layer, a silicon dioxide layer, an aluminum oxide layer or a silicon nitride layer, or a zinc oxide mixed layer formed by mixing one of magnesium oxide, gallium oxide and aluminum oxide with zinc oxide, or a silicon dioxide mixed layer formed by mixing one of silicon nitride and aluminum oxide with silicon dioxide.
2. The transparent conductive film with low sheet resistance according to 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 with low sheet resistance according to claim 1, wherein: the transition layer is a zinc magnesium oxide layer and is 6nm thick.
4. The transparent conductive film with low sheet resistance according to claim 1, wherein: the dielectric barrier layer is a silicon dioxide layer and is 10nm thick.
5. The transparent conductive film with low sheet resistance according to 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.
6. The transparent conductive film with low sheet resistance according to claim 5, wherein: the transparent substrate layer is made of PET and has a thickness of 0.125 μm.
7. The transparent conductive film with low sheet resistance according to 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 layer are at least one of palladium, gold, copper, platinum and rhodium, and the proportion of silver is more than 95%; the rest alloy components in the copper alloy layer 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.
8. The transparent conductive film with low sheet resistance according to claim 7, 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.
9. The transparent conductive film with low sheet resistance according to claim 1, wherein: the first transparent conducting layer is a tin oxide layer, or a zinc oxide layer, or an indium tin oxide layer, or a zinc oxide mixed layer formed by mixing zinc oxide with one of magnesium oxide, gallium oxide and aluminum oxide, and the thickness of the first transparent conducting layer is 5nm-40 nm.
10. The transparent conductive film with low sheet resistance according to claim 1, wherein: the second transparent conducting layer is a tin oxide layer or an indium tin oxide layer, and the thickness of the second transparent conducting layer is 20-80 nm.
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| WO2023114434A1 (en) * | 2021-12-17 | 2023-06-22 | Adam Trexler | Precious metal laminate and methods of manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023114434A1 (en) * | 2021-12-17 | 2023-06-22 | Adam Trexler | Precious metal laminate and methods of manufacture |
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