CN206711623U - A kind of flexible composite transparent conductive film - Google Patents

A kind of flexible composite transparent conductive film Download PDF

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Publication number
CN206711623U
CN206711623U CN201720087128.5U CN201720087128U CN206711623U CN 206711623 U CN206711623 U CN 206711623U CN 201720087128 U CN201720087128 U CN 201720087128U CN 206711623 U CN206711623 U CN 206711623U
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Prior art keywords
film
transparent conductive
conductive film
metal
thickness
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杨钊
张晓东
常远程
雷国伟
田占元
邓增社
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Abstract

The utility model provides a kind of flexible composite transparent conductive film and preparation method thereof, including substrate and the metal oxide film being sequentially placed on substrate, interlayer film, and metal nanowire film, wherein, interlayer film is the film that bending resistance and electric conductivity are all higher than ITO.The utility model adds the metal level to electric conductivity with outstanding contributions, effectively reduces the square resistance of transparent conductive film, and metal level also has bending resistance more more preferable than ITO layer.Meanwhile the nano silver wire film of top layer plays a part of bending protective layer, the metal oxide more superior compared to current photoelectric comprehensive performance/metal/metal oxide composite construction transparent conductive film, the utility model has more preferable bending resistance.

Description

A kind of flexible composite transparent conductive film
【Technical field】
It the utility model is related to a kind of transparent conductive film, more particularly to a kind of metal oxide/metal/metal nano wire The MULTILAYER COMPOSITE flexible transparent conductive film of structure.
【Background technology】
Transparent conductive oxide film headed by tin indium oxide (ITO) is widely used in electronics, information, the energy, built The field such as build, transparent conductive film has almost monopolized flat board within suitable long-term with its excellent comprehensive photoelectric properties and shown Show, the electronic product transparency electrode market such as touch-screen.Indium is a kind of scarce resource, is increased with the production capacity of global FPD industry Long, the continuous innovation of all kinds of photoelectric devices, more harsh to transparency electrode performance requirement in addition, also more diversification, finds ITO Transparent conductive film substitute is imperative.In recent years, flexible display technologies went to material object from concept, and part shows industry tap Enterprise has stepped into the volume production preparatory stage, and flexible transparent conductive film industry will welcome industry spring.
Preparing flexible transparent conductive film needs to prepare in flexible substrate (such as PET, PEN, PI etc.), because these are flexible Substrate high temperature resistant is limited, and the preparation of transparent conductive film need to be carried out under normal temperature or relatively low heating-up temperature.Tied because under low temperature Crystalline state is incomplete, and the ito thin film sheet resistance deposited on flexible substrates is higher, and transmitance is also poor, goes out to solve this problem The transparent conductive film of the composite constructions such as metal oxide/metal/metal oxide is showed, the addition of metal level substantially improves The electric conductivity of flexible transparent conductive film.But the either single metal oxide transparent conductive film or gold of flexible substrate Belonging to the composite construction transparent conductive film of oxide composition, resistivity all can be significantly raised after bending repeatedly, and not being suitable for can be with The flexible display device flexibly deformed, the bending resistance for solving flexible substrate transparent conductive film have highly important practicality Meaning.
【Utility model content】
The utility model aims to solve the problem that single metal oxide and MULTILAYER COMPOSITE flexible transparent conductive film repeatedly after bending The problem of resistivity is significantly raised, there is provided a kind of flexible composite transparent conductive film, make transparent conductive film that there is lower side Resistance, and change in resistance is smaller after multiple bending.
A kind of flexible composite transparent conductive film, the structure of the film are:Flexible substrate/metal-oxide film/metal Film/metal nanowire thin-films.
The material of the metallic film is silver, gold, or electrum.
The thickness of metallic film is 5nm~25nm.
The metal-oxide film is ito thin film, AZO films, IZO films or IGZO films, thickness between 20nm~ Between 100nm.
The metal nanowire thin-films are silver nanowire film, and thickness is 2~5 times of metal nano line length.
A diameter of 30nm~180nm of described metal nanometer line, length are 30nm~200 μm.
Described metal-oxide film, metallic film film, and the thickness of metal nanowire thin-films ensure flexible compound For average transmittance of the transparent conductive film in visible-range 400nm~700nm up to more than 82%, average square resistance is small In 7.5 Ω/.
The flexible substrate is one kind in PET, PEN, PI.
Compared with individual layer transparent conductive film, individual layer nano silver wire transparent conductive film in existing flexible substrate, this reality With the new metal level for adding and there are outstanding contributions to electric conductivity, the square resistance of transparent conductive film is effectively reduced, Metal level also has bending resistance more more preferable than ITO layer.Meanwhile the nano silver wire film of top layer plays the work of bending protective layer With the metal oxide more superior compared to current photoelectric comprehensive performance/metal/metal oxide composite construction electrically conducting transparent Film, the utility model have more preferable bending resistance.
【Brief description of the drawings】
Fig. 1 is film layer structure schematic diagram of the present utility model;
Reference:1- flexible transparent substrates, 2- metal oxide layers, 3- metal levels, 4- metal nanometer line layers;
Fig. 2 is ITO/Ag/AgNW MULTILAYER COMPOSITEs transparent conductive film in 380nm~780nm range of wavelengths transmittance curves Figure;
Fig. 3 is that ITO/Ag/AgNW MULTILAYER COMPOSITEs transparent conductive film film rectangular resistance under different bending numbers changes Situation.
【Embodiment】
Below in conjunction with the accompanying drawings 1 and specific embodiment to this programme further illustrate:
Refer to shown in Fig. 1, the utility model provides a kind of transparent conductive oxide film of multi-layer compound structure, bag Flexible substrate 1 is included, being sputtered successively from bottom to top in flexible substrate 1 has metal oxide ito thin film 2, metal Ag films 3, Metal Ag films 3, which are used above coating method and prepared, nano silver wire film 4.
The material of the flexible substrate 1 includes polyethylene terephthalate (PET), PEN Or polyimides (PI) (PEN).
The thickness of bottom ito thin film 2 is prepared, background is true between 20nm~100nm using magnetically controlled sputter method It is empty:1.0×10-3Pa~3.0 × 10-3Pa, working gas:Ar+O2, sputtering pressure:0.2Pa~0.8Pa, sputtering power:30W~ 200W, underlayer temperature:25 DEG C~220 DEG C, with continuous winding method plated film, the convoluting speed 0.005m/min of PET substrate 1~ 0.040m/min.Certainly, in the utility model, bottom ito thin film 2 can also be AZO films, IZO films, IGZO films etc. Metal-oxide film
For the thickness of metallic intermediate layer film 3 between 5nm~25nm, the film has excellent electric conductivity, its Visible light transmissivity and Ag thickness degree are in close relations.In order to realize the utility model purpose, the metal level of the centre can also be Au films, or Ag-Au alloy films.Metallic intermediate layer film is prepared using radio frequency magnetron sputtering method, base vacuum:1.0×10- 3Pa~3.0 × 10-3Pa, working gas:Ar, sputtering pressure:0.2Pa~0.8Pa, sputtering power:100W~200W, in room temperature Lower preparation.
The thickness of top layer nano silver wire film 4 is 2-5 times of nano silver wire length, Ag nanowire diameters between 30nm~ Between 180nm, length is between 30 μm~200 μm.It is coated with and prepares under room temperature, normal pressure, coating speed:50mm/s~ 200mm/s。
By adjusting each thickness degree, make three-layer composite structure transparent conductive film that there is higher transmission to visible region Rate, at the same have than the more excellent electric conductivity of the structured transparent conductive film such as individual layer ITO, individual layer nano silver wire on PET substrate and Visible light transmissivity.
Embodiment 1
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide ito thin film 2 successively from bottom to top, and Ag films 3, coating method, which is used above, and prepares in Ag films 3 has Nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 80nm of bottom ito thin film 2, is prepared, base vacuum using magnetically controlled sputter method:3.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.6Pa, sputtering power:200W, underlayer temperature:220 DEG C, with continuous winding method plated film, The convoluting speed 0.040m/min of PET substrate 1.
The thickness 25nm of intermediate layer Ag films 3, is prepared, base vacuum using radio frequency magnetron sputtering method:3.0×10- 3Pa, working gas:Ar, sputtering pressure:0.5Pa, sputtering power:200W, prepare at room temperature.
Thickness 100nm, Ag the nanowire diameter 50nm of top layer nano silver wire film 4,50 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:200mm/s.
Embodiment 2
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide AZO films 2 successively from bottom to top, and Ag films 3, coating method, which is used above, and prepares in Ag films 3 has Nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 85nm of bottom AZO films 2, is prepared, base vacuum using magnetically controlled sputter method:1.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.2Pa, sputtering power:30W, underlayer temperature:25 DEG C, with continuous winding method plated film, PET The convoluting speed 0.005m/min of substrate 1.
The thickness 5nm of intermediate layer Ag films 3, is prepared, base vacuum using radio frequency magnetron sputtering method:1.0×10- 3Pa, working gas:Ar, sputtering pressure:0.3Pa, sputtering power:100W, prepare at room temperature.
Thickness 120nm, Ag the nanowire diameter 30nm of top layer nano silver wire film 4,30 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:50mm/s.
Embodiment 3
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide ito thin film 2 successively from bottom to top, and Ag films 3, coating method, which is used above, and prepares in Ag films 3 has Nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 100nm of bottom ito thin film 2, is prepared, base vacuum using magnetically controlled sputter method:2.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.5Pa, sputtering power:110W, underlayer temperature:60 DEG C, with continuous winding method plated film, The convoluting speed 0.005m/min of PET substrate 1.
The thickness 12nm of intermediate layer Ag films 3, is prepared, base vacuum using radio frequency magnetron sputtering method:2.0×10- 3Pa, working gas:Ar, sputtering pressure:0.5Pa, sputtering power:150W, prepare at room temperature.
Thickness 240nm, Ag the nanowire diameter 60nm of top layer nano silver wire film 4,75 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:60mm/s.
Embodiment 4
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PEN substrates 1, in flexible substrate 1 Sputtering has metal oxide AZO films 2 successively from bottom to top, and gold thin film 3, coating method, which is used above, and prepares in gold thin film 3 has Nano silver wire film 4.
150 μm of 1 thickness of flexible PEN substrates.
The thickness 80nm of bottom AZO films 2, is prepared, base vacuum using magnetically controlled sputter method:3.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.8Pa, sputtering power:60W, underlayer temperature:220 DEG C, with continuous winding method plated film, The convoluting speed 0.01m/min of PEN substrates 1.
The thickness 10nm of intermediate layer gold thin film 3, is prepared, base vacuum using radio frequency magnetron sputtering method:3.0×10- 3Pa, working gas:Ar, sputtering pressure:0.6Pa, sputtering power:100W, prepare at room temperature.
Thickness 360nm, Ag the nanowire diameter 120nm of top layer nano silver wire film 4,100 μm of length.In room temperature, often Prepared by pressure coating, coating speed:100mm/s.
Embodiment 5
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide AZO films 2 successively from bottom to top, and gold thin film 3, coating method, which is used above, and prepares in gold thin film 3 has Nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 100nm of bottom AZO films 2, is prepared, base vacuum using magnetically controlled sputter method:1.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.3Pa, sputtering power:80W, underlayer temperature:150 DEG C, with continuous winding method plated film, The convoluting speed 0.03m/min of PET substrate 1.
The thickness 15nm of gold thin film 3, is prepared, base vacuum using radio frequency magnetron sputtering method:1.0×10-3Paa, work Make gas:Ar, sputtering pressure:0.6Pa, sputtering power:130W, prepare at room temperature.
Thickness 150nm, Ag the nanowire diameter 50nm of top layer nano silver wire film 4,30 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:150mm/s.
Embodiment 6
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide IZO films 2 successively from bottom to top, and gold thin film 3, coating method, which is used above, and prepares in gold thin film 3 has Nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 100nm of bottom IZO films 2, is prepared, base vacuum using magnetically controlled sputter method:2.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.4Pa, sputtering power:110W, underlayer temperature:100 DEG C, with continuous winding method plated film, The convoluting speed 0.02m/min of PET substrate 1.
The thickness 20nm of gold thin film 3, is prepared, base vacuum using radio frequency magnetron sputtering method:2.0×10-3Pa, work Gas:Ar, sputtering pressure:0.4Pa, sputtering power:150W, prepare at room temperature.
Thickness 260nm, Ag the nanowire diameter 130nm of top layer nano silver wire film 4,135 μm of length.In room temperature, often Prepared by pressure coating, coating speed:175mm/s.
Embodiment 7
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PI substrates 1, in flexible substrate 1 Sputtering has metal oxide ito thin film 2 successively from bottom to top, electrum film 3, painting is used above in electrum film 3 Prepared by mode for cloth have nano silver wire film 4.
100 μm of 1 thickness of flexible PI substrates.
The thickness 100nm of bottom ito thin film 2, is prepared, base vacuum using magnetically controlled sputter method:3.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.7Pa, sputtering power:180W, underlayer temperature:200 DEG C, with continuous winding method plated film, The convoluting speed 0.04m/min of PI substrates 1.
The thickness 25nm of electrum film 3, is prepared, base vacuum using radio frequency magnetron sputtering method:3.0×10- 3Pa, working gas:Ar, sputtering pressure:0.8Pa, sputtering power:180W, prepare at room temperature.
Thickness 180nm, Ag the nanowire diameter 90nm of top layer nano silver wire film 4,100 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:200mm/s.
Embodiment 8
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide ito thin film 2 successively from bottom to top, electrum film 3, painting is used above in electrum film 3 Prepared by mode for cloth have nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 20nm of bottom ito thin film 2, is prepared, base vacuum using magnetically controlled sputter method:1.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.6Pa, sputtering power:90W, underlayer temperature:150 DEG C, with continuous winding method plated film, The convoluting speed 0.005m/min of PET substrate 1.
The thickness of intermediate layer electrum film 3 is 5nm, is prepared using radio frequency magnetron sputtering method, base vacuum: 1.0×10-3Pa, working gas:Ar, sputtering pressure:0.3Pa, sputtering power:200W, prepare at room temperature.
Thickness 220nm, Ag the nanowire diameter 110nm of top layer nano silver wire film 4,120 μm of length.In room temperature, often Prepared by pressure coating, coating speed:180mm/s.
Embodiment 9
A kind of transparent conductive oxide film of multi-layer compound structure, it includes flexible PET substrate 1, in flexible substrate 1 Sputtering has metal oxide IGZO films 2 successively from bottom to top, electrum film 3, painting is used above in electrum film 3 Prepared by mode for cloth have nano silver wire film 4.
200 μm of 1 thickness of flexible PET substrate.
The thickness 20nm of bottom IGZO films 2, is prepared, base vacuum using magnetically controlled sputter method:2.0×10-3Pa, work Make gas:Ar+O2, sputtering pressure:0.5Pa, sputtering power:200W, underlayer temperature:100 DEG C, with continuous winding method plated film, The convoluting speed 0.020m/min of PET substrate 1.
The thickness 18nm of intermediate layer electrum film 3, is prepared, base vacuum using radio frequency magnetron sputtering method:2.0 ×10-3Pa, working gas:Ar, sputtering pressure:0.5Pa, sputtering power:150W, prepare at room temperature.
Thickness 60nm, Ag the nanowire diameter 30nm of top layer nano silver wire film 4,115 μm of length.In room temperature, normal pressure Prepared by lower coating, coating speed:200mm/s.
Because using flexible PET substrate 1, the ito thin film 2, Ag films 3, nano silver wire film 4 can be achieved takeup type and connect Continuous formula production, and the breadth of PET substrate 1 is adjustable, can put forward the production efficiency of this kind of multi-layer compound structure transparent conductive film significantly, In the practical application of field of flexible display, potentiality are notable.Using other several flexible substrate materials described in the utility model and Underlying metal sull has same effect.
Refer to shown in Fig. 3, be that ITO/Ag/AgNW compound transparent electricity conductive films are repeatedly bending the square of rear film repeatedly The situation of change of resistance value.Tested using positive and negative 120 ° bendings, crooked process radius 5mm at square resistance test point.Wherein, 0~ 2000 times bending stage sheet resistance has been raised, and film rectangular resistance is kept not substantially during 2000~10000 bendings Become, ITO/Ag/AgNW compound transparent electricity conductive films present more stable electric property.As a result of flexible substrate, this reality Volume to volume continuous production can be realized with new middle multi-layer compound structure transparent conductive film, the breadth of flexible substrate flexibly may be used Adjust, there are large scale, efficient, serialization productive potentialities, there is higher application potential quality in field of flexible display.
After tested, compound transparent electricity conductive film described in the utility model being averaged in visible-range 400nm~700nm For light transmittance up to more than 82%, average square resistance is less than 7.5 Ω/.

Claims (8)

  1. A kind of 1. flexible composite transparent conductive film, it is characterised in that:Including flexible substrate (1), in flexible substrate (1) under Sputtering has metal-oxide film successively on and, metallic film, there is metal nanowire thin-films on metallic film.
  2. A kind of 2. flexible composite transparent conductive film according to claim 1, it is characterised in that:The material of the metallic film Expect for silver, gold, or electrum.
  3. A kind of 3. flexible composite transparent conductive film according to claim 1 or 2, it is characterised in that:The thickness of metallic film Spend for 5nm~25nm.
  4. A kind of 4. flexible composite transparent conductive film according to claim 1, it is characterised in that:The metal oxide film For ito thin film, AZO films, IZO films or IGZO films, thickness is between 20nm~100nm.
  5. A kind of 5. flexible composite transparent conductive film according to claim 1, it is characterised in that:The metal nanometer line is thin Film is silver nanowire film, and thickness is 2~5 times of metal nano line length.
  6. A kind of 6. flexible composite transparent conductive film according to claim 1 or 5, it is characterised in that:Described metal is received A diameter of 30nm~180nm of rice noodles, length are 30 μm~200 μm.
  7. A kind of 7. flexible composite transparent conductive film according to claim 1 or 5, it is characterised in that:Described metal oxygen Compound film, metallic film, and the thickness of metal nanowire thin-films ensure flexible composite transparent conductive film in visible ray model The average transmittance in 400nm~700nm is enclosed up to more than 82%, and average square resistance is less than 7.5 Ω/.
  8. A kind of 8. flexible composite transparent conductive film according to claim 1, it is characterised in that:The flexible substrate is One kind in PET, PEN, PI.
CN201720087128.5U 2017-01-23 2017-01-23 A kind of flexible composite transparent conductive film Active CN206711623U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108221392A (en) * 2018-03-09 2018-06-29 海安浩驰科技有限公司 A kind of conductive water repellent film
CN110416431A (en) * 2019-07-26 2019-11-05 云谷(固安)科技有限公司 A kind of display panel and display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108221392A (en) * 2018-03-09 2018-06-29 海安浩驰科技有限公司 A kind of conductive water repellent film
CN110416431A (en) * 2019-07-26 2019-11-05 云谷(固安)科技有限公司 A kind of display panel and display device

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