# US 12,002,602 B2 · Optically consistent transparent conductive film and preparation method thereof

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- Number: US 12,002,602 B2
- Document ID: US12002602B2
- Status: Granted
- Kind: B2
- Application number: 17/631,854
- Filed: 2020-08-31
- Published: 2022-09-08
- Granted: 2024-06-04
- Earliest claimed: 2019-07-29
- Assignees: Jiangsu Nanomeida Optoelectronics Technology Co., Ltd.
- Applicants: Jiangsu Nanomeida Optoelectronics Technology Co., Ltd
- Inventors: Tengjiao Liu; Yanping Su; Xin Li; Yuan Hu
- Web page: https://patentgrep.com/patent/US12002602B2

## CPC

- H10F 77/244: {made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers}
- B05D 1/26: performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D 3/0254: {After-treatment}
- B05D 3/06: by exposure to radiation (B05D3/02 takes precedence {; plasma treatment B05D3/141})
- B05D 3/067: {Curing or cross-linking the coating}
- B05D 3/142: {Pretreatment}
- B05D 7/54: {No clear coat specified}
- G02B 1/11: Anti-reflection coatings
- G02B 1/14: Protective coatings, e.g. hard coatings
- G06F 3/044: by capacitive means
- H01B 5/14: comprising conductive layers or films on insulating-supports
- H10K 71/60: Forming conductive regions or layers, e.g. electrodes
- G06F 2203/04103: Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
- G06F 2203/04112: Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
- H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K 50/828: Transparent cathodes, e.g. comprising thin metal layers
- H10K 2102/101: {comprising transparent conductive oxides [TCO]}
- H10K 2102/331: {Nanoparticles used in non-emissive layers, e.g. in packaging layer}
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G06F: ELECTRIC DIGITAL DATA PROCESSING (computer systems based on specific computational models G06N)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

An optically consistent transparent conductive film and a preparation method thereof solve the problems of obvious etching marks, poor optical stability, easy corrosion of nanomaterials, and migration of metal ions of the metal nanowire transparent conductive film. The addition of nanoparticles with a matchable refractive index and a high corrosion resistance, the addition of an optical compensation layer, the use of a substrate with an anti-glare layer and other such means can solve the problem of obvious post-treatment etching marks of metal nanowire conductive films. A dense full-plate conductive transparent conductive film with improved corrosion resistance can be achieved by using an electric compensation layer. An ultraviolet stabilizer is added into a protective solution to improve the optical stability of the conductive film. An antioxidant, a dendrimer, and a complexing agent in the protective solution solve the problem of easy corrosion of nanomaterials and migration of metal ions.

## Claims

### Claim 1

An optically consistent transparent conductive film, wherein the optically consistent transparent conductive film comprises a substrate, an optically consistent conductive layer and a protective layer;
wherein the substrate comprises a rigid or/and flexible substrate;
the optically consistent conductive layer comprises a conductive area, the conductive area comprises metal nanowires A and nanoparticles B, the metal nanowires A superimpose or crosslink to form a network in a conductive area, the nanoparticles B function to weld the metal nanowires A; the nanoparticles B are uniformly distributed in the conductive area, the influence of the nanoparticles B on the conductivity of the metal nanowires A is less than 50%; the optically consistent conductive layer comprises a non-conductive area obtained by etching the metal nanowires A in the conductive area, the non-conductive area comprises uniformly distributed nanoparticles B, the nanoparticles B do not form a continuous conductive pathway with each other in the non-conductive area; the vaporization temperature of the nanoparticles B is higher than that of the metal nanowires A; the corrosion rate of the metal nanowires A is faster than nanoparticles B; and the refractive index of the nanoparticles B is adapted to that of the metal nanowires A; and
the protective layer is coated on the surface of the optically consistent conductive layer, and the surface resistance value is not changed; the protective layer contains dendrimers having a chelating effect, the dendrimer has an effect of trapping metal ions to form a chelate to inhibit migration of metal ions; the protective layer further comprises dispersed nanoparticles B, and the nanoparticles B have the effect of reducing the chromaticity of the conductive area.

### Claim 2 (depends on 1)

The optically consistent transparent conductive film of claim 1, wherein the rigid substrate comprises one of glass, PMMA organic glass, PC polycarbonate or acrylic resin; and the flexible substrate comprises one of polyester, polyethylene, cycloolefin polymer, colorless polyimide, polypropylene, or polyethylene.

### Claim 3 (depends on 1)

The optically consistent transparent conductive film of claim 1, wherein the protective layer comprises dendrimers with a chelating effect, the dendrimer comprises one or more of a polyamidoamine dendrimer, a carboxyl modified polyamidoamine dendrimer and a hydroxyl modified polyamidoamine dendrimer.

### Claim 4 (depends on 1)

The optically consistent transparent conductive film of claim 1, wherein the optically consistent transparent conductive film further comprises functional layers, and the functional layers comprise one or any combination of a transmission enhancement layer, an anti-reflective layer, an anti-glare layer, an optical adaptation layer, an electrical adaptation layer, and a hardened layer.

### Claim 5 (depends on 4)

The optically consistent transparent conductive film of claim 4, wherein the transmission enhancement layer comprises a fluoropolymer, and the transmission enhancement layer is arranged between the substrate and the conductive layer, or on the back side of the substrate, or above the protective layer;
the anti-reflective layer comprises a fluoropolymer or a perfluoropolymer, and the anti-reflective layer is arranged between the substrate and the conductive layer, or on the back side of the substrate, or above the protective layer;
the composition of the anti-glare layer comprises one or more of a fluorine-based compound, a siloxane-based compound, nanomaterials doped with oxides or a transparent organic polymer, and the anti-glare layer is arranged on the back side of the substrate;
the optical adaptation layer is a metal layer or a ceramic layer formed by sputtering, evaporation or coating, the optical adaptation layer comprises metals, alloys, oxide nanomaterials and combinations thereof, and the optical adaptation layer is arranged between the conductive layer and the substrate; and
the electrical adaptation layer is a dense planar conductive layer or an electrostatic layer, wherein the dense planar conductive layer or the electrostatic layer comprises one or more of PEDOT:PSS, transparent conductive metal oxides, graphene, carbon nanotubes and carbon black, and the electrical adaptation layer is arranged above or below the protective layer.

### Claim 6 (depends on 1)

The optically consistent transparent conductive film of claim 1, wherein the morphology of nanoparticles B comprises a spherical shape, a core-shell, a rod, a heterojunction, or any combination thereof; the material of the nanoparticles B comprises metals, alloys, oxides, semiconductors, conductors, insulators or any combination thereof; the size of the nanoparticles B is less than or equal to 200 nm, the structure of the metal nanowire A comprises one or more of core-shell nanowire, hollow nanowire and solid nanowire; and the metal nanowire A has a diameter of 5-200 nm and an aspect ratio of more than or equal to 100.

### Claim 7 (depends on 1)

A preparation method of the optically consistent transparent conductive film of claim 1, comprising the following steps or a combination thereof:
S1, coating conductive ink on the substrate to form a conductive area, wherein the conductive ink includes nanoparticles B and metal nanowires A;
S2, etching the metal nanowires A at the conductive area prepared in S1 to form a non-conductive area, vaporizing or corroding the metal nanowires A, while retaining the nanoparticles B at the etched position; and
S3, constituting an optically consistent conductive layer by the conductive area formed in S1 and the non-conductive area formed in S2, coating protective layer formulation solution containing dendrimer on the conductive layer, and performing thermal curing or ultraviolet curing to form a protective layer.

### Claim 8 (depends on 7)

The preparation method of claim 7, wherein the conductive ink formulation comprises 0.01-0.5% of metal nanoparticles B, 0.01%-5% of film-forming agent, 0.002-1% of leveling agent, and 0.05-5% of metal nanowires A, and comprises 70-99% of conductive ink solvent.

### Claim 9 (depends on 7)

The preparation method of claim 7, wherein the protective layer formulation solution comprises 0.001%-0.05% of dendrimers, 0.07%-8% of monomers, 0.05%-1.5% of initiators, and 0.1%-5% of prepolymers, wherein the monomer comprises one or more of HEA, TPGDA, HPA, DAA, TMPTA, TMPTMA, EO-TMPTA, epoxy propylene ester, EO-CHA, DPGDA, IBOA, PGDA, PDDA, TEGDA, HDDA and BDDA; the initiator comprises one or more of α-hydroxyketone-based initiators, acylphosphine oxides and ketone-based initiators; the prepolymer comprises one or more of aliphatic polyurethane acrylate prepolymer, aromatic polyurethane acrylate prepolymer, polyurethane methacrylate, diallyl phthalate prepolymer, epoxy acrylate and epoxy methacrylate.

### Claim 10 (depends on 9)

The preparation method of claim 9, wherein the protective layer formulation solution also contains one or more of 0.003%-0.3% of complexing agent, 0.005%-0.4% of stabilizer and 0.003%-0.5% of antioxidant;
wherein the complexing agent complexes metal ions, the complexing agent comprises one or more of complexone, 8-hydroxyquinoline, dithizone, 2,2′-bipyridine (bipy), o-phenanthroline (C12H8N2), potassium sodium tartrate, ammonium citrate and inorganic complexing agent polyphosphate; the stabilizing agent comprises one or more of BASF ultraviolet absorber C81, Chimassorb 944, Tinuvin 770DF, Tinuvin 900, Tinuvin 123, Tinuvin 326, Tinuvin 234, Tinuvin 765, Tinuvin 791FB, Tinuvin 384-2, Tinuvin 144, UV70 and UV90; and the antioxidant comprises one or more of SONGNOX 4150, Irganox 1098, Irganox 1076, Irganox 1010 and Irganox 168.

### Claim 11 (depends on 7)

The preparation method of claim 7, wherein step S1 further comprises first optimization treatment, the first optimization treatment is applicable to any stage of the step, the first optimization treatment comprises: corona treatment and plasma treatment; step S2 further comprises second optimization treatment, the second optimization treatment is applicable to any stage of the step; step S3 comprises second optimization treatment, the second optimization treatment is applicable to all stages of the step; and the second optimization treatment comprises: infrared radiation treatment, microwave radiation treatment, xenon lamp pulse treatment and photon sintering treatment.

### Claim 12 (depends on 1)

A product that includes therein the optically consistent transparent conductive film of claim 1, wherein the product is selected from the group consisting of rigid or flexible touch screens, rigid or flexible displays, cell phone antenna circuits, infrared optical imaging elements, photoelectric sensors, electromagnetic shielding, smart windows, smart handwriting boards and solar cells.