# US 10,319,487 B2 · Graphene oxide-metal nanowire transparent conductive film

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- Number: US 10,319,487 B2
- Document ID: US10319487B2
- Status: Granted
- Kind: B2
- Application number: 15/353,906
- Filed: 2016-11-17
- Published: 2017-03-16
- Granted: 2019-06-11
- Earliest claimed: 2013-02-21
- Assignees: Nanotek Instruments, Inc.
- Applicants: Nanotek Instruments, Inc.
- Inventors: Yi-Jun Lin; Aruna Zhamu; Bor Z. Jang
- Web page: https://patentgrep.com/patent/US10319487B2

## CPC

- H01B 1/02: mainly consisting of metals or alloys
- B05D 1/005: {Spin coating}
- B05D 1/02: performed by spraying
- B05D 1/04: involving the use of an electrostatic field {(B05D1/025 and B05D1/14 take precedence)}
- B05D 1/18: performed by dipping
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- H01B 1/04: mainly consisting of carbon-silicon compounds, carbon or silicon
- H01B 1/08: oxides
- B05D 1/12: Applying particulate materials (B05D1/06, B05D1/10 take precedence)
- B05D 1/24: Applying particulate materials
- B05D 5/12: to obtain a coating with specific electrical properties
- C23C 4/04: characterised by the coating material
- C23C 4/12: characterised by the method of spraying
- H05K 3/12: using {thick film techniques, e.g.} printing techniques to apply the conductive material {or similar techniques for applying conductive paste or ink patterns}
- 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})
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS

## Abstract

A process for producing a transparent conductive film, comprising (a) providing a graphene oxide gel; (b) dispersing metal nanowires in the graphene oxide gel to form a suspension; (c) dispensing and depositing the suspension onto a substrate; and (d) removing the liquid medium to form the film. The film is composed of metal nanowires and graphene oxide with a metal nanowire-to-graphene oxide weight ratio from 1/99 to 99/1, wherein the metal nanowires contain no surface-borne metal oxide or metal compound and the film exhibits an optical transparence no less than 80% and sheet resistance no higher than 300 ohm/square. This film can be used as a transparent conductive electrode in an electro-optic device, such as a photovoltaic or solar cell, light-emitting diode, photo-detector, touch screen, electro-wetting display, liquid crystal display, plasma display, LED display, a TV screen, a computer screen, or a mobile phone screen.

## Claims

### Claim 1

An optically transparent and electrically conductive film comprising metal nanowires and graphene oxide or reduced graphene oxide, having a metal nanowire-to-graphene oxide weight ratio of from 1/9 to 9/1, wherein said metal nanowires are free of surface-borne metal oxides or metal compounds, wherein said film exhibits an optical transparence no less than 85% and sheet resistance from 19 ohm/square to 50 ohm/square, and wherein said film further comprises carbon nanotubes, carbon nanofibers, or a combination thereof.

### Claim 2 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires have a length to thickness or diameter ratio greater than 3 and the smallest dimension of said metal nanowires is no greater than 200 nm.

### Claim 3 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein the smallest dimension of said metal nanowires is no greater than 100 nm.

### Claim 4 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires are selected from the group consisting of silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), alloys thereof, and combinations thereof.

### Claim 5 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires contain silver (Ag) nanowires.

### Claim 6 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires contain copper (Cu) nanowires.

### Claim 7 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires are composed of a transition metal or an alloy of a transition metal.

### Claim 8 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said metal nanowires are embedded in said graphene oxide.

### Claim 9 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said film is supported on a transparent substrate.

### Claim 10 (depends on 9)

The optically transparent and electrically conductive film of claim 9, wherein said transparent substrate is a glass or a polymer.

### Claim 11 (depends on 10)

The optically transparent and electrically conductive film of claim 10, wherein said polymer is selected from the group consisting of polyethylene terephthalate (PET) and polycarbonate.

### Claim 12 (depends on 9)

The optically transparent and electrically conductive film of claim 9, wherein said transparent substrate has chemical functional groups on the surface.

### Claim 13 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said film is patterned.

### Claim 14 (depends on 1)

The optically transparent and electrically conductive film of claim 1, wherein said film is coated onto two planar surfaces of a transparent substrate.

### Claim 15 (depends on 1)

The optically transparent and electrically conductive film of claim 1, where said graphene oxide has an oxygen content from 2 weight % to 20 weight % on a dry weight basis.

### Claim 16 (depends on 1)

The optically transparent and electrically conductive film of claim 1, where said graphene oxide or reduced graphene oxide-comprises single layer graphene oxide having a thickness of less than 10 atomic planes.

### Claim 17 (depends on 1)

The film of claim 1, wherein said film exhibits an optical transparence no less than 90% and sheet resistance from 19 ohm/square to 100 ohm/square.

### Claim 18 (depends on 1)

The film of claim 1, wherein said film has an average thickness from 0.34 nm to 10 nm.

### Claim 19 (depends on 1)

The film of claim 1, wherein said film has an average thickness from 10 nm to 100 nm.

### Claim 20 (depends on 1)

The film of claim 1, wherein said film has an average thickness from 100 nm to less than 1 μm.

### Claim 21 (depends on 1)

An electro-optic device comprising the optically transparent and electrically conductive film of claim 1 as an electrode.

### Claim 22 (depends on 1)

An electro-optic device comprising the film of claim 1, which device is a photovoltaic or solar cell, organic solar cell, light-emitting diode, photo-detector, touch screen, electro-wetting display, liquid crystal display, plasma display, LED display, a TV screen, a computer screen, or a mobile phone screen.