# US 12,120,896 B2 · Transparent conductive film

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,120,896 B2
- Document ID: US12120896B2
- Status: Granted
- Kind: B2
- Application number: 17/257,398
- Filed: 2019-07-03
- Published: 2021-09-02
- Granted: 2024-10-15
- Earliest claimed: 2018-07-05
- Assignees: BASF Coatings GmbH
- Applicants: BASF Coatings GmbH
- Inventors: Boram Cho; Jean-Charles Flores; Michael Reinke; Myung Mo Sung; Jin Won Jung
- Web page: https://patentgrep.com/patent/US12120896B2

## CPC

- C23C 28/00: Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C03C 17/38: at least one coating being a coating of an organic material
- C23C 16/45525: {Atomic layer deposition [ALD]}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- C23C 28/02: only coatings {only including layers} of metallic material
- C23C 28/30: {Coatings combining at least one metallic layer and at least one inorganic non-metallic layer}
- C23C 28/322: {only coatings of metal elements only}
- C23C 28/34: {including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates}
- C23C 28/345: {with at least one oxide layer}
- C23C 28/3455: {with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer}
- C23C 28/40: {Coatings including alternating layers following a pattern, a periodic or defined repetition}
- C23C 28/42: {characterized by the composition of the alternating layers}
- C23C 28/44: {characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness}
- H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- C03C 2217/94: Transparent conductive oxide layers [TCO] being part of a multilayer coating
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/549: Organic PV cells
- Y10T 428/31678: Of metal
- 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)
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Described herein is a transparent conductive film including (a) a first laminate including at least two layers containing TiO2, ZrO2 or HfO2, and a layer containing an organic compound in between the two layers containing TiO2, ZrO2 or HfO2, (b) a metal layer, and (c) a second laminate including at least two layers containing ZnO, a layer containing an organic compound between the two layers containing ZnO, and a metallic dopant other than zinc.

## Claims

### Claim 1

A transparent conductive film comprising
(a) a first laminate comprising
at least two layers containing TiO2, ZrO2 or HfO2, and
a layer containing a sulfur-containing organic compound in between the two layers containing TiO2, ZrO2 or HfO2,
wherein each layer containing a sulfur-containing organic compound is in between two layers containing TiO2, ZrO2 or HfO2,
wherein the layers containing TiO2, ZrO2 or HfO2 each have a thickness of 0.1 to 5 nm,
(b) a metal layer, and
(c) a second laminate comprising
at least two layers containing ZnO,
a layer containing a sulfur-containing organic compound between the two layers containing ZnO, and
a metallic dopant other than zinc,
wherein each layer containing a sulfur-containing organic compound is in between two layers containing ZnO,
wherein the layers containing ZnO each have a thickness of 0.1 to 5 nm,
wherein the metal layer is between the first and the second laminate;
wherein a sheet resistance of the film increases by less than 10% after bending the film for 500 times around a radius of 1 cm.

### Claim 2 (depends on 1)

The transparent conductive film according to claim 1, wherein the metal layer contains Al, Cu, Ag, or Au.

### Claim 3 (depends on 1)

The transparent conductive film according to claim 1, wherein the metal layer has a thickness of 3 to 30 nm.

### Claim 4 (depends on 3)

The transparent conductive film according to claim 3, wherein the sulfur-containing organic compound is an organic thiol.

### Claim 5 (depends on 1)

The transparent conductive film according to claim 1, wherein the first laminate has a thickness of 5 to 40 nm.

### Claim 6 (depends on 1)

The transparent conductive film according to claim 1, wherein the film further comprises a transparent flexible substrate.

### Claim 7 (depends on 1)

The transparent conductive film according to claim 1, wherein the film has a sheet resistance of 200Ω/sq or less.

### Claim 8 (depends on 1)

The transparent conductive film according to claim 1, wherein the film has a resistivity of 0.02 Ω·cm or less.

### Claim 9 (depends on 1)

A method of using the film according to claim 1, the method comprising using the film as an electrode in an opto-electronic device.

### Claim 10

A process for preparing a transparent conductive film comprising depositing on a substrate
(a) a first laminate comprising
at least two layers containing TiO2, ZrO2 or HfO2, and
a layer containing a sulfur-containing organic compound in between the two layers containing TiO2, ZrO2 or HfO2,
wherein each layer containing a sulfur-containing organic compound is in between two layers containing TiO2, ZrO2 or HfO2,
wherein the layers containing TiO2, ZrO2 or HfO2 each have a thickness of 0.1 to 5 nm,
(b) a metal layer, and
(c) a second laminate comprising
at least two layers containing ZnO,
wherein the layers containing ZnO each have a thickness of 0.1 to 5 nm,
a layer containing a sulfur-containing organic compound between the two layers containing ZnO, and
a metallic dopant other than zinc,
wherein each layer containing a sulfur-containing organic compound is in between two layers containing ZnO,
wherein the metal layer is between the first and the second laminate;
wherein a sheet resistance of the film increases by less than 10% after bending the film for 500 times around a radius of 1 cm.

### Claim 11 (depends on 10)

The process according to claim 10, wherein the deposition is performed by atomic layer deposition.

### Claim 12 (depends on 10)

The process according to claim 10, wherein the deposition is performed at a temperature of 100 to 220° C.