# US 9,040,119 B2 · Method for producing transparent conductive film, transparent conductive film, transparent conductive substrate and device comprising the same

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- Number: US 9,040,119 B2
- Document ID: US9040119B2
- Status: Granted
- Kind: B2
- Application number: 12/998,767
- Filed: 2009-12-01
- Published: 2011-09-22
- Granted: 2015-05-26
- Earliest claimed: 2008-12-01
- Assignees: Sumitomo Metal Mining Co., Ltd.
- Applicants: Masaya Yukinobu; Yoshihiro Otsuka
- Inventors: Masaya Yukinobu; Yoshihiro Otsuka
- Web page: https://patentgrep.com/patent/US9040119B2

## CPC

- H10F 71/138: {Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes}
- C23C 18/1216: {Metal oxides (C23C18/1212 takes precedence)}
- C23C 18/1275: {performed under inert atmosphere}
- C23C 18/1279: {performed under reactive atmosphere, e.g. oxidising or reducing atmospheres}
- C23C 18/1283: {Control of temperature, e.g. gradual temperature increase, modulation of temperature}
- H10H 20/833: Transparent materials
- G02F 1/13439: {characterised by their electrical, optical, physical properties; materials therefor; method of making}
- Y02E 10/50: Photovoltaic [PV] energy
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- 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)
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Provided is a method for producing a transparent conductive film which is formed via a coating step, a drying step and a baking step, wherein the baking step is characterized in that the dried coating film containing the organic metal compound as the main component is baked by being heated to a baking temperature or higher, at which at least the inorganic component is crystallized, under an oxygen-containing atmosphere having a dewpoint of −10° C. or lower, whereby an organic component contained in the dried coating film is removed therefrom by a heat decomposition, a combustion or the combination thereof to thereby form a conductive oxide microparticle layer densely filled with conductive oxide microparticles containing the metal oxide as a main component.

## Claims

### Claim 1

A method for producing a transparent conductive film, comprising the steps of:
(a) coating a heat-resistant substrate with a coating liquid to form a transparent conductive coating film containing an organic metal compound as a main component;
(b) drying the transparent conductive coating film to form a dried coating film;
(c) baking the dried coating film obtained in step (b) to form an inorganic film containing an inorganic component comprising a metal oxide as a main component by heating to at least a baking temperature at which at least the inorganic component is crystallized in an oxygen-containing atmosphere having a dewpoint of −10° C. or lower, whereby an organic component contained in the dried coating film is removed therefrom by heat decomposition, combustion or a combination thereof, to thereby form a conductive oxide microparticle layer densely filled with conductive oxide microparticles containing the metal oxide as a main component; wherein the organic metal compound comprises at least one compound selected from the group consisting of organic indium compounds, organic tin compounds and organic zinc compounds, and wherein the metal oxide consists of at least one oxide selected from the group consisting of indium oxide, tin oxide and zinc oxide, and
(d) subsequent to step (c) baking at a temperature of 300° C. or higher under an oxygen-containing atmosphere having a dewpoint of 0° C. or higher.

### Claim 2 (depends on 1)

The method for producing a transparent conductive film according to claim 1, wherein the organic indium compound consists of acetylacetone indium.

### Claim 3 (depends on 1)

The method for producing a transparent conductive film according to claim 1, including subsequent to step (d), a step (e) of baking at a temperature of 250° C. or higher under a neutral atmosphere or a reducing atmosphere.

### Claim 4 (depends on 1)

The method for producing a transparent conductive film according to claim 1, wherein the dewpoint in step (c) is −20° C. or lower.

### Claim 5 (depends on 1)

The method for producing a transparent conductive film according to claim 1, wherein step (a) comprises an ink jet printing method, a screen printing method, a gravure printing method, an offset printing method, a flexo printing method, a dispenser printing method, a slit coating method, a die coating method, a doctor blade coating method, a wire bar coating method, a spin coating method, a dip coating method and a spray coating method.

### Claim 6

A method for producing a transparent conductive film, comprising the steps of:
(a) coating a heat-resistant substrate with a coating liquid to form a transparent conductive coating film containing an organic metal compound as a main component and an organic metal compound as a dopant;
(b) drying the transparent conductive coating film to form a dried coating film;
(c) baking the dried coating film obtained in step (b) to form an inorganic film containing an inorganic component comprising a metal oxide containing a dopant metal compound as a main component by heating to at least a baking temperature at which at least the inorganic component is crystallized in an oxygen-containing atmosphere having a dewpoint of −10° C. or lower, whereby an organic component contained in the dried coating film is removed therefrom by heat decomposition, combustion or a combination thereof to thereby form a conductive oxide microparticle layer densely filled with conductive oxide microparticles containing the metal oxide as a main component and the dopant metal compound, wherein the organic metal compound comprises of at least one compound selected from the group consisting of organic indium compounds, organic tin compounds and organic zinc compounds, and wherein the metal oxide consists of at least one member of the oxides selected from indium oxide, tin oxide and zinc oxide, and
(d) subsequent to step (c) baking at a temperature of 300° C. or higher under an oxygen-containing atmosphere having a dewpoint of 0° C. or higher.

### Claim 7 (depends on 6)

The method for producing a transparent conductive film according to claim 6, wherein content ratio of the organic metal compound and the organic metal compound as a dopant is within a molar ratio range of 99.9:0.1 to 66.7:33.3.

### Claim 8 (depends on 6)

The method for producing a transparent conductive film according to claim 6, wherein the organic metal compound consists of the organic indium compound; and
the organic metal compound as a dopant is at least one compound selected from the group consisting of organic tin compounds, organic titanium compounds, organic germanium compounds, organic zinc compounds, organic tungsten compounds, organic zirconium compounds, organic tantalum compounds, organic niobium compounds, organic hafnium compounds and organic vanadium compounds; and the dopant metal compound is any one or more of tin oxide, titanium oxide, germanium oxide, zinc oxide, tungsten oxide, zirconium oxide, tantalum oxide, niobium oxide, hafnium oxide and vanadium oxide.

### Claim 9 (depends on 6)

The method for producing a transparent conductive film according to claim 6, wherein the organic metal compound consists of the organic tin compound; and the organic metal compound for a dopant is at least one compound selected from the group consisting of organic indium compounds, organic antimony compounds and organic phosphorous compounds.

### Claim 10 (depends on 6)

The method for producing a transparent conductive film according to claim 6, wherein the organic metal compound consists of the organic zinc compound; and the organic metal compound as a dopant is at least one compound selected from the group consisting of organic aluminum compounds, organic indium compounds and organic gallium compounds.