# US 7,608,294 B2 · Transparent substrate with transparent conductive film, method of manufacturing the same, and photoelectric conversion element including the substrate

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- Number: US 7,608,294 B2
- Document ID: US7608294B2
- Status: Granted
- Kind: B2
- Application number: 10/558,663
- Filed: 2004-11-18
- Published: 2007-02-01
- Granted: 2009-10-27
- Earliest claimed: 2003-11-18
- Assignees: Nippon Sheet Glass Co., Ltd.
- Inventors: Yasunori Seto; Hidemasa Yoshida; Akira Fujisawa; Yukio Sueyoshi
- Web page: https://patentgrep.com/patent/US7608294B2

## CPC

- H10F 71/138: {Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes}
- C03C 15/00: Surface treatment of glass, not in the form of fibres or filaments, by etching (etching or surface-brightening compositions, in general C09K13/00)
- C03C 17/22: with other inorganic material (C03C17/34, C03C17/44 take precedence)
- H10F 77/707: {of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate}
- C03C 2217/77: Coatings having a rough surface
- Y02E 10/50: Photovoltaic [PV] energy
- Y10T 428/24975: No layer or component greater than 5 mils thick
- Y10T 428/265: 1 mil or less
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- 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
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention provides a transparent substrate with a transparent conductive film that is thin but has a surface with concavities and convexities of increased height. A manufacturing method of the present invention includes a process of forming a transparent conductive film containing crystalline metal oxide as its main component on a transparent substrate by a pyrolytic oxidation method. In the method, a gaseous material containing a metal compound, an oxidizing material, and hydrogen chloride is supplied onto the transparent substrate. The process includes sequentially: a first step in which a mole ratio of the hydrogen chloride to the metal compound in the gaseous material is 0.5 to 5; and a second step in which the mole ratio is 2 to 10 and is higher than the mole ratio to be employed in the first step. With the present invention, a transparent substrate with a transparent conductive film can be provided that has a haze ratio of at least 15% and includes a transparent conductive film whose thickness is 300 nm to 750 nm.

## Claims

### Claim 1

A method of manufacturing a transparent substrate with a transparent conductive film, comprising a process of forming a transparent conductive film containing crystalline metal oxide as its main component on a transparent substrate by a pyrolytic oxidation method,
in the method, a gaseous material containing a metal compound, an oxidizing material, and hydrogen chloride being supplied onto the transparent substrate,
wherein the process comprises sequentially:
a first step in which a mole ratio of the hydrogen chloride to the metal compound in the gaseous material is 0.5 to 5 and crystalline initial grains are formed on the transparent substrate;
a second step in which the mole ratio is 2 to 10 and is higher than the mole ratio to be employed in the first step, and crystals of the metal oxide grow with the crystalline initial grains serving as starting points; and
a third step in which the mole ratio is lower than 1.5 and the crystal growth is promoted.

### Claim 2 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, wherein the mole ratio to be employed in the first step is 1 to 5.

### Claim 3 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, wherein the mole ratio to be employed in the first step is lower than 4, and the mole ratio to be employed in the second step is at least 3.

### Claim 4 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, further comprising a process of forming at least one undercoating layer on the transparent substrate, before the first step.

### Claim 5 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, further comprising a process of forming two undercoating layers on the transparent substrate, before the first step.

### Claim 6 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, wherein the transparent substrate is a glass ribbon having a surface temperature of at least 600° C. located on a molten metal bath in a process of manufacturing glass by a float glass process.

### Claim 7 (depends on 1)

The method of manufacturing a transparent substrate with a transparent conductive film according to claim 1, wherein the metal compound is a tin compound, and a metal oxide is tin oxide.