METHOD OF MANUFACTURING TRANSPARENT CONDUCTIVE FILM, THE TRANSPARENT CONDUCTIVE FILM, ELEMENT AND TRANSPARENT CONDUCTIVE SUBSTRATE USING THE FILM, AS WELL AS DEVICE USING THE SUBSTRATE

• US 20120313055A1
• Filed: 02/15/2011
• Published: 12/13/2012
• Est. Priority Date: 02/17/2010
• Status: Active Grant

• Current Assignee: Sumitomo Metal Mining Company Limited
• Original Assignee: Sumitomo Metal Mining Company Limited
• Inventors: Yukinobu, Masaya, Otsuka, Yoshihiro, Nagano, Takahito
• Granted Patent: US 9,701,849 B2
• Time in Patent Office: Days
• US Class Current: 252/519.5
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C23C 18/1216 Metal oxides C23C18/1212 takes precedence
• CPC Class Codes: C23C 18/1275 performed under inert atmosphere
• CPC Class Codes: C23C 18/1279 performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
• CPC Class Codes: C23C 18/1295 with after-treatment of the deposited inorganic material
• CPC Class Codes: C23C 18/143 Radiation by light, e.g. photolysis or pyrolysis
• CPC Class Codes: H01L 21/02565 Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
• CPC Class Codes: H01L 21/02628 using solutions
• CPC Class Codes: H01L 31/1884 Manufacture of transparent electrodes, e.g. TCO, ITO
• CPC Class Codes: Y02E 10/50 Photovoltaic [PV] energy

Abstract

By using a coating method, which is a simple method of manufacturing a transparent conductive film at low cost, a transparent conductive film formed with heating at a low temperature, in particular, lower than 300° C. with both of excellent transparency and conductivity and also with excellent film strength and a method of manufacturing this transparent conductive film are provided.

Claims

1. (canceled)

7. The method of manufacturing the transparent conductive film according to claim 1, wherein

the heat energy ray irradiating process is a process of performing irradiation with energy rays in a pattern shape to form a conductive oxide fine-particle layer having the pattern shape.

2. A method of manufacturing a transparent conductive film to be formed through following processes:

a coating process of coating a substrate with a coating liquid for forming transparent conductive film containing an organometallic compound and a dopant organometallic compound as main components to form a coating film;

a drying process of drying the coating film to form a dried coating film; and

a heat energy ray irradiating process of irradiating the dried coating film with energy rays while heating the dried coating film to form an inorganic film having an inorganic component, which is a metal oxide containing a dopant metal compound, as a main component, wherein

the heat energy ray irradiating process is a process of irradiating the dried coating film having the organometallic compound and the dopant organometallic compound as the main components formed in the drying process with the energy rays while heating the dried coating film under an oxygen-containing atmosphere having a dew-point temperature equal to or lower than −

10°

C. to a heating temperature lower than 300°

C. to remove an organic component contained in the dried coating film by decomposition or burning, or decomposition and burning, thereby forming a conductive oxide fine-particle layer densely packed with conductive oxide fine particles having the metal oxide containing the dopant metal compound as a main component,

the organometallic compound is formed from any one or more types of an organic indium compound, an organic tin compound, and an organic zinc compound, and

the metal oxide is any one or more types of indium oxide, tin oxide, and zinc oxide.

3. The method of manufacturing the transparent conductive film according to claim 2, wherein

a content ratio between the organometallic compound and the dopant organometallic compound is in a range of 99.9:

0.1 to 66.7;

33.3 in terms of a molar ratio of the organometallic compound;

the dopant organometallic compound.

4. The method of manufacturing the transparent conductive film according to claim 2, wherein

the organometallic compound is made of an organic indium compound, and

the dopant organometallic compound is any one or more types of an organic tin compound, an organic titanium compound, an organic germanium compound, an organic zinc compound, an organic tungsten compound, an organic zirconium compound, an organic tantalum compound, an organic niobium compound, an organic hafnium compound, and an organic vanadium compound, and the dopant metal compound is any one or more types of tin oxide, titanium oxide, germanium oxide, zinc oxide, tungsten oxide, zirconium oxide, tantalum oxide, niobium oxide, hafnium oxide, and vanadium oxide.

5. The method of manufacturing the transparent conductive film according to claim 2, wherein

the organometallic compound is made of an organic tin compound, and

the dopant organometallic compound is any one or more types of an organic indium compound, an organic antimony compound, and an organic phosphorus compound.

6. The method of manufacturing the transparent conductive film according to claim 2, wherein

the organometallic compound is made of an organic zinc compound, and

the dopant organometallic compound is any one or more of an organic aluminum compound, an organic indium compound, and an organic gallium compound.

8. The method of manufacturing the transparent conductive film according to claim 2, wherein

subsequently to the energy ray irradiation under the oxygen-containing atmosphere while heating to the heating temperature lower than 300°

C., a reducing treatment of heating under a neutral atmosphere or a reducing atmosphere at a heating temperature equal to or lower than 600°

C. is performed.

9. The method of manufacturing the transparent conductive film according to claim 2, wherein

subsequently to the energy ray irradiation under the oxygen-containing atmosphere while heating to the heating temperature lower than 300°

C., a reducing treatment of heating under a neutral atmosphere or a reducing atmosphere at a heating temperature lower than 300°

C. is performed.

10. The method of manufacturing the transparent conductive film according to claim 8, wherein

the neutral atmosphere is an atmosphere containing any one or more types of nitrogen gas or inert gas, or the reducing atmosphere is a hydrogen gas atmosphere or an atmosphere containing at least one or more types of hydrogen gas or organic solvent vapor in the neutral atmosphere.

11. The method of manufacturing the transparent conductive film according to claim 9, wherein the energy ray irradiation is performed when a reducing treatment of heating under the neutral atmosphere or the reducing atmosphere at a heating temperature lower than 300°

C. is performed.

12. The method of manufacturing the transparent conductive film according to claim 2, wherein

the energy ray irradiation under the oxygen-containing atmosphere while heating to the heating temperature lower than 300°

C. is energy ray irradiation under the oxygen-containing atmosphere while heating to a heating temperature of 100°

C. to 250°

C.

13. The method of manufacturing the transparent conductive film according to claim 2, wherein

the oxygen-containing atmosphere has a dew-point temperature equal to or lower than −

30°

C.

14. The method of manufacturing the transparent conductive film according to claim 2, wherein

the energy ray irradiation is irradiation of ultraviolet rays containing at least a component having a wavelength equal to or smaller than 200 nm as a main component.

15. The method of manufacturing the transparent conductive film according to claim 14, wherein

the irradiation of the ultraviolet rays containing at least the component having the wavelength equal to or smaller than 200 nm as the main component is irradiation of ultraviolet rays emitted from any of a low-pressure mercury lamp, an amalgam lamp, or an excimer lamp.

16. The method of manufacturing the transparent conductive film according to claim 2, wherein

the organic indium compound is indium acetylacetonate.

17. The method of manufacturing the transparent conductive film according to claim 2, wherein

the coating of the substrate with the coating liquid for forming transparent conductive film in the coating process is performed by a method which is any of an inkjet printing method, a screen printing method, a gravure printing method, an offset printing method, a flexor 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, or a spray coating method.

18. A transparent conductive film obtained by the method of manufacturing the transparent conductive film according to claim 2.

19. An element including a conductive oxide fine-particle layer, wherein

the conductive oxide fine-particle layer is the transparent conductive film according to claim 18.

20. The element according to claim 19, wherein

the element is a thin-film transistor using the conductive oxide fine-particle layer as a channel active layer of a thin-film transistor.

21. A transparent conductive substrate including a transparent conductive film on a substrate, wherein

the transparent conductive film is the transparent conductive film according to claim 18.

22. A device including a transparent electrode, wherein the transparent electrode is the transparent conductive substrate according to claim 21.

23. The device according to claim 22, wherein

the device is of one type selected from among a light-emitting device, an electric power generating device, a display device, and an input device.

24. The method of manufacturing the transparent conductive film according to claim 9, wherein

the neutral atmosphere is an atmosphere containing any one or more types of nitrogen gas or inert gas, or the reducing atmosphere is a hydrogen gas atmosphere or an atmosphere containing at least one or more types of hydrogen gas or organic solvent vapor in the neutral atmosphere.

25. The method of manufacturing the transparent conductive film according to claim 11, wherein

the energy ray irradiation is irradiation of ultraviolet rays containing at least a component having a wavelength equal to or smaller than 200 nm as a main component.

26. The method of manufacturing the transparent conductive film according to claim 25, wherein

the irradiation of the ultraviolet rays containing at least the component having the wavelength equal to or smaller than 200 nm as the main component is irradiation of ultraviolet rays emitted from any of a low-pressure mercury lamp, an amalgam lamp, or an excimer lamp.