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 9,701,849 B2
• Filed: 02/15/2011
• Issued: 07/11/2017
• Est. Priority Date: 02/17/2010
• Status: Expired due to Fees

• Current Assignee: Sumitomo Metal Mining Company Limited
• Original Assignee: Sumitomo Metal Mining Company Limited
• Inventors: Nagano, Takahito, Yukinobu, Masaya, Otsuka, Yoshihiro
• Primary Examiner(s): Padgett, Marianne L
• Application Number:
  US13/579,380
• Publication Number:
  US 20120313055A1
• Time in Patent Office: 2,338 Days
• Field of Search: 427553, 427554, 427555, 427557, 427558, 427559, 4271263, 427168, 427170, 427226
• 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. A method of manufacturing a transparent conductive film comprising:

coating a substrate with a coating liquid containing an organometallic compound selected from an acetylacetonate of indium, tin, or zinc and a dopant organometallic compound thereby forming a coating film;

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

then

mineralizing the dried coating film by irradiating the dried coating film with ultraviolet light while heating the dried coating film to a temperature of 100°

C. to 200°

C. under an air atmosphere having a dew point temperature equal to or lower than −

10°

C. thereby forming an inorganic film that includes a metal oxide and a dopant; and

then

flowing a reducing atmosphere over the inorganic film at a temperature of 150°

C. to 600°

C. thereby reducing the inorganic film and forming the transparent conductive film;

wherein the reducing atmosphere includes hydrogen gas, wherein the hydrogen gas has an amount of 0.1 to 7 vol. %;

wherein the transparent conductive film includes a metal selected from the group consisting of indium, tin, and zinc.

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

the coating liquid includes a content molar ratio between the organometallic compound and the dopant organometallic compound in a range of 99.9:

0.1 to 66.7;

33.3.

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

the organometallic compound is an acetylacetonate of indium, and

the dopant organometallic compound and the dopant formed therefrom include a metal selected from the group consisting of tin, titanium, germanium, zinc, tungsten, zirconium, tantalum, niobium, hafnium, vanadium, and a mixture thereof.

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

the organometallic compound is an acetylacetonate of tin, and

wherein the dopant organometallic compound is selected from the group consisting of an organic indium compound, an organic antimony compound, an organic phosphorus compound, and a mixture thereof.

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

the organometallic compound is an acetylacetonate of zinc, and

wherein the dopant organometallic compound is selected from the group consisting of an organic aluminum compound, an organic indium compound, an organic gallium compound, and a mixture thereof.

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

irradiating the dried coating film with ultraviolet light includes applying the ultraviolet light in a pattern shape thereby forming the inorganic film having the pattern shape.

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

the inorganic film is reduced under the reducing atmosphere at the temperature of 150°

C. to 300°

C.

8. The method of manufacturing the transparent conductive film according to claim 7, further comprising

irradiating the inorganic film while the inorganic film is reduced under the reducing atmosphere at the temperature of 150°

C. to 300°

C.

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

the dew-point temperature is equal to or lower than −

30°

C.

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

the ultraviolet light has a wavelength equal to or smaller than 200 nm.

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

the ultraviolet light is emitted from a low-pressure mercury lamp, an amalgam lamp, or an excimer lamp.

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

the organometallic compound is indium acetylacetonate.

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

coating the substrate with the coating liquid includes a method selected from 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.

14. The method of manufacturing the transparent conductive film according to claim 1, wherein the amount of the hydrogen gas is 1 to 3 vol. % hydrogen gas.