Method for forming tin oxide coating on glass

• US 5,698,262 A
• Filed: 05/06/1996
• Issued: 12/16/1997
• Est. Priority Date: 05/06/1996
• Status: Expired due to Term

• Current Assignee: Libbey-Owens-Ford Co. (Eaton Corporation PLC.), Pilkington PLC
• Original Assignee: Libbey-Owens-Ford Co. (Eaton Corporation PLC.), Pilkington PLC
• Inventors: Halliwell, Anthony C., Soubeyrand, Michel J.
• Primary Examiner(s): King, Roy V.
• Application Number:
  US08/642,921
• Time in Patent Office: 589 Days
• Field of Search: 427/255.3, 427/255.2, 427/255.1, 427/255, 427/109, 427/166, 427/167, 427/419.3, 65/60.52
• US Class Current: 427/255.19
• CPC Class Codes: C03C 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 2217/211 SnO2
• CPC Class Codes: C03C 2217/241 with halides
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth

Abstract

Fluorine doped tin oxide coatings on glass are prepared by providing a uniform, vaporized reactant mixture containing an organotin compound, HF, water and oxygen, and delivering the reactant mixture to the surface of the hot ribbon of glass, where the compounds react to form the fluorine doped tin oxide coating. The fluorine doped tin oxide coatings applied in accordance with the invention exhibit lower sheet resistance, and improved uniformity in sheet resistance over the coated surface of the glass.

Claims

1. A chemical vapor deposition process for applying a fluorine doped tin oxide coating to a surface on a hot glass substrate, comprising the steps of:

A) providing a hot glass substrate, including a surface upon which a fluorine doped tin oxide coating is to be deposited;

B) providing a uniform, vaporized reactant mixture containing an organotin compound, hydrogen fluoride, oxygen and water; and

C) delivering the vaporized reactant mixture to the surface on the hot glass substrates

wherein the uniform, vaporized reactant mixture reacts to deposit a coating of fluorine doped tin oxide on the surface of the hot glass substrate.

2. The process according to claim 1, wherein the glass is selected from the group consisting of soda-lime-silica glass, alkali-lime-silica glass, boro-silicate glass, alumino-silicate glass, phosphate glass, fused silica glass, and combinations thereof.

3. The process according to claim 1, wherein the glass is soda-lime-silica glass.

4. The process according to claim 1, wherein the organotin compound is selected from the group consisting of dimethyltin dichloride, diethyltin dichloride, dibutyltin diacetate, tetra methyl tin, methyltin trichloride, triethytin chloride, trimethyltin chloride, ethyltin trichloride, propyltin trichloride, isopropyltin trichloride, sec-butyltin trichloride, t-butyltin trichloride, phenyltin trichloride, carbethoxyethyltin trichloride, and combinations thereof.

5. The process according to claim 1, wherein the organotin compound is dimethyltin dichloride.

6. The process according to claim 1, wherein the glass substrate is provided at a temperature from about 750°

F. to about 1,500°

F.

7. The process according to claim 1, wherein the uniform, vaporized reactant mixture additionally comprises one or more compounds selected from the group consisting of helium, nitrogen, argon, and nitrous oxide.

8. The process according to claim 1, further comprising the step of depositing on said surface of said hot glass substrate a layer of a material which acts as a sodium diffusion barrier, so that said material is interposed between said surface of said glass substrate and said fluorine doped tin oxide coating.

9. The process according to claim 8, wherein a layer of silica is deposited on the surface of said hot glass substrate prior to the deposition of said fluorine doped tin oxide coating.

10. The process according to claim 9, wherein said layer of silica is deposited on the surface of said hot glass substrate by a chemical vapor deposition process.

11. The process according to claim 9, wherein a layer of tin oxide is deposited on the surface of said hot glass substrate prior to the deposition of said layer of silica.

12. The process according to claim 1, wherein said gaseous reactant mixture includes from about 0.2 to about 2 mole % hydrogen fluoride.

13. The process according to claim 2, wherein said gaseous reactant mixture includes from about 0.5 to about 1.5 mole % hydrogen fluoride.

14. The process according to claim 1, wherein said gaseous reactant mixture includes from about 2 to about 50 mole % water.

15. The process according to claim 14, wherein said gaseous reactant mixture includes from about 15 to about 35 mole % water.

16. The process according to claim 1, wherein said gaseous reactant mixture includes from about 10 to about 60 mole % oxygen.

17. The process according to claim 16, wherein said gaseous reactant mixture includes from about 30 to about 50 mole % oxygen.

18. A chemical vapor deposition process for applying a fluorine doped tin oxide coating to a surface on a hot glass substrate, comprising the steps of:

A) providing a hot glass substrate at a temperature from about 750°

F. to about 1,500°

F., including a surface upon which a fluorine doped tin oxide coating is to be deposited;

B) providing a uniform, vaporized reactant mixture containing an organotin compound, from about 0.2 to about 2 mole % hydrogen fluoride, from about 2 to about 50 mole % water, and from about 10 to about 60 mole % oxygen; and

C) delivering the vaporized reactant mixture to said surface on the hot glass substrate;

wherein the uniform, vaporized reactant mixture reacts to deposit a coating of fluorine doped tin oxide on the surface of the hot glass substrate.

19. A chemical vapor deposition process for applying a fluorine doped tin oxide coating to a surface on a hot glass substrate, comprising the steps of:

A) providing a hot glass substrate at a temperature from about 750°

F. to about 1,500°

F., including a surface upon which a fluorine doped tin oxide coating is to be deposited, said surface having a layer of silica applied thereto;

B) providing a uniform, vaporized reactant mixture containing an organotin compound, from about 0.2 to about 2 mole % hydrogen fluoride, from about 2 to about 50 mole % water, and from about 10 to about 60 mole % oxygen; and

C) delivering the vaporized reactant mixture to said surface on the hot glass substrate;

wherein the uniform, vaporized reactant mixture reacts to deposit a coating of fluorine doped tin oxide on said layer of silica on the surface of the hot glass substrate.