Method for depositing titanium oxide coatings on flat glass

• US 6,238,738 B1
• Filed: 09/07/2000
• Issued: 05/29/2001
• Est. Priority Date: 08/13/1996
• Status: Expired due to Term

• Current Assignee: Libbey-Owens-Ford Co. (Eaton Corporation PLC.)
• Original Assignee: Libbey-Owens-Ford Co. (Eaton Corporation PLC.)
• Inventors: McCurdy, Richard J.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): CHEN, BRET P
• Application Number:
  US09/657,275
• Time in Patent Office: 264 Days
• Field of Search: 427/255.11, 427/255.19, 427/255.31, 427/255.36, 427/255.7, 427/166, 65/60.5, 65/60.52, 65/60.2
• US Class Current: 427/255.19
• CPC Class Codes: C03C 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 17/2456 Coating containing TiO2
• CPC Class Codes: C03C 2217/211 SnO2
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium

Abstract

A chemical vapor deposition process for laying down a tin or titanium oxide coating on a glass substrate through the use of an organic oxygen-containing compound and the corresponding metal tetrachloride. The organic oxygen compound is preferably an ester having an alkyl group with a β hydrogen in order to obtain a high deposition rate. The resulting article has a tin or titanium oxide coating which can be of substantial thickness because of the high deposition rates attainable with the novel process, and, in the case of titanium oxide coating possesses a desirable refractive index greater than 2.4. The coating growth rates resulting from the method of the present invention may be at least 130 Å per second.

Claims

1. A chemical vapor deposition process for depositing a titanium oxide coating on a glass substrate at deposition rates of at least 130 Å

/sec, comprising;

(a) pre-mixing a uniform, precursor gas mixture containing titanium tetrachloride and an ester, said ester having an alkyl group with a β

hydrogen;

(b) delivering said precursor gas mixture at a temperature below the thermal decomposition temperature of said ester to a location near a glass substrate to be coated, said substrate being at a temperature above the thermal decomposition temperature of said ester; and

c) introducing said precursor gas mixture into a vapor space above said glass substrate wherein said ester thermally decomposes and thereby initiates a reaction with said titanium tetrachloride to produce a titanium oxide coating on said glass substrate.

2. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein said ester is selected from the group consisting of ethyl formate, ethyl acetate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate.

3. A process for depositing titanium oxide coating on a glass substrate as recited in claim 1, wherein the glass substrate is a float glass ribbon having a temperature in the range of about 1100°

-1320°

F./590°

C.-715°

C.

4. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein the titanium tetrachloride in the precursor gas mixture is at a concentration of about 0.1-5.0% by volume.

5. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein the organic oxygen containing compound in the precursor gas mixture is at a concentration of about 1 to 5 times the concentration of the titanium tetrachloride.

6. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein said ester is ethyl acetate and said glass substrate is a float glass ribbon.

7. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein the glass substrate has a silica coating thereon, and said titanium oxide coating is deposited over the silica coating.

8. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein a silicon coating is first deposited on said glass substrate, a silica coating is deposited on said silicon coating, and said titanium oxide coating is deposited over the silica coating.

9. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein said titanium oxide coating has a refractive index greater than 2.4.

10. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein the titanium oxide coating has a residual carbon content less than 4 atomic percent.

11. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 1, wherein said precursor gas mixture includes helium as a carrier gas.

12. A process for depositing a titanium oxide coating a glass substrate as recited in claim 1, wherein the ester has an alkyl group having 2-10 carbon atoms.

13. A process for depositing a titanium oxide coating on hot flat glass as recited in claim 1, wherein the precursor gas mixture flows over the glass surface to be coated under laminar flow conditions.

14. A chemical vapor deposition process for depositing a titanium oxide coating on a float glass ribbon at deposition rates of at least 130 Å

/sec comprising;

(a) pre-mixing a uniform, precursor gas mixture containing titanium tetrachloride and an ester, said ester having an alkyl group with a β

hydrogen;

(b) delivering said precursor gas mixture at a temperature below the thermal decomposition temperature of said ester to a location near a float glass ribbon to be coated, said float glass ribbon being at a temperature range above the thermal decomposition temperature of said ester; and

(c) introducing said precursor gas mixture into a vapor space above said float glass ribbon wherein said ester thermally decomposes and thereby initiates a reaction with said titanium tetrachloride to produce a titanium oxide coating on said float glass ribbon.

15. A chemical vapor deposition process for depositing a titanium oxide coating on a substrate at a conversion efficiency such that, depending on the desired coating thickness, deposition rates of at least 130 Å

/sec can be attained, comprising;

(a) pre-mixing a uniform, precursor gas mixture containing titanium tetrachloride and an ester, said ester having an alkyl group with a β

hydrogen;

(b) delivering said precursor gas mixture at a temperature below the thermal decomposition temperature of said ester to a location near a substrate to be coated, said substrate being at a temperature above the thermal decomposition temperature of said ester; and

(c) introducing said precursor gas mixture into a vapor space above said substrate wherein said ester thermally decomposes and thereby initiates a reaction with said titanium tetrachloride to produce a titanium oxide coating on said substrate.

16. A process for depositing a titanium oxide coating on a substrate as recited in claim 15, wherein said ester is selected from the group consisting of ethyl formate, ethyl acetate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate.

17. A process for depositing titanium oxide coating on a substrate as recited in claim 15, wherein the substrate is a float glass ribbon.

18. A process for depositing a titanium oxide coating on hot flat glass as recited in claim 17, wherein the precursor gas mixture flows over the float glass ribbon to be coated under laminar flow conditions.

19. A process for depositing titanium oxide coating on a substrate as recited in claim 15, wherein said substrate is a float glass ribbon at a temperature in the range of about 1100°

-1320°

F./590°

C.-715°

C.

20. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 15, wherein said ester is ethyl acetate and said substrate is a float glass ribbon.

21. A process for depositing a titanium oxide coating on a substrate as recited in claim 15, wherein the substrate has a silica coating thereon, and said titanium oxide coating is deposited over the silica coating.

22. A process for depositing a titanium oxide coating on a glass substrate as recited in claim 15, wherein a silicon coating is first deposited on said substrate, a silica coating is deposited on said silicon coating, and said titanium oxide coating is deposited over the silica coating.

23. A process for depositing a titanium oxide coating a glass substrate as recited in claim 15, wherein the ester has an alkyl group having 2-10 carbon atoms.