Alkali metal diffusion barrier layer

• US 5,830,252 A
• Filed: 02/01/1996
• Issued: 11/03/1998
• Est. Priority Date: 10/04/1994
• Status: Expired due to Term

• Current Assignee: Vitro Flat Glass LLC (Compagnie De Saint-Gobain)
• Original Assignee: PPG Industries Incorporated (Nouryon BV)
• Inventors: Finley, James J., Gillery, F. Howard
• Primary Examiner(s): Ahmad, Nasser
• Application Number:
  US08/597,543
• Time in Patent Office: 1,006 Days
• Field of Search: 156/634, 156/656, 156/659.1, 156/145, 428/426, 428/428, 428/432, 428/433, 428/702, 65/60.5, 65/60.53, 65/60.1, 427/108, 427/126.2, 427/126.3, 204/192.1, 204/192.12
• US Class Current: 65/60.5
• CPC Class Codes: C03C 17/245 by deposition from the vapour phase
• CPC Class Codes: C03C 17/3411 with at least two coatings of inorganic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3607 Coatings of the type glass/inorganic compound/metal
• CPC Class Codes: C03C 17/3642 the multilayer coating containing a metal layer
• CPC Class Codes: C03C 17/3655 the multilayer coating containing at least one conducting layer
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/22 ZrO2
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/445 Organic continuous phases
• CPC Class Codes: C03C 2217/477 Titanium oxide
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C03C 2217/94 Transparent conductive oxide layers [TCO] being part of a multilayer coating
• CPC Class Codes: C03C 2218/156 by magnetron sputtering

Abstract

Amorphous metal oxide barrier layers of titanium oxide, zirconium oxide and zinc/tin oxide are effective as alkali metal ion barrier layers at thicknesses below 180 Angstroms. The amorphous metal oxide barrier layers are most effective when the density of the layer is equal to or greater than 90% of the crystalline density. The barrier layers prevent migration of alkali metal ions such as sodium ions from glass substrates into a medium e.g. electrolyte of a photochromic cell, liquid material of a liquid crystal display device contacting the glass surface. The properties of the medium, particularly electroconductive metal oxide coatings, are susceptible to deterioration by the presence of sodium ions migrating from the glass.

Claims

1. A method of depositing a metal oxide barrier film over a glass substrate surface comprising the steps of:

providing a sputter coating station, the sputter station comprising;

a generally horizontal path of travel, and

a sputter coating chamber above the path, the sputter chamber comprising;

a cathode target above the path, and

a shield on one side of the cathode target extending downward toward the path defined as a first shield and a shield on the opposite side of the cathode target extending downward toward the path defined as a second shield;

positioning said glass substrate on the path of travel;

energizing the cathode target in an oxidizing atmosphere to direct sputtered metal toward the path of travel;

moving the substrate and coating chamber relative to one another to pass the substrate under the first shield, under the cathode target and under the second shield;

coating the metal oxide barrier film over the substrate surface when the glass substrate is between the first shield and the second shield, said barrier film providing effective diffusion barrier of alkali metal ions from the glass substrate.

2. The method according to claim 1, wherein the barrier film is an amorphous zirconium oxide having a thickness between 30 and 120 Angstroms and a density equal to or greater than 5.0 grams per cubic centimeter.

3. The method according to claim 1, wherein the barrier film is an amorphous titanium oxide having a thickness in the range of 45 to 180 Angstroms and a density greater than 3.8 grams per cubic centimeter.

4. The method according to claim 1, wherein the barrier film is a zinc/tin oxide having a thickness in the range of 60 to 120 Angstroms and a density of 5.7 grams per cubic centimeter.

5. The method according to claim 1, wherein only sputtered metal traveling along a path generally normal to the substrate surface is deposited on the substrate surface.

6. The method according to claim 1 wherein the film is a titanium oxide layer having a thickness in the range of about 45 to 180 angstroms.

7. The method according to claim 1 wherein the film is titanium oxide layer having a density equal to or greater than 3.8 grams per cubic centimeter.

8. The method according to claim 6 wherein the titanium oxide layer has a thickness of 90 to 180 angstroms.

9. The method according to claim 1 wherein the layer is a zinc/tin oxide film.

10. The method according to claim 9 wherein the zinc/tin oxide layer has a density of 5.7 grams per cubic centimeter.

11. The method according to claim 9 wherein the zinc/tin oxide layer has a thickness of 90 to 120 angstroms.

12. The method according to claim 1 wherein the film is a zirconium oxide layer.

13. The method according to claim 12 wherein the density of the zirconium oxide layer is equal to or greater than 5.0 grams per cubic centimeter.

14. The method according to claim 12 wherein the thickness of the zirconium oxide layer is in the range of 30 to 60 angstroms.

15. The method according to claim 1 further including the step of providing over the barrier film an electroconductive coating selected from the group consisting of indium oxide, tin oxide, indium/tin oxide and zinc aluminum oxide.

16. The method according to claim 1 further comprising the step of providing over the barrier film a liquid crystal.

17. The method according to claim 1 further including the step of providing over the barrier film an electrolyte.

18. The method according to claim 1 wherein the moving step includes moving the cathode target over the surface of the substrate.

19. The method according to claim 1 wherein the film is an amorphous film having a density of at least 90% of its crystalline density.

20. The method according to claim 1 wherein the first and second shields are made of aluminum.