PROCESS FOR MAKING OF GLASS ARTICLES WITH OPTICAL AND EASY-TO-CLEAN COATINGS

• US 20140113083A1
• Filed: 11/30/2012
• Published: 04/24/2014
• Est. Priority Date: 11/30/2011
• Status: Abandoned Application

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Lee, Christopher Morton, Lu, Xiao-feng, Ouyang, Michael Xu, Zhang, Junhong
• Application Number:
  US13/690,904
• Publication Number:
  US 20140113083A1
• Time in Patent Office: Days
• US Class Current: 427/569
• CPC Class Codes: C03C 17/002 for flat glass, e.g. float glass
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 2217/734 comprising an alternation of high and low refractive indexes
• CPC Class Codes: C03C 2217/76 Hydrophobic and oleophobic coatings
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/151 by vacuum evaporation
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C03C 2218/32 After-treatment
• CPC Class Codes: G02B 1/11 Anti-reflection coatings
• CPC Class Codes: G02B 1/111 using layers comprising organic materials
• CPC Class Codes: G02B 1/18 Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films G02B1/16 takes precedence
• CPC Class Codes: G02B 27/0006 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation G02B1/18 takes precedence; cleaning in general B08B

Abstract

A process in which both an optical coating, for example, an AR coating, and an ETC coating are deposited on a glass substrate article, in sequential steps, with the optical coating being deposited first and the ETC coating being deposited second, using the same apparatus and without exposing the article to the atmosphere at any time during the application of the optical coating and ETC coating.

Claims

1. A process for making glass articles having an optical coating and an easy-to-clean (ETC) coating on the optical coating, the process comprising:

providing a coating apparatus having at least one coating chamber for deposition of an optical coating and an ETC coating;

providing within the at least one coating chamber, optical coating source materials and ETC coating source materials, wherein when a plurality of optical coating source materials are deposited, each of the plurality of optical coating source materials is provided in a separate optical coating source container;

providing a substrate to be coated, the substrate having a length, a width and a thickness and at least one edge between surfaces of the substrate defined by the length and width;

evacuating the at least one coating chamber to a pressure of less than or equal to 10<sup>−

4</sup> Torr;

depositing the optical coating source materials on the substrate to form an optical coating;

depositing the ETC coating source materials on the optical coating to form an ETC coating;

removing the substrate from the at least one coating chamber to provide a glass article having the optical coating and the ETC coating; and

post-treating the glass article at a temperature of from about 60°

C. to about 200°

C. for a period of time from about 5 minutes to about 60 minutes in an air or humid environment having a relative humidity RH of 40%<

RH<

100% to facilitate cross-linking between ETC molecules;

wherein the optical coating is a multilayer coating comprising alternating layers of a high refractive index material H having a refractive index greater than 1.7 and less than or equal to 3.0, and one of (i) a low refractive index material L having a refractive index greater than or equal to 1.3 and less than or equal to 1.6 or (ii) a medium refractive index material M having a refractive index greater than 1.6 and less than or equal to 1.7, laid down in the order H(L or M) or (L or M)H, wherein each H(L or M) or (L or M)H pair of layers is a coating period; and

wherein a thickness of an H layer and an (L or M) layer, independent of each other, in each coating period is from about 5 nm to about 200 nm.

2. The process according to claim 1, wherein a number of coating periods in the multilayer coating is from 2 to 20, and the multilayer coating has a thickness from about 100 nm to about 2000 nm.

3. The process according to claim 1, wherein the high refractive index material H is selected from the group consisting of ZrO₂, HfO₂, Ta₂O₅, Nb₂O₅, TiO₂, Y₂O₃, Si₃N₄, SrTiO₃, and WO₃.

4. The process according to claim 1, wherein the low refractive index material L is selected from the group consisting of silica, fused silica, fluorine doped fused silica, MgF₂, CaF₂, YF, and YbF₃, and wherein the medium refractive index material M is Al₂O₃.

5. The process according to claim 1, wherein the ETC coating source materials are selected from the group consisting of:

a perfluoroalkyl silane of formula (R_F)_ySiX_4-y, where R_F is a linear perfluoroalkyl having a carbon chain length of 6-130 carbon atoms from the silicon atom to an end of the chain at its greatest length, X=Cl, acetoxy, —

OCH₃ or —

OCH₂H₃ and y=1 or 2; and

a perfluoropolyether silane of formula [CF₃—

CF₂CF₂O)_a]_y—

SiX_4-y where a is 5-10, y=1 or 2, and X is —

Cl, acetoxy, —

OCH₃ or —

OCH₂H₃, wherein a total perfluoropolyether chain length is 6-130 carbon atoms from the silicon atom to the end of the chain at its greatest length.

6. The process according to claim 5, wherein a thickness of the ETC coating is from about 1 nm to about 20 nm.

7. The process according to claim 1, wherein the optical coating source materials are deposited in a first chamber and the ETC coating source materials are deposited in a second chamber, the first chamber and the second chamber being connected by a vacuum seal/isolation-lock for transferring the substrate from the first chamber to the second chamber without exposing the substrate to atmosphere.

8. The process according to claim 7, wherein the first chamber is divided into an even number of sub-chambers of from 2 to 10, and a coating period of the multilayer optical coating is applied in an odd/even pair of sub-chambers;

wherein the odd numbered sub-chambers are used to deposit either the high refractive index material H or the low refractive index material L and the even numbered sub-chambers are used to deposit the other of the high refractive index material H or the low refractive index material L; and

wherein, if a last layer of a last coating period of the optical coating is a high refractive index layer, a capping layer of SiO₂ is applied over the high refractive index layer.

9. The process according to claim 1, wherein the substrate is selected from the group consisting of borosilicate glass, aluminosilicate glass, soda-lime glass, chemically strengthened borosilicate glass, chemically strengthened aluminosilicate glass and chemically strengthened soda-lime glass, and wherein the substrate has a thickness of from about 0.2 mm to about 1.5 mm.

10. The process according to claim 1, wherein the substrate is an aluminosilicate glass having a compressive stress of greater than 400 MPa and a depth of layer greater than 14 μ

m.

11. The process according to claim 1, wherein after post-treating the glass article, the glass article has an average water contact angle of at least 70°

after abrasion testing.

12. A process for making glass articles having an optical coating and an easy-to-clean (ETC) coating on the optical coating using a coating apparatus, the process comprising:

introducing a substrate into a coating apparatus having at least one coating chamber for depositing an optical coating and an ETC coating, the at least one coating chamber comprising at least one source container;

lowering the pressure in the at least one coating chamber to less than or equal to 10<sup>−

4</sup> Torr to form a vacuum;

depositing at least one optical coating source materials onto the substrate to form an optical coating;

depositing a ETC coating source materials onto the optical coating to form an ETC coating;

removing the substrate from the at least one coating chamber to provide a glass article having the optical coating and the ETC coating; and

post-treating the glass article at a temperature of from about 60°

C. to about 200°

C. for a period of time from about 5 minutes to about 60 minutes to facilitate cross-linking between ETC molecules.

13. The process according to claim 12, the process further comprising depositing a SiO₂ capping source material onto the optical coating to form a SiO₂ capping layer if a last deposited layer of the optical coating is not SiO₂.

14. The process according to claim 12, the process comprising depositing at least one optical coating source materials in a first coating chamber under vacuum, transferring the substrate from the first coating chamber to a second coating chamber without breaking vacuum, and depositing the ETC coating source materials in the second coating chamber under vacuum.

15. The process according to claim 12, the process comprising depositing two or more optical coating source materials layers to form the optical coating, wherein each optical coating source material layer is deposited in a separate coating chamber under vacuum;

and transferring the substrate from each of the separate coating chambers without breaking vacuum.

16. The process according to claim 12, wherein the optical coating is a multilayer coating comprising alternating layers of a high refractive index material H having a refractive index greater than 1.7 and less than or equal to 3.0, and one of (i) a low refractive index material L having a refractive index greater than or equal to 1.3 and less than or equal to 1.6 or (ii) a medium refractive index material M having a refractive index greater than 1.6 and less than or equal to 1.7, wherein each H(L or M) or (L or M)H pair of layers is a coating period.

17. The process according to claim 12, wherein after post-treating the glass article, the glass article has an average water contact angle of at least 70°

after abrasion testing.

18. The process according to claim 12, wherein depositing comprises chemical vapor deposition, plasma enhanced chemical vapor deposition, physical vapor deposition, laser ablation, vacuum arc deposition, thermal evaporation, sputtering, ion-assisted electron beam deposition, or atomic layer deposition.

19. The process according to claim 12, wherein the ETC coating source materials are selected from the group consisting of:

a perfluoroalkyl silane of formula (R_F)_ySiX_4-y, where R_F is a linear perfluoroalkyl having a carbon chain length of 6-130 carbon atoms from the silicon atom to an end of the chain at its greatest length, X=Cl, acetoxy, —

OCH₃ or —

OCH₂H₃ and y=1 or 2; and

a perfluoropolyether silane of formula [CF₃—

CF₂CF₂O)_a]_y—

SiX_4-y where a is 5-10, y=1 or 2, and X is —

Cl, acetoxy, —

OCH₃ or —

OCH₂H₃, wherein a total perfluoropolyether chain length is 6-130 carbon atoms from the silicon atom to the end of the chain at its greatest length.

20. The process according to claim 12, wherein the high refractive index material H is selected from the group consisting of ZrO₂, HfO₂, Ta₂O₅, Nb₂O₅, TiO₂, Y₂O₃, Si₃N₄, SrTiO₃, and WO₃, the low refractive index material L is selected from the group consisting of silica, fused silica, fluorine doped fused silica, MgF₂, CaF₂, YF, and YbF₃, and the medium refractive index material M is Al₂O₃.