Method of making heat treated coated article using TCO and removable protective film

• US 9,255,029 B2
• Filed: 04/17/2012
• Issued: 02/09/2016
• Est. Priority Date: 04/17/2012
• Status: Active Grant

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Original Assignee: Guardian Industries Corporation (KOCH Industries Incorporated)
• Inventors: Veerasamy, Vijayen S.
• Primary Examiner(s): Talbot, Brian K
• Application Number:
  US13/448,733
• Publication Number:
  US 20130273377A1
• Time in Patent Office: 1,393 Days
• Field of Search: 427/108, 427/126.2, 427/154, 427/162, 427/165
• US Class Current: 1/1
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: B05D 3/068 using ionising radiations (gamma, X, electrons)
• CPC Class Codes: B05D 5/12 to obtain a coating with specific electrical properties
• CPC Class Codes: B05D 7/56 Three layers or more
• CPC Class Codes: B32B 17/06 comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• CPC Class Codes: B32B 9/00 Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• CPC Class Codes: C03C 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 17/3423 at least one of the coatings comprising a suboxide
• CPC Class Codes: C03C 17/3429 at least one of the coatings being a non-oxide coating
• CPC Class Codes: C03C 17/3435 comprising a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3441 comprising carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 2217/231 In2O3/SnO2
• CPC Class Codes: C03C 2217/948 Layers comprising indium tin oxide [ITO]
• CPC Class Codes: C03C 2218/355 Temporary coating
• CPC Class Codes: C03C 2218/365 Coating different sides of a glass substrate
• CPC Class Codes: H01L 31/02021 for solar cells electrical connection means, e.g. junction boxes, specially adapted for structural association with photovoltaic modules H02S40/34
• CPC Class Codes: H01L 31/0216 Coatings H01L31/041 takes precedence
• CPC Class Codes: H01L 31/0224 Electrodes
• CPC Class Codes: Y02E 10/50 Photovoltaic [PV] energy

Abstract

A method for making a heat treated (HT) coated article including an electrode, to be used in applications such as windows, electronic devices, or other applications. The method may include heat treating a substrate coated with at least a transparent conductive oxide (TCO) layer and an overlying film. From the TCO outwardly, the overlying film may include any combination of two, three or four of: (i) a gettering and/or doping layer(s); (ii) a stabilizing layer(s); (iii) a release layer(s); and (iv) an oxygen blocking or barrier layer. After HT, the protective film may be entirely or partially removed. Other embodiments relate to the pre-HT coated article, or the post-HT coated article.

Claims

1. A method of making a heat treated coated article adapted to be used in window, the method comprising:

heat treating a coated substrate comprising a substrate, a transparent conductive oxide (TCO) layer on the substrate, a gettering layer on the substrate over and in direct contact with the TCO layer, wherein the gettering layer comprises carbon and fluorine so as to getter oxygen during said heat treating and help dope the TCO layer with F to improve conductivity, and a protective film on the substrate over at least the TCO layer and the gettering layer, wherein the protective film includes a release layer and an oxygen barrier layer where the release layer and the oxygen barrier layer are of different material and/or different stoichiometry relative to each other,

wherein the heat treating comprises heating at least the substrate to temperature(s) of at least 500 degrees C.;

during said heat treating of the coated substrate with the TCO layer and the gettering layer and the protective film thereon, the protective film protects the TCO layer so that the TCO layer does not lose a significant amount of electrical conductivity and does not lose a significant amount of visible transmission during said heat treating so that the coated article is to be used in a window, and the gettering layer getters oxygen and provides fluorine for doping the TCO layer to improve conductivity thereof; and

exposing the protective film to a release liquid and removing at least part of the protective film during and/or after said heat treating, before the window is formed.

2. The method of claim 1, wherein the substrate is a glass substrate.

3. The method of claim 1, wherein the TCO layer comprises indium tin oxide (ITO).

4. The method of claim 1, wherein the release layer comprises zinc oxide.

5. The method of claim 1, wherein the barrier layer comprises aluminum nitride.

6. The method of claim 1, wherein the release layer comprises zinc oxide and the barrier layer comprises aluminum nitride.

7. The method of claim 1, wherein the release layer comprises a suboxide of Zn so that the release layer is substoichiometric at least prior to said heat treating.

8. The method of claim 7, wherein, prior to said heat treating, the release layer comprises ZnO_y where “

y”

is from about 0.1 to 0.9.

9. The method of claim 1, wherein, in the protective film prior to said heat treating, the release layer is more metallic than is the barrier layer.

10. The method of claim 1, wherein said heat treating comprises heating the substrate to temperature(s) of at least 580 degrees C.

11. The method of claim 1, wherein, prior to said heat treating, the coated substrate further comprises a stabilizing layer located between at least the release layer and the TCO layer.

12. The method of claim 11, wherein the stabilizing layer comprises zinc oxynitride.

13. The method of claim 1, wherein the release liquid comprises water and/or vinegar.

14. The method of claim 1, wherein the coated article is substantially transparent and following the heat treating the TCO layer is provided as an electrode in an electronic device.

15. The method of claim 1, wherein after said removing step at least part of the TCO layer is exposed so as to be an outermost layer of the coated article.

16. The method of claim 1, wherein the barrier layer comprises zirconium nitride.

17. The method of claim 1, wherein the protective film further includes a layer comprising zirconium nitride located directly under or directly over the barrier layer.

18. The method of claim 1, wherein the coated substrate further comprises an underlayer located between the substrate and the TCO layer.

19. The method of claim 1, wherein the coated substrate further comprises a layer comprising silver located between the TCO layer and the substrate.

21. The method of claim 1, wherein the gettering layer comprises amorphous carbon and said fluorine.

22. The method of claim 1, wherein the gettering layer is formed via an ion beam.

23. The method of claim 1, wherein the gettering layer is from about 5-40 angstroms thick.

26. The method of claim 1, wherein after the TCO layer has been deposited but before the gettering layer has been deposited, directing an ion beam including at least Ar ions onto the surface of the TCO layer 11 in order to peen the surface of the TCO layer so as to densify the surface of the TCO layer, wherein this peening by the ion beam cleans and smoothes the upper surface of the TCO layer.

20. A method of making a heat treated coated article adapted to be used in window, the method comprising:

heat treating a coated glass substrate comprising a glass substrate, a transparent conductive layer comprising ITO on the glass substrate, a gettering layer on the glass substrate over and in direct contact with the layer comprising ITO, wherein the gettering layer comprises carbon and fluorine so as to getter oxygen during said heat treating and help dope the TCO layer with F to improve conductivity, and a protective film on the glass substrate over at least the layer comprising ITO and the gettering layer, wherein the protective film includes a release layer comprising zinc oxide and an oxygen barrier layer comprising metal nitride;

during said heat treating of the coated glass substrate with the layer comprising ITO, the gettering layer and the protective film thereon, the protective film protects the layer comprising ITO so that the layer comprising ITO does not lose a significant amount of electrical conductivity and does not lose a significant amount of visible transmission during said heat treating so that the coated article is to be used in a window, and the gettering layer getters oxygen and provides fluorine for doping the layer comprising ITO to improve conductivity thereof; and

removing at least part of the protective film during and/or after said heat treating, before the window is formed.

24. The method of claim 20, wherein the gettering layer is from about 5-40 angstroms thick.

25. The method of claim 20, wherein the gettering layer comprises amorphous carbon and said fluorine.