Method for deposition of electrochromic layers

• US 4,996,083 A
• Filed: 06/12/1989
• Issued: 02/26/1991
• Est. Priority Date: 02/19/1987
• Status: Expired due to Fees

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Moser, Frank H., Lynam, Niall R.
• Primary Examiner(s): Bell, Janyce
• Application Number:
  US07/365,216
• Time in Patent Office: 624 Days
• Field of Search: 427/108, 427/126.2, 427/126.3, 427/126.5, 427/226, 427/165
• US Class Current: 427/108
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 2217/229 Non-specific enumeration
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2218/111 by dipping, immersion
• CPC Class Codes: C03C 2218/112 by spraying
• CPC Class Codes: C03C 2218/116 by spin-coating, centrifugation
• CPC Class Codes: C09K 9/00 Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
• CPC Class Codes: G02F 1/1524 Transition metal compounds

Abstract

The specification discloses a method for coating a substrate with electrochromic coatings by dipping a substrate having a conductive surface into, or spraying, or spin coating with, a solution prepared by reacting an anhydrous halide of an electrochromically active transition metal with a C₁ to C₅ anhydrous alcohol, most preferably under a stream of inert gas, at 0 to 80 degrees C. The dipped substrate is removed at a rate necessary to give a desired thickness, and the resulting coating is dried and hydrolyzed and further condensed to create an electrochromically active coating.

Claims

1. A method for preparing transition metal coating solutions which are suitable for preparing electrochromic layers and the like, comprising:

forming a first solution by reacting an anhydrous halide for an electrochromically active transition metal with a C₁ to C₅ carbon anhydrous at 0 to 80 degrees C., and

blending in a coating solution, in alcohol, comprising about 5% to about 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate coating solution to said solution being about 10;

90 to about 75;

25.

20. The method of claim 1 in which a stream of inert gas is passed over said coating solution during said reaction.

2. The method of claim for preparing transition metal coating solutions which are suitable for preparing electrochromic layers and the like, comprising:

forming a first solution by reacting an anhydrous halide for an electrochromically active transition metal with a C₁ to C₅ carbon anhydrous at 0 to 80 degrees C. while simultaneously passing a stream comprising at least one inert gas over said first solution during said reaction; and

blending in a coating solution, in alcohol, comprising about 5% to about 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate coating solution being about 10;

90 to about 75;

25.

3. The method of claim 2 in which the ratio of transition metal halide to alcohol is from about 5 to 20 weight/volume percent.

4. The method of claim 3 in which includes filtering said first solution after the reaction has completed.

5. The method of claim 4 in which a stream of inert gas is passed over said coating solution during said reaction.

6. The method of claim 4 in which from 5 to 20% of a wetting agent is added to said coating solution to facilitate good cosmetic appearance in thicker coatings.

7. The method of claim 6 in which from 10 to 15% of said wetting agent is added to said coating solution.

8. The method of claim 4 in which said first solution reaction is allowed to continue for several hours.

9. The method of claim 8 in which said transition metals used ar selected from the group consisting of vanadium, chromium, molybdenum, tungsten, iridium, manganese and nickel whereby electrochromic coatings can be obtained.

10. The method of claim 9 in which said transition metal is tungsten.

11. The method of claim 10 in which said transition metal is nickel and an alkali metal alkoxy compound is added to the reaction mixture in a ratio of from about 10% to about 100% by weight of said transition metal halide.

12. The method of claim 11 in which said alkali metal alkoxy includes an alkoxy group which corresponds to at least one of the alcohols being reacted with said transition metal halide.

13. The method of claim 4 in which includes mixing two or more of said first solutions each being formed from a different transition metal halide.

14. The method of claim 4 in which includes using a mixture of two or more of said C₁ to C₅ alcohols.

15. The method of claim 2 in which said transition metals used are selected from the group consisting of vanadium, chromium, molybdenum, tungsten, iridium, manganese and nickel whereby electrochromic coatings can be obtained.

16. The method of claim 2 in which said transition metal is tungsten.

17. The method of claim 2 in which said transition metal is nickel and an alkali metal alkoxy compound is added to the reaction mixture in a ratio of from about 10% to about 100% by weight of said transition metal halide.

18. The method of claim 2 in which includes mixing 2 or more of said first solutions each being formed from a different transition metal halide.

19. The method of claim 2 in which includes using a mixture of two or more of said C₁ to C₅ alcohols.

21. The method of claim 2 in which from 5 to 20% of a wetting agent is added to said coating solution to facilitate good cosmetic appearance in thicker coatings.

22. The method of claim 21 in which from 10 to 15% of said wetting agent is added to said coating solution.

23. A method for preparing an electrochromic coating on a substrate having an electrically conductive surface comprising:

preparing a coating solution by reacting at least one nickel halide compound, at least one C₁ to C₅ anhydrous alcohol and at least one alkali metal alkoxide at 0 to 80 degrees C.;

coating the conductive surface of said substrate with the resulting solution to give a coating of a desired thickness; and

drying and hydrolyzing and further condensing said coating to an electrochromically active coating.

24. The method of claim 23 wherein said coating solution is blended with a coating solution, in alcohol, comprising from 5 to 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate solution to said solution being about 10:

90 to about 75;

25.

25. The method of claim 23 in which from 5 to 20% of the wetting agent is added to said blend.

26. The method of claim 24 in which from 5 to 20% of the wetting agent is added to said blend.

27. The method of claim 23 wherein said nickel halide comprises nickel chloride.

28. The method of claim 23 wherein said alkali metal alkoxide comprises sodium ethylate.

29. The method of claim 24 wherein said tetraethyl orthosilicate coating solution comprises partially hydrolyzed tetraethylorthosilicate.

30. The method of claim 27 wherein said coating solution is blended with a coating solution, in alcohol, comprising from 5 to 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate coating to said solution being about 10:

90 to about 75;

25.

31. The method of claim 27 wherein said coating solution contains from 5 to 20% of at least one wetting agent.

32. The method of claim 30 wherein said silica coating comprises nickel chloride.

33. The method of claim 28 wherein said nickel halide comprises nickel chloride.

34. The method of claim 33 wherein said coating solution is blended with a silica coating solution, in alcohol, comprising from 5 to 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate coating to said solution being about 10:

90 to about 75;

25.

35. The method of claim 33 wherein said coating solution contains from 5 to 20% of at least one wetting agent.

36. A method for preparing an electrochromic coating on a substrate having an electrically conductive surface comprising:

preparing a coating solution by reacting at least one anhydrous halide of an electrochromically active transition metal, at least one C₁ to C₅ anhydrous alcohol and at least one alkali metal alkoxy compound, wherein the ratio of transition metal halide to alcohol is from about 5 to 20 weight/volume percent and the ratio of alkali metal alkoxy compound to transition metal halide is from about 0 to 100 weight/volume weight percent, at 0 to 80 degrees C. while simultaneously passing a stream of inert gas over said coating solution during said reaction;

coating the conductive surface of said substrate with the resulting solution to give a coating of a desired thickness; and

drying and hydrolyzing and further condensing said coating to an electrochromically active coating.

37. The method of claim 36 which includes filtering said solution after the reaction has been completed.

38. The method of claim 37 wherein said coating solution contains from 5 to 20% by weight of at least one wetting agent.

39. The method of claim 38 wherein the amount of said wetting agent is from 10 to 15% by weight.

40. The method of claim 37 wherein said reaction is allowed to continue for several hours.

41. The method of claim 40 in which said transition metals used are selected from the group consisting of vanadium, chromium, molybdenum, tungsten, iridium, manganese and nickel whereby electrochromic coatings can be obtained.

42. The method of claim 41 in which said transition metal is tungsten.

43. The method of claim 41 in which said transition metal is nickel.

44. The method of claim 43 in which said alkali metal alkoxy compound includes an alkoxy group which corresponds to at least one of the alcohols being reacted with said transition metal halide.

45. The method of claim 43 in which said solution is blended with a coating solution, in alcohol,

comprising about 5% to about 10% tetraethyl orthosilicate, the ratio of said tetraethyl orthosilicate coating solution to said solution being about 10:

90 to about 75;

25.

46. The method of claim 36 in which said transition metal is nickel.

47. The method of claim 46 in which said solution is blended with a coating solution, in alcohol, comprising about 5% to about 10% tetraethyl/orthosilicate the ratio of said tetraethyl/orthos coating solution to said solution being about 10:

90 to about 75;

25.