Method for depositing electrochromic layers

• US 5,252,354 A
• Filed: 05/20/1992
• Issued: 10/12/1993
• Est. Priority Date: 05/20/1992
• Status: Expired due to Fees

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Agrawal, Anoop, Cronin, John P., Zhang, Raymond L., Tarico, Daniel J.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): DANG, VI
• Application Number:
  US07/886,505
• Time in Patent Office: 510 Days
• Field of Search: 427/58, 427/126.3, 427/126.5, 427/126.6
• US Class Current: 427/58
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence

Abstract

Electrochromic coating solutions are prepared by reacting a transition metal with a mixture of hydrogen peroxide and an organic acid. The resulting transition metal-peroxy acid product is esterified by reacting with lower carbon alcohols to produce a peroxyester-transition metal derivative. This derivative in solution in lower carbon alcohols provides a working solution into which a substrate having a conductive surface is preferably dipped and removed at a rate sufficient to give a coating of a desired thickness over the conductive surface. Spray or spin coating can be used to apply the coating to the conductive surface of the substrate. The coating is then dried and is externally fired in an oven to complete the necessary reactions to yield an electrochromic oxide coating having exceptional electrochromic properties.

Claims

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

providing a substrate having an electrically conductive surface;

reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product and reacting said transition metal-peroxy acid product with a lower carbon alcohol to form a peroxyester-transition metal derivative;

coating the conductive surface of said substrate with said peroxyester-transition metal derivative to give a coating of a desired thickness; and

converting said coating to an electrochromically active coating.

2. A method in accordance with claim 1 wherein said transition metal-peroxy acid product is isolated prior to reacting with said lower carbon alcohol.

3. A method in accordance with claim 2 wherein said transition metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium and nickel.

4. A method in accordance with claim 3 wherein said lower carbon alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

5. A method in accordance with claim 4 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

6. A method in accordance with claim 5 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

7. A method in accordance with claim 1 further comprising the steps of isolating said peroxyester-transition metal derivative and subsequently mixing said isolated derivative in a carrier to form a coating solution.

8. A method in accordance with claim 7 wherein said transition metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium and nickel.

9. A method in accordance with claim 8 wherein said lower carbon alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

10. A method in accordance with claim 9 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

11. A method in accordance with claim 10 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is the refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

12. A method in accordance with claim 1 further comprising the step of refluxing said transition metal, peroxide and organic acid reactants to form said transition metal-peroxy acid product.

13. A method in accordance with claim 12 wherein said refluxing is conducted for from about 10 to about 18 hours.

14. A method in accordance with claim 13 wherein said refluxing is conducted at a temperature of from about 45°

C. to about 60°

C.

15. A method in accordance with claim 1 further comprising the step of reacting a second metal with hydrogen peroxide and an organic acid to form a second metal-peroxy acid product and mixing said second metal-peroxy acid product with said peroxyester-transition metal derivative to form a peroxyester-transition metal/second metal-peroxy acid mixture.

16. A method in accordance with claim 15 further comprising the step of reacting said second metal-peroxy acid product with a lower carbon alcohol to form a peroxyester-second metal derivative prior to mixing with said peroxyester-transition metal derivative.

17. A method in accordance with claim 16 wherein said second metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium, nickel, silicon and titanium.

18. A method in accordance with claim 17 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

19. A method in accordance with claim 18 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

20. The method of claim 1 which includes providing a coating solution of said peroxyester-transition metal derivative in an organic solvent prior to dissolving.

21. A method in accordance with claim 10 wherein said transition metal-peroxy acid product is isolated prior to reacting with said lower carbon alcohol.

22. A method in accordance with claim 7 wherein said carrier is an organic solvent.

23. The method of claim 1 in which said conversion step is conducted by firing in the presence of oxygen at 100°

C. to 350°

C. for 15 to 120 minutes.

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

providing a substrate having an electrically conductive surface;

reacting tungsten with hydrogen peroxide and acetic acid to form a tungsten peroxy acid product, and reacting said tungsten peroxy acid product with a lower carbon alcohol to form a peroxyester-tungsten derivative;

coating the conductive surface of said substrate with said peroxyester-tungsten derivative to give a coating of a desired thickness; and

converting said coating to an electrochromically active coating.

25. A method in accordance with claim 24 wherein said tungsten-peroxy acid product is isolated as a powder prior to reacting with said lower carbon alcohol.

26. A method in accordance with claim 25 wherein said lower carbon alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

27. A method in accordance with claim 26 wherein said tungsten metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said tungsten metal-peroxy acid product.

28. A method in accordance with claim 24 wherein said tungsten metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said tungsten metal-peroxy acid product.

29. A method in accordance with claim 24 further comprising the step of reacting a second metal with hydrogen peroxide and an organic acid to form a second metal peroxy acid product and mixing said second metal peroxy acid product with said peroxyester-tungsten derivative to form a peroxyester tungsten/second metal-peroxy acid mixture.

30. A method in accordance with claim 29 further comprising the step of reacting said second metal-peroxy acid product with a lower carbon alcohol to form a peroxyester-second metal derivative prior to mixing with said peroxyester-transition metal derivative.

31. A method in accordance with claim 30 wherein said second metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium, nickel, silicon and titanium.

32. A method in accordance with claim 31 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

33. A method in accordance with claim 32 wherein said tungsten metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said tungsten metal-peroxy acid product.

34. A method for preparing an inorganic oxide coating on a substrate comprising:

providing a substrate having a surface;

reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product;

reacting said transition metal peroxy acid product with a lower carbon alcohol to form a peroxyester-transition metal derivative;

providing a coating solution of said peroxyester-transition metal derivative dissolved in an organic solvent;

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

converting said coating to an inorganic oxide.

35. A method in accordance with claim 34 wherein said transition metal-peroxy acid product is isolated prior to reacting with said lower carbon alcohol.

36. A method in accordance with claim 35 wherein said lower carbon alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

37. A method in accordance with claim 36 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

38. A method in accordance with claim 37 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

39. A method in accordance with claim 34 wherein said organic solvent is a low boiling solvent.

40. A method in accordance with claim 39 wherein said organic solvent comprises at least one of the group consisting of an alcohol, a furan and an ether.

41. A method in accordance with claim 40 wherein said alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol, and mixtures thereof.

42. A method in accordance with claim 34 further comprising the step of refluxing said transition metal, peroxide and organic acid reactants to form said transition metal-peroxy acid product.

43. A method in accordance with claim 42 wherein said refluxing is conducted for from about 10 to about 18 hours.

44. A method in accordance with claim 43 wherein said refluxing is conducted at a temperature of from about 45°

C. about 60°

C.

45. A method in accordance with claim 34 wherein said inorganic oxide coating is at least one of an electrically conducting coating, an optical coating, a wear-resistant coating, an anti-reflective coating, and an electrochromic coating.

46. A method in accordance with claim 34 further comprising the step of isolating said peroxyester-transition metal derivative prior to providing said coating solution.

47. A method in accordance with claim 46 wherein said isolated peroxyester-transition metal derivative is stored prior to reacting with said alcohol.

48. A method in accordance with claim 46 wherein said isolated peroxyester-transition metal derivative is stored at a temperature below 10°

C.

49. A method in accordance with claim 46 wherein said organic solvent is a low boiling solvent.

50. A method in accordance with claim 49 wherein said organic solvent comprises at least one of the group consisting of an alcohol, a furan and an ether.

51. A method in accordance with claim 50 wherein said alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol, and mixtures thereof.