Method for depositing high performing electrochromic layers

• US 5,277,986 A
• Filed: 07/15/1992
• Issued: 01/11/1994
• Est. Priority Date: 07/15/1992
• 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): LUSIGNAN, MICHAEL R
• Application Number:
  US07/914,435
• Time in Patent Office: 545 Days
• Field of Search: 427/108, 427/110, 427/126.2, 427/126.3, 427/126.5, 427/226, 427/126.6, 427/164, 427/165, 428/432, 428/469, 428/702
• US Class Current: 428/432
• 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: C03C 17/3417 all coatings being oxide coatings
• 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

An electrochromic coating is produced by adding an organic moiety to a solution of an electrochromic precursor, said organic moiety having a decomposition temperature greater than, or a vapor pressure sufficiently low at, the temperature at which solution solvent is removed, such that said organic moiety remains integral with the electrochromic precursor coating on said substrate after said solvent evaporates, and said organic moiety having a decomposition temperature lower than, or a vapor pressure sufficiently high at, the temperature at which said electrochromic precursor coating is converted to an electrochromic coating that said moiety is substantially removed from said coating before or during said conversion.

Claims

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

providing a substrate having an electrically conductive surface;

providing a solution of an (1) electrochromic precursor, which can be converted to an electrochromic material, and (2) a removable moiety in (3) a carrier solvent;

said solvent, said moiety and said electrochromic precursor being selected such that said solvent is preferentially removed in a first removal step from a coating of said solution, leaving a matrix film of said electrochromic precursor and said moiety, and said moiety is preferentially removed from said matrix in a second removal step, prior to or during conversion of said electrochromic precursor to an electrochromic material;

coating the conductive surface of said substrate with said solution to form a coated substrate having a coating of a desired thickness;

removing said solvent from said coating in a first removal step to form an electrochromic precursor/moiety matrix film on said substrate;

performing a second removal step to remove moiety from said matrix; and

converting said electrochromic precursor to an electrochromic material to form an electrochromic coating.

2. A method in accordance with claim 1 wherein the molar ratio of said moiety to said electrochromic precursor is from about 0.1:

1 to about 2;

1.

3. A method in accordance with claim 2 wherein the molar ratio of said organic moiety to said electrochromic precursor is from about 0.3:

1 to about 1;

1.

4. The method of claim 1 in which said electrochromic precursor is selected such that it is converted to an electrochromic material at an elevated conversion temperature;

said first removal step being conducted by one of (1) evaporating said solvent in a vacuum, (2) evaporating said solvent at an elevated first temperature which is below said conversion temperature at which said electrochromic precursor is converted to an electrochromic material, or (3) a combination of both; and

said second removal step being conducted by heating said electrochromic precursor and moiety matrix to said conversion temperature at which said electrochromic precursor is converted to an electrochromic material.

5. The method of claim 4 in which said removable moiety is an organic moiety having a decomposition temperature greater than, or a vapor pressure sufficiently low at the temperature at which said solvent is removed, that said organic moiety and said electrochromic precursor form a matrix film on said substrate after said solvent evaporates, and said organic moiety having a decomposition temperature lower than, or a vapor pressure sufficiently high at said conversion temperature at which said electrochromic precursor is converted to an electrochromic material that said organic moiety is substantially removed from said coating before or during said conversion.

6. A method in accordance with claim 5 wherein said organic moiety has a carbon content of six carbon atoms or less per molecule.

7. A method in accordance with claim 6 wherein the molar ratio of said moiety to said electrochromic precursor is from about 0.1:

1 to about 2;

1.

8. A method in accordance with claim 7 wherein the molar ratio of said organic moiety to said electrochromic precursor is from about 0.3:

1 to about 1;

1.

9. A method in accordance with claim 7 wherein said organic moiety is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, formamide and glycerol.

10. A method in accordance with claim 9 wherein said electrochromic precursor is selected to form a metallic oxide selected from the group of tungsten oxide, molybdenum oxide, manganese oxide, chromium oxide, rhenium oxide, iridium oxide, nickel oxide and mixtures thereof.

11. A method in accordance with claim 10 wherein said carrier solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

12. The method of claim 11 in which said electrochromic precursor is a peroxyester-transition metal derivative.

13. The method of claim 12 in which said second removal step is conducted by heating to a temperature of from about 250°

C. to about 400°

C.

14. The method of claim 13 in which said second removal step is conducted by heating to a sufficiently high temperature to crystallize the resulting electrochromic coating.

15. The method of claim 7 in which said second removal step is conducted by heating to a temperature of from about 250°

C. to about 400°

C.

16. A method in accordance with claim 5 wherein the molar ratio of said moiety to said electrochromic precursor is from about 0.1:

1 to about 2;

1.

17. The method of claim 16 in which said second removal step is conducted by heating to a temperature of from about 250°

C. to about 400°

C.

18. A method in accordance with claim 5 wherein said second removal step comprises heating said coated substrate to said conversion temperature at a rate of from about 5°

C. to about 10°

C. per minute.

19. A method in accordance with claim 18 wherein said coated substrate is held at said conversion temperature for about 15 to about 120 minutes.

20. A method in accordance with claim 18 wherein said first removal step comprises heating said coated substrate from room temperature to said first elevated temperature at a rate of from about 5°

C. to about 10°

C. per minute.

21. The method of claim 4 in which said conversion is conducted by heating to a sufficiently high temperature to crystallize the resulting electrochromic coating.

22. A method in accordance with claim 21 wherein said electrochromic precursor is selected to form a metallic oxide selected from the group of tungsten oxide, molybdenum oxide, manganese oxide, chromium oxide, rhenium oxide, iridium oxide, nickel oxide and mixtures thereof.

23. A method in accordance with claim 4 in which said said first removal step is conducted by heating in a humid atmosphere.

24. A method in accordance with claim 23 wherein said first removal step includes holding said substrate in a humid atmosphere at about 100°

C. for about one hour.

25. A method in accordance with claim 24 wherein said coated substrate is heated in said first removal step from room temperature to about 100°

C. at a rate of from about 5°

C. to about 10°

C. per minute.

26. The method of claim 23 in which said removable moiety is an organic moiety having a decomposition temperature greater than, or a vapor pressure sufficiently low at the temperature at which said solvent is removed, that said organic moiety and said electrochromic precursor form a matrix film on said substrate after said solvent evaporates, and said organic moiety having a decomposition temperature lower than, or a vapor pressure sufficiently high at the temperature at which said electrochromic precursor is converted to an electrochromic material that said organic moiety is substantially removed from said coating before or during said conversion.

27. A method in accordance with claim 26 wherein the molar ratio of said moiety to said electrochromic precursor is from about 0.1:

1 to about 2;

1.

28. The method of claim 27 in which said second removal step is conducted by heating to a sufficiently high temperature to crystallize the resulting electrochromic coating.

29. The method of claim 27 in which said second removal step is conducted by heating to a temperature of from about 250°

C. to about 400°

C.

30. A method in accordance with claim 4 wherein said electrochromic precursor is selected to form a metallic oxide selected from the group of tungsten oxide, molybdenum oxide, manganese oxide, chromium oxide, rhenium oxide, iridium oxide, nickel oxide and mixtures thereof.

31. The method in accordance with claim 30 in which said precursor is formed by reacting a first transition metal with hydrogen peroxide and an organic acid to form a first metal-peroxy acid product, which is then reacted with a lower alcohol to form a first peroxyester-transition metal derivative;

and by reacting a second transition metal with hydrogen peroxide and an organic acid to form a second transition metal-peroxy acid product, which is then mixed with said first peroxyester-transition metal derivative.

32. The method in accordance with claim 31 which further comprises the step of reacting said second transition metal-peroxy acid product with a lower carbon alcohol to form a second peroxyester-transition metal derivative prior to mixing with said first peroxyester-transition metal derivative.

33. The method of claim 1 which additionally includes covering said electrochromic coating with a layer of tantalum pentoxide, a proton conductor on a layer which is a lithium conductor.

34. A method in accordance with claim 33 wherein the molar ratio of said moiety to said electrochromic precursor is from about 0.1:

1 to about 2;

1.

35. The method of claim 34 in which said electrochromic precursor is selected such that it is converted to an electrochromic material at an elevated conversion temperature;

said first removal step being conducted by one of (1) evaporating said solvent in a vacuum, (2) evaporating said solvent at an elevated first temperature which is below said conversion temperature at which said electrochromic precursor is converted to an electrochromic material, or (3) a combination of both; and

said second removal step being conducted by heating said electrochromic precursor and moiety matrix to said conversion temperature at which said electrochromic precursor is converted to an electrochromic material.

36. The method of claim 35 in which said removable moiety is an organic moiety having a decomposition temperature greater than, or a vapor pressure sufficiently low at the temperature at which said solvent is removed, that said organic moiety and said electrochromic precursor form a matrix film on said substrate after said solvent evaporates, and said organic moiety having a decomposition temperature lower than-, or a vapor pressure sufficiently high at said conversion temperature at which said electrochromic precursor is converted to an electrochromic material that said organic moiety is substantially removed from said coating before or during said conversion.

37. A method in accordance with claim 36 wherein said organic moiety has a carbon content of six carbon atoms or less per molecule.

38. An electrochromic coating on a substrate having an electrically conductive surface formed by:

providing a substrate having an electrically conductive surface;

providing a solution of an (1) electrochromic precursor, which can be converted to an electrochromic material, and (2) a removable moiety in (3) a carrier solvent;

said solvent, said moiety and said electrochromic precursor being selected such that said solvent is preferentially removed in a first removal step from a coating of said solution, leaving a matrix film of said electrochromic precursor and said moiety, and said moiety is preferentially removed from said matrix in a second removal step, prior to or during conversion of said electrochromic precursor to an electrochromic material;

coating the conductive surface of said substrate with said solution to form a coated substrate having a coating of a desired thickness;

removing said solvent from said coating in a first removal step to form an electrochromic precursor/moiety matrix film on said substrate;

performing a second removal step to remove moiety from said matrix; and

converting said electrochromic precursor to an electrochromic material to form an electrochromic coating.