Electrochromic variable transmission glazing

• US 5,241,411 A
• Filed: 03/23/1992
• Issued: 08/31/1993
• Est. Priority Date: 07/02/1987
• Status: Expired due to Fees

• Current Assignee: Saint-Gobain Vitrage
• Original Assignee: Saint-Gobain Vitrage
• Inventors: Arribart, Herve, Reboul-Salze, Veronique, Padoy, Christian, Buffat, Bernard
• Primary Examiner(s): Arnold, Bruce Y.
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US07/859,598
• Time in Patent Office: 526 Days
• Field of Search: 350/357, 359/265, 359/269, 359/270
• US Class Current: 359/269
• CPC Class Codes: G02F 1/15245 based on iridium oxide or hydroxide

Abstract

An electrochromic variable transmission glazing comprising first and second glass sheets substrates which are joined by an organic polymer whose proton conductivity is greater than or equal to 10^-5 ohm^-1 cm^-1 at 20° C. The glass sheets are coated on their joining faces with transparent electroconductive layers. The first transparent substrate further comprises a layer of electrochromic material, such as tungsten oxide, in contact with the proton conductive polymer. The glazing is characterized by an iridium oxide layer on the second transparent substrate which is interposed between the layer of electroconductive material and the organic polymer. The glazing further comprises a pair of current leads attached to the electroconductive layer which connect the glazing to a generator.

Claims

1. An electrochromic variable transmission glazing comprising:

first and second transparent substrates joined by an organic polymer having a proton conductivity greater than or equal to 10^-5 ohm^-1 cm^-1 at 20°

C., each of said transparent substrates having an electroconductive layer coated on one face thereof facing said polymer, said first transparent substrate further comprising a layer of an electrochromic material between said electroconductive layer and said organic polymer, and said second transparent substrate further comprising a layer of a material which acts as a counterelectrode between said electroconductive layer and said organic polymer, said counterelectrode comprising protonated iridium oxide deposited by cathode sputtering in the presence of hydrogen and oxygen, and said glazing further comprising a pair of current leads connecting the layers of said substrates to a generator wherein current passing through said layers and said polymer causes said glazing to change color.

2. The glazing of claim 1 wherein said first and second transparent substrates are glass sheets.

3. The glazing of claim 1 wherein said organic polymer comprises a solid solution of anhydrous phosphoric acid in poly (oxyethylene) with a molecular weight between 1,000,000 and 5,000,000, and a ratio of the number of oxygen atoms of the polymer to the number of hydrogen atoms of the acid between about 0.4 and 1.

4. The glazing of claim 1 wherein the resistance of each electroconductive layer is less than 10 ohms per square.

5. The glazing of claim 4 wherein said electroconductive layers comprise indium oxide doped with tin which is deposit on said substrates to a thickness of about 400 nm.

6. The glazing of claim 1 wherein said electrochromic material is a tungsten oxide layer deposited on the electroconductive layer of said first substrate to a thickness of about 260 nm.

7. The glazing of claim 6 wherein said counterelectrode comprises a layer of iridium oxide deposited on the electroconductive layer of said second substrate to a thickness between about 200 and 1,000 angstroms.

18. A method for changing the color of a glazing which comprises supplying an electric current to the glazing of claim 1 in an amount sufficient to cause said glazing to change color.

23. The glazing of claim 18, wherein said organic polymer comprises a solid solution of anhydrous phosphoric acid in poly(oxyethylene) with a molecular weight between 1,000,000 and 5,000,000 and a ratio of the number of oxygen atoms of the polymer to the number of hydrogen atoms of the acid between about 0.4 and 1.

8. A method for making an electrochromic variable transmission glazing comprising:

coating one face of first and second transparent substrates with a transparent electroconductive layer thereupon;

coating the electroconductive layer of said first transparent substrate with a layer of electrochromic material;

coating the electroconductive layer of said second transparent substrate with a counterelectrode material layer by depositing protonated iridium oxide by cathode sputtering in the presence of hydrogen and oxygen;

joining said substrates by an organic polymer placed between the electrochromic layer of said first transparent substrate and the counterelectrode of said second substrate, wherein said organic polymer has a proton conductivity greater than or equal to 10^-5 ohm^-1 at 20°

C.; and

connecting said electroconductive layers of said transparent substrates to a generator by a pair of current leads attached thereto.

9. The method of claim 8 wherein said first and second transparent substrates are glass sheets.

10. The method according claim 9, which comprises applying a transparent electroconductive layer having a resistance of less than 10 ohms per square to said transparent substrates.

11. The method according to claim 10 which comprises applying transparent electroconductive layers have a base of indium oxide doped with tin.

12. The method of claim 10 which comprises applying electroconductive layers having a base of tin oxide doped with fluorine.

13. The method according to claim 8 wherein the proton conductive polymer is a solid solution of anhydrous phosphoric acid in poly(oxyethylene) with a molecular weight between 1,000,000 and 5,000,000, and a ratio of the number of oxygen atoms of the polymer to the number of hydrogen atoms of the acid between 0.4 and 1.

14. The method according to claim 8 wherein said layer of electrochromic material is a tungsten oxide layer applied to the electroconductive layer of said first transparent substrate deposited by reactive sputtering assisted by a magnetic field.

15. The method according to claim 8 wherein said layer of electrochromic material is a tungsten oxide layer applied to the electroconductive layer of said first transparent substrate by metallization by vacuum evaporation.

16. The method according to claim 8 wherein said counterelectrode layer comprises applying a layer of iridium oxide to the electroconductive layer of said second transparent substrate by reactive sputtering assisted by a magnetic field from a metal iridium target in an oxygen/hydrogen gas mixture.

17. The method according to claim 16 wherein the iridium oxide layer is applied to a thickness of between 200 and 1,000 angstroms.

19. A method for changing the color of a glazing which comprises making a glazing according to the method of claim 8;

and supplying an electric current to the glazing in an amount sufficient to cause said glazing to change color.

20. An electrochromic variable transmission glazing comprising:

first and second transparent glass sheet substrates joined by an organic polymer having a proton conductivity greater than or equal to 10^-5 ohm^-1 cm^-1 at 20°

C., each of said transparent substrates having an electroconductive layer coated on one face thereof facing said polymer, said first transparent substrate further comprising a layer of a cathodic electrochromic material of tungsten trioxide between said electroconductive layer and said organic layer, and said second transparent substrate further comprising a counterelectrode comprising a layer of iridium copolymer;

wherein said organic polymer comprises a substantially anhydrous solution of an inorganic acid in poly(oxyethylene), and said glazing further comprising a pair of current leads connecting the electroconductive layers of said substrates to a generator, wherein current passing through said layers and said polymers causes said glazing to switch between a neutral faded state and a colored state.

21. The glazing of claim 20, wherein said cathodic electrochromic material is selected from the group of tungsten oxide, vanadium oxide and molybdenum oxide.

22. The glazing of claim 20, wherein said counterelectrode of iridium oxide is deposited on the electroconductive layer of said second substrate to a thickness of between about 200 and 1000 Angstroms.

24. The glazing of claim 20, wherein the resistance of said electroconductive layer is less than 5 ohms per square.

25. The glazing of claim 20, wherein the electroconductive layers each comprise indium oxide doped with tin deposited on said substrates to a thickness of about 400 nm.

26. A method for making an electrochromic variable transmission glazing comprising:

coating one face of each of first and second transparent substrates with a transparent electroconductive layer thereupon,

coating the electroconductive layer of said first transparent substrate with a layer of a cathodic electrochromic material,

coating the electroconductive layer of said second transparent substrate with a counterelectrode comprising a layer of protonated iridium oxide applied by reactive sputtering assisted by a magnetic field from a metal iridium target in an atmosphere of an oxygen/hydrogen gas mixture, said iridium oxide layer having a thickness of between about 200 and 1000 Angstroms;

joining said substrates by an organic polymer having a proton conductivity greater than or equal to 10^-5 ohm^-1 cm^-1 at 20°

C., wherein said polymer is placed between the cathodic electrochromic layer of said first transparent substrate and the counterelectrode of said second substrate, and

connecting the electroconductive layers of said transparent substrates to a generator by a pair of current leads attached thereto.

27. The method according to claim 26, wherein said first and second transparent substrates are glass sheets and which further comprises applying a transparent electroconductive layer having a resistance of less than 5 ohms per square to said sheets.

28. The method according to claim 26, which further comprises applying a transparent electroconductive layer having a base of indium oxide doped with tin to said transparent substrates.

29. The method according to claim 26, which comprises applying an electroconductive layer having a base of tin oxide doped with fluorine to said transparent substrates.

30. The method according to claim 26, which further comprises selecting the proton conductive polymer to be a solid solution of anhydrous phosphoric acid in poly (oxyethylene) with a molecular weight between 1,000,000 and 5,000,000 and a ratio of the number of oxygen atoms of the polymer to the number of hydrogen atoms of the acid between 0.4 and 1.

31. The method according to claim 26, wherein said layer of cathodic electrochromic material is a tungsten oxide layer and is deposited by reactive sputtering assisted by a magnetic field.

32. The method according to claim 26, wherein said layer of cathodic electrochromic material is a tungsten oxide layer and is deposited by vacuum evaporation.