Electrochromic devices

• US 20030227664A1
• Filed: 11/13/2002
• Published: 12/11/2003
• Est. Priority Date: 05/24/2000
• Status: Active Grant

• Current Assignee: Dritte Patentportfolio Beteiligungsgesellschaft mbH & Co. KG
• Original Assignee: SCHOTT North America, Inc. (Carl-Zeiss-Stiftung), Magna Donnelly Corporation (Magna International Incorporated)
• Inventors: Agrawal, Anoop, Tonazzi, Juan Carlos L., Cronin, John P., Feinstein, Yelena, Holdmann, Torsten, Gudgel, Todd J., Hansen, Stephan G., Zhang, Raymond L., Ingle, Andrew R.
• Granted Patent: US 6,906,842 B2
• Time in Patent Office: Days
• US Class Current: 359/269
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 1/157 Structural association of cells with optical devices, e.g. reflectors or illuminating devices
• CPC Class Codes: G02F 2001/1555 Counter electrode
• CPC Class Codes: G02F 2203/48 Variable attenuator

Abstract

The invention includes many applications for electrochromic devices that require neutral colors and patterned electrodes. It uses novel materials, ways of making the materials, device configurations and applications. In one aspect, the device also includes electrical leads (115,116), transparent conductor layers (135,136), patterned EC layers (143,144), an etch line (99) and a substrate (125).

Claims

1. A counterelectrode for use in an electrochromic device comprising vanadium oxide doped with at least one dopant selected from the group consisting of tin oxide and antimony oxide.

2. An electrochromic device having an electrochromic layer including an electrochromic coating and a counterelectrode according to claim 1.

3. An electrochromic device according to claim 2 wherein the electrochromic coating comprising tungsten oxide.

4. An electrochromic device according to claim 3 wherein the electrochromic coating additionally comprises at least one dopant selected from the group consisting of alkali metal oxides and transition metal oxides.

5. An electrochromic device according to claim 4 wherein the alkali metal oxide dopant is lithium oxide, sodium oxide or potassium oxide.

6. An electrochromic device according to claim 4 wherein the transitional metal oxide dopant is vanadium oxide, molybdenum oxide, cobalt oxide, chromium oxide or copper oxide.

7. An electrochromic device according to claim 3 wherein the electrochromic coating has an atomic ratio of vanadium and molybdenum to tungsten is in the range of 0.03 to 0.4 and the ratio of molybdenum to vanadium is in the range of 0.2 to 2.

8. A method of making an electrochromic coating according to claim 3 comprising the steps of:

(a) preparing a solution comprising soluble sources of tungsten, vanadium and molybdenum and an organic solvent;

(b) applying the solution to a substrate; and

(c) heating the substrate to form the electrochromic coating thereon.

9. A method according to claim 8 wherein the step of preparing the solution comprises combining (i) a solution of tungsten peroxy ester in ethanol with (ii) the product of the reaction of molybdenum (II) acetate dimer and hydrogen peroxide and with (iii) a solution of vanadic acid in ethanol.

10. A method according to claim 8 wherein the heating step is carried out at a temperature of about 250°

C.

11. In a method for making a vanadium oxide-coated substrate comprising the steps of (a) combining (i) an organic solvent, and (ii) a soluble vanadium source to form a solution;

(b) applying the solution to a substrate; and

(c) heating the substrate to form a coating thereon, the improvement comprising adding an organic base to the solution prior to applying the solution to the substrate.

12. A method according to claim 11 wherein the organic base is triethylamine.

13. A method according to claim 11 or 12 wherein the heating step includes a humid firing step.

14. A vanadium oxide coating made by the method of claim 13 and having a charge capacity of at least 20 mC/cm² and a haze less than 10%.

15. A method according to claim 11, 12, 13 or 14 wherein step (a) comprises, in addition, combining a soluble lithium source.

16. An electrochromic device having an electrochromic layer comprising a patterned tungsten oxide coating and having a patterned, planar substrate.

17. A device according to claim 16 wherein at least in one state of coloration the pattern on the coating and the pattern on the substrate interfere to provide Moiré

fringes.

18. A device according to claim 16 or 17 wherein the pattern on the coating is selected from the group of patterns consisting of concentric circles, wavy lines, circular dots of non-uniform size, spots, straight lines and straight lines converging toward center.

19. A device according to claim 16 or 17 wherein the pattern on the coating and the pattern on the substrate are selected from the group of patterns consisting of concentric circles, wavy lines, circular dots of non-uniform size, spots, straight lines and straight lines converging toward center.

20. Use of a device of claim 16, 17, 18 or 19 in a lens, prism, optical or photographic filter.

21. Use of a device of claim 16, 17, 18 or 19 in a microscope, gunsight, telescope, binocular, endoscope, periscope, theodilite or microwave attenuation device.

22. An electrochromic device comprising a lens having two plano-convex substrates having faces disposed in opposing relation to each other and being coated with a transparent conducting material, an electrochromic layer coating the inside face of at least one of the substrates, an electrolyte layer containing an electrolyte disposed between the substrates and means for sealing the lens.

23. An electrochromic lens device comprising two concave substrates having faces disposed in opposing relation to each other and being coated with a layer of transparent conductor material, an electrochromic layer coating at least one of the layers of transparent conductor material, an electrolyte layer containing an electrolyte and being disposed between the electrochromic layer and the layer of transparent conductor material, and means for sealing the lens.

24. An electrochromic prism device comprising a first substrate having a planar face coated with a transparent conducting coating layer, a second substrate having a planar face coated with stripes of transparent conductive coating, the coated planar faces being disposed in opposing relation to each other, an electrochromic layer coating the transparent conductive coating of the second substrate, an electrolyte layer containing an electrolyte and being disposed between the transparent conducting coating layer of the first substrate and the electrochromic layer of the second substrate, and means for sealing the prism.

25. A reflective modulator device comprising a first substrate having a planar face coated with a reflective coating layer and an electrochromic layer coating the reflective coating layer, a second substrate having a planar face disposed in opposing relation to the electrochromic layer of the first substrate and being coated with a conductive coating layer, the conductive coating layer having at least one aperture, an electrolyte layer containing an electrolyte and being disposed between the electrochromic layer coating the first substrate and the conductive coating layer coating the second substrate, and means for sealing the device.

26. A reflective modulator device according to claim 25 wherein the at least one aperture is a single hole, a single slit or a multiplicity of holes.

27. A reflective modulator device according to claim 25 or 26 wherein the aperture has a diameter less than the thickness of the electrolyte layer.

28. A waveguide device comprising a planar silicon substrate having a channel in a face of the substrate, the channel being coated with an electrochromic layer, a planar substrate having a conductive layer coating one face thereof, the face being disposed in opposing relation to the channel face of the silicon substrate, an electrolyte layer containing an electrolyte disposed between the conductive coating layer and the channel face of the silicon substrate, and means for sealing the device.

29. A waveguide device according to claim 28 wherein the electrochromic layer comprises tungsten oxide and the layer fills the channel.

30. A waveguide device according to claim 28 or 29 wherein the electrolyte layer has a refractive index lower than the refractive index of the electrochromic layer.

31. A microwave attenuator device comprising a planar substrate, a conductive film coating one face of the substrate, the film having a series of offsetting parallel grooves in the surface of the film, electric terminals attached to the conductive firm, means for controlling the temperature of the device connected to the terminals, and a thermochromic film coating the conductive film.

32. A microwave attenuator device according to claim 31 wherein the conductive film is chrome, copper, gold or stainless steel and the thermochromic film is vanadium oxide.

33. An electrochromic device for microwave attenuation comprising two planar substrates having inside faces and outside faces, the faces being disposed in opposing relation to each other, a first conductive coating layer coating at least one of the inside faces, an electrochromic layer coating one of the first conductive coating layers, wherein the electrochromic layer comprises tungsten oxide, an electrolyte layer containing an electrolyte disposed between the electrochromic layer and the first conductive coating layer and a second conductive coating layer coating at least one of the outside faces of the substrate and having an aperture therethrough.

34. An electrochromic device for microwave attenuation comprising two planar substrates having inside faces disposed in opposing relation to each other, two conductive coating layers coating the inside face of each substrate, each conductive coating layer comprising a series of longitudinal stripes arranged in parallel relation on the face of the substrate, an electrochromic layer coating one of the conductive coating layers and an electrolyte layer containing electrolyte disposed between the electrochromic layer and conductive coating layer.

35. An electrochromic device comprising two planar substrates having inside faces disposed in opposing relation to each other, an electrode layer comprising two parallel stripes disposed along the edges of one of the inside faces and having a plurality of interdigitated fingers, an electrochromic layer coating the electrode layer, an insulating layer between the electrode layer and the electrochromic layer and an electrolyte layer containing electrolyte disposed between the electrochromic layer and the inside face of the opposed substrate.