Electropolymerization of enhanced electrochromic (EC) polymer film

• US 20070188845A1
• Filed: 08/13/2004
• Published: 08/16/2007
• Est. Priority Date: 06/25/2001
• Status: Active Grant

• Current Assignee: University of Washington, Washington University In St Louis
• Original Assignee: University of Washington
• Inventors: Taya, Minoru, Xu, Chunye, Liu, Lu
• Granted Patent: US 7,450,290 B2
• Time in Patent Office: Days
• US Class Current: 359/273
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1096 containing other heteroatoms
• CPC Class Codes: C09K 2211/1458 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/1466 containing nitrogen as the only heteroatom
• CPC Class Codes: C09K 2211/1491 containing other combinations of heteroatoms
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G01N 21/553 and using surface plasmons fluorescence excitation G01N21/648; enhanced Raman G01N21/658
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 2001/1555 Counter electrode

Abstract

Electropolymerization of EC monomers is employed to obtain an EC polymer film deposited on a substrate. A first embodiment of a method to produce the film employs cyclic voltammetry alone, while a second embodiment deposits a very thin homogeneous layer using chronoamperometry, and then cyclic voltammetry is employed to increase the density of the film. Another aspect of the present invention is directed to specific web like configurations for a grid of conductive material deposited onto a transparent substrate. The web like configuration is based either on concentric circles, or on concentric ellipses. Yet another aspect of the present invention is directed to an imaging system including a digital window that is disposed between a prism and a patterned analytic layer.

Claims

1. A surface plasmon resonance imaging system, comprising:

(a) a flow cell;

(b) a patterned analytic layer;

(c) a light source directing light to the analytic layer along a first path;

(d) a first optical element in the first path that polarizes the light;

(e) a prism disposed in the first light path between the first optical element and the analytic layer, such that light traveling along the first path passes through the prism;

(f) a digital window disposed between the prism and the analytic layer configured for selectively controlling whether light from the light source traveling along the first path reaches the analytic layer, without effecting the transmission of light from the light source through the prism, the digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and a non-transparent state by applying a voltage thereto, each pixel comprising a laminated electrochromic structure having a cathodic electrochromic polymer layer;

(g) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually selectively applied to each pixel;

(h) a power supply electrically coupled to said electrical conductors and said light source;

(i) a second optical element disposed along a second path, said second optical element focusing light traveling from said analytic layer and passing the light that is focused through said prism; and

(j) a detector disposed in the second path, said detector receiving light focused by the second optical element.

2. The surface plasmon resonance imaging system of claim 1, wherein each laminated electrochromic structure includes:

(a) a first layer comprising a transparent electrode;

(b) a second layer comprising a cathodic polymer layer including a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) a third layer comprising a solid electrolyte;

(d) a fourth layer comprising an anodic polymer layer including a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(e) a fifth layer comprising a transparent electrode.

3. The surface plasmon resonance imaging system of claim 2, the anodic polymer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

4. The surface plasmon resonance imaging system of claim 2, the cathodic polymer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

5. The surface plasmon resonance imaging system of claim 1, wherein each laminated electrochromic structure includes:

(a) a first layer comprising a transparent electrode;

(b) a second layer comprising a cathodic polymer layer including a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) a third layer comprising a solid electrolyte; and

(d) a fourth layer comprising a counter-electrode.

6. The surface plasmon resonance imaging system of claim 5, the cathodic polymer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

7. The surface plasmon resonance imaging system of claim 5, wherein the counter-electrode comprises:

(a) a transparent non-conductive substrate; and

;

(b) a conductive material deposited on the non-conductive substrate in a substantially web-shaped pattern, configured such that the patterned does not reduce a transmittance of the transparent non-conductive substrate by more than about 25 percent.

8. The surface plasmon resonance imaging system of claim 7, wherein the generally web-shaped grid pattern is includes at least one of concentric circles and concentric ellipses.

9. A method for producing a high quality electrochromic polymer film, comprising the steps of:

(a) providing an electrochromic monomer that when polymerized yields an electrochromic polymer; and

(b) using cyclic voltammerty to polymerize the electrochromic monomer, producing the high quality electrochromic polymer film.

10. The method of claim 9, wherein the step of using cyclic voltammerty to polymerize the electrochromic monomer comprises the step of depositing the polymer as a film on a substrate.

11. The method of claim 10, wherein the step depositing the polymer as a film on a substrate comprises the step of depositing the film on a transparent electrode.

12. The method of claim 10, wherein the step depositing the polymer as a film on a substrate comprises the step of depositing the film on a transparent substrate coated with indium tin oxide.

13. The method of claim 9, wherein the step of providing an electrochromic monomer comprises the step of providing [3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

14. The method of claim 9, wherein the step of providing an electrochromic monomer comprises the step of providing dimethyl propylenedioxythiophene.

15. The method of claim 9, wherein the step of providing an electrochromic monomer comprises the step of providing [3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

16. The method of claim 9, wherein the step of providing an electrochromic monomer comprises the step of providing the monomer as a solution in which the monomer is present at a concentration of about 0.01M.

17. The method of claim 9, wherein the step of providing an electrochromic monomer comprises the step of dissolving the monomer in a solvent to achieve a monomer solution.

18. The method of claim 17, wherein the step of dissolving the monomer in a solvent to achieve a monomer solution comprises the step of dissolving the monomer in propylene carbonate.

19. The method of claim 18, wherein the step of dissolving the monomer in propylene carbonate comprises the step of using propylene carbonate to which tetrabutyl ammonium perchlorate has been added.

20. The method of claim 18, wherein the step of dissolving the monomer in propylene carbonate comprises the step of using a solution of about 0.1M of tetrabutyl ammonium perchlorate in propylene carbonate.

21. The method of claim 9, wherein the step of using cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using multiple scan cyclic voltammerty.

22. The method of claim 21, wherein the step of using multiple scan cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using a voltage ranging from about +0.8 volts to about −

1.0 volts.

23. The method of claim 21, wherein the step of using multiple scan cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using a scanning rate of about 20 mV/second.

24. The method of claim 21, wherein the step of using multiple scan cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using about 10 cycles.

25. The method of claim 21, wherein the step of using multiple scan cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using:

(a) a voltage ranging from about +0.8 volts to about −

1.0 volts;

(b) a scanning rate of about 20 mV/second; and

(c) about 10 cycles.

26. The method of claim 9, wherein the step of using cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using a platinum wire is a counter electrode.

27. The method of claim 9, wherein the step of using cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using cyclic voltammerty in the absence of moisture.

28. The method of claim 9, wherein the step of using cyclic voltammerty to polymerize the electrochromic monomer comprises the step of using cyclic voltarnmerty in the absence of water.

29. The method of claim 9, further comprising the step of using chronoamperometry to polymerize a first quantity of the monomer before using cyclic voltammerty to polymerize an additional quantity of the monomer.

30. The method of claim 29, wherein the step of using chronoamperometry to polymerize the first quantity of the monomer comprises the step of using chronoamperometry to deposit a thin film of the polymer on a substrate.

31. The method of claim 30, wherein the step of using cyclic voltammerty to polymerize an additional quantity of the monomer comprises the step of using cyclic voltammerty to deposit additional polymer onto the thin film of the polymer that was deposited using chronoamperometry.

32. The method of claim 29, wherein the step of using chronoamperometry to polymerize the first quantity of the monomer comprises the step of using chronoamperometry for about a hundred seconds at about 0.88 volts.

33. An electrochromic polymer structure comprising a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty.

34. The electrochromic polymer of claim 33, wherein the electrochromic polymer in the base layer and the upper layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

35. The electrochromic polymer of claim 33, wherein the electrochromic polymer in the base layer and the upper layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

36. A counter-electrode useful in an electrochromic device including a cathodic polymer layer;

comprising;

(a) a substantially transparent and substantially non-conductive substrate; and

(b) a conductive material deposited onto the substrate in a generally web-shaped pattern, such that the generally web-shaped pattern does not reduce a transmittance of the transparent non-conductive substrate by substantially more than 25 percent.

37. The counter-electrode of claim 36, wherein the generally web-shaped grid pattern is based on concentric circles.

38. The counter-electrode of claim 36, wherein the generally web-shaped grid pattern is based on concentric ellipses.

39. A laminated electrochromic device comprising:

(a) a first layer comprising a transparent electrode;

(b) a cathodic polymer layer comprising a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) an electrolyte layer comprising a solid electrolyte;

(d) an anodic polymer layer comprising poly a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty; and

(e) another electrode layer comprising a transparent electrode.

40. The laminated electrochromic device of claim 39, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].

41. The laminated electrochromic device of claim 39, wherein the anodic polymer layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

42. A laminated electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer comprising a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) an electrolyte layer comprising a solid electrolyte; and

(d) a counter electrode layer.

43. The laminated electrochromic device of claim 42, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].

44. The laminated electrochromic device of claim 42, wherein the counter-electrode comprises:

(a) a substantially transparent and substantially non-conductive substrate; and

(b) a conductive material deposited onto the substrate in a generally web-shaped pattern, such that the generally web-shaped pattern does not reduce a transmittance of the transparent non-conductive substrate by substantially more than 25 percent.

45. The laminated electrochromic device of claim 44, wherein the generally web-shaped grid pattern is based on at least one of concentric ellipses and concentric circles.

46. The laminated electrochromic device of claim 44, wherein the conductive material comprises gold, further comprising a titanium-tungsten (TiW) layer disposed between the transparent electrode layer and the gold.

47. A dual polymer electrochromic window suitable for architectural and structural applications, comprising:

(a) a first layer comprising a structural glass panel;

(b) a second layer comprising a transparent electrode;

(c) a third layer comprising a cathodic polymer layer including a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) an electrolyte layer comprising a solid electrolyte;

(d) a fourth layer comprising a transparent solid electrolyte;

(e) a fifth comprising an anodic polymer layer a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(c) an electrolyte layer comprising a solid electrolyte;

(f) a sixth layer comprising a transparent electrode;

(g) a seventh layer comprising a structural glass panel;

(h) a first electrical lead coupled to the second layer; and

(i) a second electrical lead coupled to the sixth layer, said first and second electrical leads applying a voltage to the second through sixth layers when coupled to a voltage source, said voltage causing the third and fifth layers to change colors.

48. The dual polymer electrochromic window of claim 47, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].

49. The dual polymer electrochromic window of claim 47, wherein the anodic polymer layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

50. A single polymer electrochromic window suitable for architectural and structural applications, comprising:

(a) a first layer comprising a structural glass panel;

(b) a second layer comprising a transparent electrode;

(c) a third layer comprising a cathodic polymer layer including a relatively thin base layer generated using chronoamperometry, and a relatively thicker upper layer generated using cyclic voltammerty;

(d) a fourth layer comprising a transparent solid electrolyte;

(e) a fifth layer comprising a counter-electrode;

(f) a sixth layer comprising a structural glass panel;

(h) a first electrical lead coupled to the second layer; and

(i) a second electrical lead coupled to the fifth layer, said first and second electrical leads applying a voltage to the second through fifth layers when coupled to a voltage source, said voltage causing the third layer to change color.

51. The single polymer electrochromic window of claim 50, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].

52. The single polymer electrochromic window of claim 50, wherein the counter-electrode comprises:

(a) a substantially transparent and substantially non-conductive substrate; and

(b) a conductive material deposited onto the substrate in a generally web-shaped pattern, such that the generally web-shaped pattern does not reduce a transmittance of the transparent non-conductive substrate by substantially more than 25 percent.

53. The laminated electrochromic device of claim 52, wherein the generally web-shaped grid pattern is based on at least one of concentric ellipses and concentric circles.

54. The laminated electrochromic device of claim 52, wherein the conductive material comprises gold, further comprising a titanium-tungsten (TiW) layer disposed between the transparent electrode layer and the gold.