Electrochromic organic polymer synthesis and devices utilizing electrochromic organic polymers

• US 7,002,722 B2
• Filed: 01/12/2004
• Issued: 02/21/2006
• Est. Priority Date: 06/25/2001
• Status: Expired due to Term

• Current Assignee: University of Washington
• Original Assignee: University of Washington
• Inventors: Taya, Minoru, Xu, Chunye
• Primary Examiner(s): Schwartz, Jordan M.
• Assistant Examiner(s): Stultz, Jessica
• Application Number:
  US10/755,433
• Publication Number:
  US 20040143091A1
• Time in Patent Office: 771 Days
• Field of Search: 359/273, 359/265, 359/267, 359/275, 359321-322, 348/817, 345/49, 345/105, 252/583, 204/290.07
• US Class Current: 359/273
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: H10K 85/1135 Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Abstract

Large contrast ratio and rapid switching laminated electrochromic (EC) polymer device includes transparent electrode, cathodic EC polymer, gel electrolyte, and counter-electrode. Preferably the cathodic EC polymer is a poly(3,4-propylenedioxythiophene) derivative, PProDOT-Me₂. Counter-electrode is a conductive coating deposited on transparent substrate, with preferred coatings including gold and highly conductive carbon. Lithography and sputtering can be employed to pattern a gold layer, while screen printing can be employed to similarly pattern graphite. Empirical studies of preferred device indicate a color change of high contrast ratio of transmittance (>50% T) is rapidly (0.5–1s) obtained upon applied 2.5V, repeatable to at least 10,000 times, as estimated by electrochemistry. Dual layer EC devices including PProDOT-Me₂ are also disclosed, as are methods for synthesizing preferred EC polymers. Preferred synthesis method for obtaining PProDOT-Me₂ involves refluxing reagents in toluene in the presence of catalyst, while continually removing methanol byproduct from refluxing solution.

Claims

1. A digital window suitable for use with pixilated addressing, comprising:

(a) a digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by selectively applying a voltage thereto, each pixel comprising a laminated electrochromic structure having a cathodic electrochromic polymer layer and no anodic electrochromic polymer layer; and

(b) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually applied to each pixel.

2. The digital window of claim 1, wherein each pixel is less than about 50 microns in size.

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

4. The digital window of claim 1, wherein each laminated electrochromic structure comprises:

(a) a first layer comprising a transparent electrode;

(b) a second layer comprising a cathodic polymer layer;

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

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

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

6. The digital window of claim 4, wherein the counter-electrode comprises:

(a) a transparent non-conductive substrate; and

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

7. The digital window of claim 6, wherein the conductive material comprises gold, further comprising a layer comprising a titanium-tungsten (TiW) layer disposed between the transparent non-conductive substrate and the gold.

8. The digital window of claim 6, wherein the conductive material comprises highly conductive carbon.

9. The digital window of claim 6, wherein the patterned layer comprises a grid.

10. A multicolor display comprising:

(a) a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by applying a voltage, each pixel comprising a laminated electrochromic structure including a cathodic electrochromic polymer layer, at least some of the pixels further comprising an anodic polymer layer switchable between two different colors, the anodic polymer layer comprising poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole]; and

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

11. The multicolor display of claim 10 wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

12. A digital window suitable for use with pixilated addressing, comprising:

(a) a digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by selectively applying a voltage thereto, each pixel comprising a laminated electrochromic structure including;

(i) a transparent electrode;

(ii) a cathodic electrochromic polymer layer comprising poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine];

(iii) an electrolyte layer comprising a solid electrolyte;

(iv) an anodic polymer layer; and

(v) another transparent electrode; and

(b) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually applied to each pixel.

13. The digital window of claim 12, wherein the anodic polymer layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole].

14. A digital window suitable for use with pixilated addressing, comprising:

(a) a digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by selectively applying a voltage thereto, each pixel comprising a laminated electrochromic structure including;

(i) a transparent electrode;

(ii) a cathodic electrochromic polymer layer;

(iii) an electrolyte layer comprising a solid electrolyte;

(iv) an anodic polymer layer comprising poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole]; and

(v) another transparent electrode; and

(b) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually applied to each pixel.