Electrochromic display device and electrodeposition display device

• US 20030156314A1
• Filed: 03/06/2003
• Published: 08/21/2003
• Est. Priority Date: 12/27/2000
• Status: Active Grant

• Current Assignee: Sony Deutschland GmbH (Sony Group Corp.)
• Original Assignee: Sony Deutschland GmbH (Sony Group Corp.)
• Inventors: Noda, Kazuhiro, Shinozaki, Kenji, Yasuda, Akio, Kuwahara, Mieko, Udaka, Toru
• Granted Patent: US 6,992,808 B2
• Time in Patent Office: Days
• US Class Current: 359/273
• CPC Class Codes: G02F 1/1508 using a solid electrolyte
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/1635 the pixel comprises active switching elements, e.g. TFT
• CPC Class Codes: G02F 2001/164 the electrolyte is made of polymers

Abstract

Between each transparent pixel electrode driven by TFT as a drive device and a common electrode, a polymer layer located in contact with the transparent pixel electrode and electrically active to change in color by electrochemical oxidization or reduction and a polymeric solid electrolytic layer located in contact with the polymer layer and containing a coloring agent are interposed. since electrochemical oxidization or reduction brings about a color change, the contrast and the black concentration can be enhanced, and bronzing after long-time use does not occur.

Claims

1. An electrochromic display device comprising:

a first transparent electrode controlled by a drive device;

a polymer material layer located in contact with said transparent electrode and electrically active to be changeable in color by electrochemical oxidation or reduction;

a polymeric solid electrolytic layer located in contact with said polymer material layer and containing a coloring agent; and

a second electrode located to interpose said polymer material layer and said polymeric solid electrolytic layer between said first transparent electrode and said second electrode.

2. The electrochromic display device according to claim 1 wherein the polymer material forming said polymer material layer is polypyrole, polyaniline, polythiophene, polyazulene, or a mixture thereof.

3. The electrochromic display device according to claim 1 wherein the polymer material forming said polymer material layer is a polymer obtained by electric oxidizing polymerization of pryrole, aniline, thiophene, azulene, or their derivatives.

4. The electrochromic display device according to claim 1 wherein the polymeric solid electrolyte forming said polymeric solid electrolytic layer is polyethylene oxide, polypropylene oxide, polyethylene imine or polystyrene sulfide whose framework structure unit is expressed by —

(C—

C—

O)_n—

, —

(C—

C(CH₃)—

O)_n—

, —

(C—

C—

N)_n—

or —

(C—

C—

S)_n—

, or a polymer material including any of those materials as the main chain structure thereof and having branches, or polymethylmethacrylate, polyvinylidene fluoride, polyvinylidene chloride, polycarbonate, or a mixture or lamination thereof mixed with metallic salt, or alkyl ammonium salt.

5. The electrochromic display device according to claim 1 wherein said polymeric solid electrolytic layer is a lamination of a plurality of layers, and said coloring agent is contained only in one or some of said layers.

6. The electrochromic display device according to claim 1 wherein a plasticizer selected from water, ethyl alcohol, isopropyl alcohol, propylene carbonate, dimethyl carbonate, ethylene carbonate, γ

-butylolactone, acetonitrile, sulfolane, dimethoxyethane, dimethylformamide, dimethylsulfoxide, or mixtures thereof, is added to said polymeric solid electrolytic layer.

7. The electrochromic display device according to claim 1 wherein said coloring agent is an inorganic pigment, an organic pigment or a coloring matter.

8. The electrochromic display device according to claim 1 wherein said inorganic pigment is powder of titanium dioxide, calcium carbonate, magnesium oxide or aluminum oxide.

9. The electrochromic display device according to claim 1 wherein said first transparent electrode contains SnO₂, In₂O₃ or their mixture as a major component thereof.

10. The electrochromic display device according to claim 1 wherein said second electrode is a metal thin film.

11. The electrochromic display device according to claim 1 further comprising a third electrode independent from said first transparent electrode and said second electrode.

12. The electrochromic display device according to claim 1 wherein said third electrode is located as an electrically insulated element on a common plane together with said first transparent electrode and said second electrode.

13. An electrodeposition type display device comprising:

a first transparent electrode controlled by a drive device;

a polymeric solid electrolytic layer containing a coloring agent and metal ions; and

a second electrode located to interpose said polymeric solid electrolytic layer between said first transparent electrode and said second electrode.

14. The electrodeposition type display device according to claim 13 wherein said metal ions are bismuth, copper, silver, lithium, iron, chromium, nickel or cadmium ions, or a combination thereof.

15. The electrodeposition type display device according to claim 13 wherein the polymeric solid electrolyte forming said polymeric solid electrolytic layer is polyethylene oxide, polypropylene oxide, polyethylene imine or polystyrene sulfide whose framework structure unit is expressed by —

(C—

C—

O)_n—

, —

(C—

C(CH₃)—

O)_n—

, —

(C—

C—

N)_n—

or —

(C—

C—

S)_n—

, or a polymer material including any of those materials as the main chain structure thereof and having branches, or polymethylmethacrylate, polyvinylidene fluoride, polyvinylidene chloride, polycarbonate, or a mixture or lamination thereof mixed with metallic salt, or alkyl ammonium salt.

16. The electrodeposition type display device according to claim 13 wherein said polymeric solid electrolytic layer is a lamination of a plurality of layers, and said coloring agent is contained only in one or some of said layers.

17. The electrodeposition type display device according to claim 13 wherein a plasticizer selected from water, ethyl alcohol, isopropyl alcohol, propylene carbonate, dimethyl carbonate, ethylene carbonate, γ

-butylolactone, acetonitrile, sulfolane, dimethoxyethane, dimethylformamide, dimethylsulfoxide, or mixtures thereof, is added to said polymeric solid electrolytic layer.

18. The electrodeposition type display device according to claim 13 wherein said coloring agent is an inorganic pigment, an organic pigment or a coloring matter.

19. The electrodeposition type display device according to claim 18 wherein said inorganic pigment is powder of titanium dioxide, calcium carbonate, magnesium oxide or aluminum oxide.

20. The electrodeposition type display device according to claim 13 wherein said first transparent electrode contains SnO₂, In₂O₃ or their mixture as a major component thereof.

21. The electrodeposition type display device according to claim 13 wherein said second electrode is a metal thin film.

22. The electrodeposition type display device according to claim 13 wherein a material layer capable of introducing and releasing ions or a material layer capable of producing an electrochemical oxidation-reduction reaction is placed between said polymeric solid electrolytic layer and said second electrode.

23. The electrodeposition type display device according to claim 22 wherein said material layer contains carbon.

24. The electrodeposition type display device according to claim 22 wherein said polymeric solid electrolytic layer contains a growth inhibitor for inhibiting deposition of said metal ions.

25. The electrodeposition type display device according to claim 13 wherein said growth inhibitor has a group including an oxygen atom or a sulfur atom.

26. The electrodeposition type display device according to claim 13 wherein said polymeric solid electrolytic layer contains a reducing agent or a oxidizer for suppressing side reaction which may occur in any of said first transparent electrode and said second electrode when said metal ions deposit.

27. The electrodeposition type display device according to claim 13 wherein quantity of electricity supplied to between said electrodes is adjusted in the range not smaller than 5 mC and not larger than 20 mC per square centimeter.

28. An electrochromic display apparatus comprising a sheet-like array of a plurality of electrochromic display elements each including:

a first transparent electrode controlled by a drive device;

a polymer material layer located in contact with said transparent electrode and electrically active to be changeable in color by electrochemical oxidation or reduction;

a polymeric solid electrolytic layer located in contact with said polymer material layer and containing a coloring agent; and

a second electrode located to interpose said polymer material layer and said polymeric solid electrolytic layer between said first transparent electrode and said second electrode.

29. An electrodeposition type display device comprising a sheet-like array of a plurality of electrodeposition type display elements each including:

a first transparent electrode controlled by a drive device;

a polymeric solid electrolytic layer containing a coloring agent and metal ions; and

a second electrode located to interpose said polymeric solid electrolytic layer between said first transparent electrode and said second electrode.

30. A method of manufacturing an electrochromic display apparatus comprising:

the step of forming transparent pixel electrodes and drive devices on a transparent support structure;

the step of forming a polymer material layer electrically active and changeable in color by electrochemical oxidization or reduction, and a polymeric solid electrolytic layer containing a coloring agent on said transparent support structure having formed said transparent pixel electrodes and said drive devices; and

the step of forming a common electrode opposed to said transparent pixel electrodes.

31. A method of manufacturing an electrodeposition type display apparatus comprising:

the step of forming transparent pixel electrodes and drive devices on a transparent support structure;

the step of forming a polymeric solid electrolytic layer containing metal ions and a coloring agent on said transparent support structure having formed said transparent pixel electrodes and said drive devices; and

the step of forming a common electrode opposed to said transparent pixel electrodes.