Electrophoretic displays using nanoparticles

• US 6,538,801 B2
• Filed: 11/12/2001
• Issued: 03/25/2003
• Est. Priority Date: 07/19/1996
• Status: Expired due to Term

• Current Assignee: E Ink Corporation (E Ink Holdings Incorporated)
• Original Assignee: E Ink Corporation (E Ink Holdings Incorporated)
• Inventors: McCreary, Michael, Drzaic, Paul S., Jacobson, Joseph M., Zehner, Robert W., Pullen, Anthony E., Duthaler, Gregg M., Wang, Jianna, Morrison, Ian D., Pratt, Emily J., Gray, Caprice L.
• Primary Examiner(s): Dang, Hung Xuan
• Application Number:
  US10/054,721
• Publication Number:
  US 20020145792A1
• Time in Patent Office: 498 Days
• Field of Search: 359/296, 359/529, 359/530, 359/536, 359/538, 359/539, 359/541, 349/86, 349/89, 345/107, 345/86
• US Class Current: 359/296
• CPC Class Codes: B41J 2/01 Ink jet
• CPC Class Codes: B41J 2/02 generating a continuous ink jet
• CPC Class Codes: B41J 3/4076 printing on rewritable, bistable "electronic paper" by a focused electric or magnetic field
• CPC Class Codes: B82Y 20/00 Nanooptics, e.g. quantum optics or photonic crystals
• CPC Class Codes: C09D 11/30 Inkjet printing inks
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: G02B 26/026 based on the rotation of particles under the influence of an external field, e.g. gyricons, twisting ball displays based on orientable dipolar particles G02F1/172; based on electrophoresis G02F1/167
• CPC Class Codes: G02F 1/133305 Flexible substrates, e.g. plastics, organic film
• CPC Class Codes: G02F 1/13336 Combining plural substrates to produce large-area displays, e.g. tiled displays
• CPC Class Codes: G02F 1/1334 based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• CPC Class Codes: G02F 1/13439 characterised by their electrical, optical, physical properties; materials therefor; method of making
• CPC Class Codes: G02F 1/1347 Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
• CPC Class Codes: G02F 1/167 by electrophoresis
• CPC Class Codes: G02F 1/16757 Microcapsules
• CPC Class Codes: G02F 2201/16 series; tandem
• CPC Class Codes: G02F 2201/44 Arrangements combining different electro-active layers, e.g. electrochromic, liquid crystal or electroluminescent layers
• CPC Class Codes: G02F 2202/28 Adhesive materials or arrangements
• CPC Class Codes: G02F 2202/36 Micro- or nanomaterials
• CPC Class Codes: G04B 47/00 Time-pieces combined with other articles which do not interfere with the running or the time-keeping of the time-piece clockwork cases for special purposes G04B37/12; clocks with magnifying glass built in the face G04B39/00; time-pieces in which parts or cases produce special effects, e.g. aesthetic effects, G04B45/00, particularly with inscriptions or pictures moved by hand G04B45/003, with specially shaped cases or parts G04B45/0069; combination of writing or drawing implements with devices for indicating time B43K29/087; combined with cameras, projectors, or photographic printing apparatus G03B29/00
• CPC Class Codes: G09F 9/372 the positions of the elements being controlled by the application of an electric field
• CPC Class Codes: H05K 1/097 : Inks comprising nanoparticles and specially adapted for being sintered at low temperature H05K1/095 takes precedence
• CPC Class Codes: H05K 3/105 : by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
• CPC Class Codes: H05K 3/1241 : by ink-jet printing or drawing by dispensing
• CPC Class Codes: H10K 10/46 : Field-effect transistors, e.g. organic thin-film transistors [OTFT] H10K10/43 takes precedence
• CPC Class Codes: H10K 10/462 : Insulated gate field-effect transistors [IGFETs]
• CPC Class Codes: H10K 85/30 : Coordination compounds
• CPC Class Codes: H10K 85/60 : Organic compounds having low molecular weight H10K85/10 - H10K85/50 take precedence

Abstract

An electrophoretic display comprises a fluid and a plurality of nanoparticles having diameters substantially less the wavelengths of visible light such that, when the nanoparticles are in a dispersed state and uniformly dispersed throughout the fluid, the fluid presents a first optical characteristic, but when the nanoparticles are in an aggregated state in which they are gathered into aggregates substantially larger than the individual nanoparticles, the fluid presents a second optical characteristic different from the first optical characteristic. The electrophoretic display further comprises at least one electrode arranged to apply an electric field to the nanoparticle-containing fluid and thereby move the nanoparticles between their dispersed and aggregated states. Various compound particles comprising multiple nanoparticles, alone or in combination with larger objects, and processes for the preparation of such compound particles, are also described.

Claims

1. A process for forming a nanoparticle assembly comprising a nanoparticle secured to an object via a linking group, which process comprises:

treating a nanoparticle with a linking reagent comprising said linking group and a first functional group capable of reacting with said nanoparticle under the conditions of said treatment, thereby causing said first functional group to react with said nanoparticle and secure said linking group to said nanoparticle;

thereafter treating said nanoparticle carrying said linking group with a modifying reagent effective to generate a second functional group on the linking group, said second functional group being capable of reacting with said object; and

thereafter contacting said nanoparticle carrying said linking group and said second functional group with said object under conditions effective to cause said second functional group to react with said object and thereby form said nanoparticle assembly.

2. A process according to claim 1 wherein said object is a second nanoparticle.

3. A process according to claim 2 wherein the two nanoparticles are formed of the same material.

4. A process according to claim 3 wherein said material is an electrically conductive metal.

5. A process according to claim 4 wherein said electrically conductive metal is silver, gold, platinum, palladium or an alloy of any of these metals.

6. A process according to claim 2 wherein the two nanoparticies bear charges of opposite polarity.

7. A process according to claim 2 wherein the two nanoparticles have diameters not greater than about 60 nm.

8. A process according to claim 1 wherein said object is an electrode, and in said process a plurality of nanoparticles are secured to said electrode via separate linking groups.

9. A process according to claim 1 wherein said generation of said second functional group is carried out in the presence of said object.

10. A process according to claim 1 wherein said first functional group comprises a thiol, amine, phosphine or hydroxyl group.

11. A process according to claim 1 wherein said linking group comprises an alkyl or alkylene group.

12. A process according to claim 1 wherein said linking group has a length not greater than about 50 nm.

13. A process according to claim 1 wherein the generation of said second functional group is effected by removal of a protecting group from a protected form of said second functional group.

14. A process according to claim 13 wherein said second functional group is a thiol, amine, phosphine or hydroxyl group.

15. A process according to claim 14 wherein said protected form of second functional group comprises a thiol group protected by a benzyl, acetyl, alkyl, carbonate or carbamate protecting group.

16. A process according to claim 14 wherein said protected form of said second functional group comprises an amine group protected by a benzyl, carbamate, carbonate or alkyl group, or in the form of an imine, amide or urea grouping.

17. A process for forming a nanoparticle assembly comprising first and second nanoparticles secured to each other via a linking group, said first and second nanoparticles bearing charges of opposite polarity, which process comprises:

treating said first nanoparticle with a linking reagent comprising said linking group and a first functional group capable of reacting with said first nanoparticle under the conditions of said treatment, thereby causing said first functional group to react with said first nanoparticle and secure said linking group to said first nanoparticle;

thereafter treating said first nanoparticle carrying said linking group with a modifying reagent effective to generate a second functional group on the linking group, said second functional group being capable of reacting with said second nanoparticle; and

thereafter contacting said first nanoparticle carrying said linking group and said second functional group with said second nanoparticle under conditions effective to cause said second functional group to react with said second nanoparticle and thereby form said nanoparticle assembly.

18. A process according to claim 17 wherein said first and second functional groups are the same, and the generation of said second functional group is effected by removal of a protecting group from a protected form of said second functional group.

19. An electrophoretic display comprising a fluid, a plurality of a first species of nanoparticles in the fluid and a plurality of a second species of nanoparticles in the fluid, the first and second species of nanoparticles differing in electrophoretic mobility, the display having a viewing surface through which the nanoparticle-containing fluid can be viewed, the display having:

(a) a first display state in which the first and second species of nanoparticles are dispersed through the fluid;

(b) a second display state in which the first species of nanoparticles are aggregated and visible through the viewing surface; and

(c) a third display state in which the second species of nanoparticles are aggregated and visible through the viewing surface,

the first, second and third display states differing in at least one optical characteristic.

20. An electrophoretic display according to claim 19 wherein the fluid is colored and the first and second species of nanoparticles bear charges of opposite polarity, and wherein the first display state displays the color of the fluid, the second display state displays the color of the first species of nanoparticles aggregated adjacent the viewing surface and the third display state displays the color of the second species of nanoparticles aggregated adjacent the viewing surface.

21. An electrophoretic display according to claim 19 wherein the fluid is light-transmissive and the display further comprises a reflective or colored surface on the opposed side of the fluid from the viewing surface, and wherein the first display state displays the reflective or colored surface through the fluid.

22. An electrophoretic display according to claim 21 wherein the first and second species of nanoparticles bear charges of opposite polarity, and wherein the second display state displays the color of the first species of nanoparticles aggregated adjacent the viewing surface and the third display state displays the color of the second species of nanoparticles aggregated adjacent the viewing surface.

23. An electrophoretic display according to claim 21 wherein the first and second species of nanoparticies bear charges of the same polarity but the first species of nanoparticles has a higher electrophoretic mobility than the second species of nanoparticles, such that in the second display state the first and second species of nanoparticles are both aggregated against the viewing surface, but with the first species of nanoparticles closer to the viewing surface, so that the first species are visible through the viewing surface, and such that in the third display state the first and second species of nanoparticles are both aggregated adjacent the reflective or colored surface, but with the first species of nanoparticles closer to the reflective or colored surface, so that the second species are visible through the viewing surface.

24. An electrophoretic display according to claim 19 wherein the fluid and the two species of nanoparticles are encapsulated within at least one capsule.

25. An electrophoretic display according to claim 24 wherein the fluid and the two species of nanoparticles are encapsulated within a plurality of microcapsules having diameters in the range of about 10 to about 500 μ

m.

26. An electronic display comprising, in order:

a light-transmissive first electrode forming a viewing surface;

an electrophoretic medium comprising a plurality of nanoparticles in a light-transmissive fluid;

a light transmissive second electrode;

an electro-optic medium; and

a third electrode,

the electro-optic medium being capable of being switched between a first optical state and a second optical state by application of an electric field between the second and third electrodes,

the electronic display having;

(a) a first display state in which the plurality of nanoparticles are dispersed through the fluid and the electro-optic medium is in its first optical state and visible through the viewing surface;

(b) a second display state in which the plurality of nanoparticles are dispersed through the fluid and the electro-optic medium is in its second optical state and visible through the viewing surface; and

(c) a third display state in which the plurality of nanoparticles are aggregated and visible through the viewing surface,

the first, second and third display states differing in at least one optical characteristic.

27. An electronic display according to claim 26 wherein said electrophoretic medium comprises a plurality of a first species of nanoparticles and a plurality of a second species of nanoparticles, the first and second species of nanoparticles differing in electrophoretic mobility, and wherein, in the third display state, the plurality of first nanoparticles are aggregated and visible through the viewing surface, the electronic display having a fourth display state in which the plurality of second nanoparticles are aggregated and visible through the viewing surface, the first, second, third and fourth display states differing in at least one optical characteristic.

28. An electronic display according to claim 27 wherein said electro-optic medium comprises a second electrophoretic medium comprising a second fluid, a plurality of a third species of nanoparticles in said second fluid, and a plurality of a fourth species of nanoparticles in said second fluid, said third and fourth species of nanoparticles differing in electrophoretic mobility, and wherein, in the first display state, the plurality of third nanoparticles are aggregated and visible through the viewing surface, and in the second display state the plurality of fourth nanoparticles are aggregated and visible through the viewing surface, the electronic display having a fifth display state in which the first and second species of nanoparticles are dispersed through the associated fluid, and the third and fourth species of nanoparticles are dispersed through the second fluid, the first, second, third, fourth and fifth display states differing in at least one optical characteristic.

29. An electronic display according to claim 28 wherein the second fluid is colored and the third and fourth species of nanoparticles bear charges of opposite polarity, and wherein the fifth display state displays the color of the second fluid.

30. An electronic display according to claim 28 wherein the second fluid is light-transmissive and the display further comprises a reflective or colored surface on the opposed side of the second fluid from the viewing surface, and wherein the fifth display state displays the reflective or colored surface through the second fluid.

31. An electronic display according to claim 28 wherein the first through fifth display states comprise white, black, red, green and blue states.

32. An electronic display according to claim 28 wherein the first through fifth display states comprise white, black, yellow, cyan and magenta states.

33. An electronic display according to claim 26 wherein said electro-optic medium comprises a second electrophoretic medium.

34. An electronic display according to claim 33 wherein said second electrophoretic medium comprises a plurality of nanoparticles in a second fluid.

35. An electronic display according to claim 34 wherein the second fluid and the third and fourth species of nanoparticles are encapsulated within at least one capsule.

36. An electronic display according to claim 35 wherein the second fluid and the third and fourth species of nanoparticles are encapsulated within a plurality of microcapsules having diameters in the range of about 10 to about 500 μ

m.

37. An electronic display according to claim 26 wherein the fluid and the nanoparticles are encapsulated within at least one capsule.

38. An electronic display according to claim 37 wherein the fluid and the nanoparticles are encapsulated within a plurality of microcapsules having diameters in the range of about 10 to about 500 μ

m.

39. A nanoparticle assembly comprising a nanoparticle having a diameter substantially less than the wavelengths of visible light, an object separate from the nanoparticle, and a flexible filament connecting the nanoparticle and the object, such that at least one optical characteristic of the nanoparticle varies with the spacing between the nanoparticle and the object.

40. A nanoparticle assembly according to claim 39 wherein at least one of the nanoparticle and the object is electrically charged such that, upon application of an electric field to the assembly, the spacing between the nanoparticle and the object will change.

41. A nanoparticle assembly according to claim 40 wherein the object is a second nanoparticle so that the assembly comprises at least two nanoparticles attached to a single filament.

42. A nanoparticle assembly according to claim 40 wherein the object comprises an electrically charged body affixed at or adjacent one end of the filament, the filament having its opposed end attached to a fixed body, the filament having a plurality of nanoparticles fixed thereto at spaced intervals between the fixed body and the electrically charged body, such that upon application of an electric field to the unit, the spacing between the fixed body and the electrically charged body will change, thereby changing the distances between the nanoparticles.

43. A nanoparticle assembly according to claim 40 wherein the object comprises a first electrically charged body affixed at or adjacent one end of the flexible filament, the filament having its opposed end attached to a second electrically charged body bearing a charge of opposite polarity to the first electrically charged body, the filament having a plurality of nanoparticles fixed thereto at spaced intervals between the two electrically charged bodies, such that upon application of an electric field to the unit, the spacing between the two electrically charged bodies will change, thereby changing the distances between the nanoparticles.

44. A nanoparticle assembly according to claim 40 comprising a plurality of nanoparticles bearing an electrical charge and attached via separate flexible filaments to the object, such that upon application of an electrical field to the nanoparticles the spacing between the nanoparticles and the fixed body will vary.

45. A nanoparticle assembly according to claim 39 wherein the nanoparticle has a diameter not in excess of about 200 nm.

46. A nanoparticle assembly according to claim 45 wherein the nanoparticle has a diameter not in excess of about 100 nm.

47. A nanoparticle assembly according to claim 46 wherein the nanoparticle has a diameter not in excess of about 50 nm.

48. A nanoparticle assembly according to claim 47 wherein the nanoparticle comprises titanium dioxide.

49. A nanoparticle assembly according to claim 47 wherein the nanoparticle comprises any one or more of zinc oxide, a clay and magnesium silicate.

50. A nanoparticle assembly according to claim 39 wherein the nanoparticle comprises at least one insulator.

51. A nanoparticle assembly according to claim 39 wherein the nanoparticle comprises at least one conductor.

52. An electrophoretic display according to claim 51 wherein the nanoparticle comprises silver, gold, platinum, palladium or an alloy of these metals.

53. A nanoparticle assembly according to claim 39 wherein the nanoparticle comprises at least one semiconductor.

54. A nanoparticle assembly according to claim 53 wherein the nanoparticle comprises cadmium selenide.

55. A nanoparticle assembly according to claim 39 wherein the color of the nanoparticle assembly varies with the spacing between the nanoparticle and the object.

56. A nanoparticle assembly according to claim 39 wherein the object is a polymer chain bearing a plurality of the nanoparticles, the nanoparticles being attached via separate filaments to spaced attachment points on the polymer chain, each nanoparticle having a first position wherein its associated filament extends away from the polymer chain so that the nanoparticles is spaced from the polymer chain, and a second position wherein the nanoparticle lies adjacent the polymer chain.

57. A nanoparticle assembly according to claim 56 wherein the nanoparticles are electrically charged and the polymer chain is electroactive, and wherein the nanoparticles are moved from their first position to their second position by changing the charge on the electroactive polymer.

58. A nanoparticle assembly according to claim 39 wherein the nanoparticle is non-spherical.

59. A nanoparticle assembly according to claim 39 wherein the nanoparticle comprises a shell of one material surrounding a core of a different material.

60. A nanoparticle assembly according to claim 59, wherein one of the shell and core is electrically insulating and the other is electrically conductive.

61. A nanoparticle assembly comprising a plurality of nanoparticles and a polymer chain, the nanoparticles being spaced from one another along the polymer chain, the polymer having first and second conformations such that the distances between adjacent nanoparticles along the chain differ in the first and second conformations and at least one optical characteristic of the nanoparticle assemblies differs between the first and second conformations.

62. A nanoparticle assembly according to claim 61 wherein the polymer chain can be changed between its first and second conformations by a redox reaction.