Organic light emitting materials and devices

• US 7,011,897 B2
• Filed: 08/18/2003
• Issued: 03/14/2006
• Est. Priority Date: 08/16/2002
• Status: Expired due to Term

• Current Assignee: Universal Display Corporation, University of Southern California
• Original Assignee: Universal Display Corporation, University of Southern California
• Inventors: Knowles, David B., Ma, Bin, Thompson, Mark E., Walters, Robert W., Kwong, Raymond, Djurovich, Peter, Tung, Yeh-Jiun, Brooks, Jason
• Primary Examiner(s): YAMNITZKY, MARIE ROSE
• Application Number:
  US10/643,413
• Publication Number:
  US 20040121184A1
• Time in Patent Office: 939 Days
• Field of Search: 428/690, 428/917, 313/504, 546/4, 252/301.16, 257/40, 257/102
• US Class Current: 428/690
• CPC Class Codes: C07F 15/004 without a metal-carbon linkage
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/185 of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: H10K 2101/10 Triplet emission
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/342 comprising iridium
• CPC Class Codes: Y10S 428/917 Electroluminescent

Abstract

An organic light emitting device is provided. The device has an anode, a cathode, and an emissive layer disposed between the anode and the cathode, the emissive layer further comprising an emissive material having the structure:
wherein each of the variables are defined herein.

Claims

1. An emissive material represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

R₃ is a substituent having a Hammett value greater than 0.6;

each of R₂, R₄, R₅, and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group;

m is an integer between 1 and 4 and n is an integer between 1 and 3; and

,

is a monoanionic non carbon coordinating ligand.

2. The emissive material of claim 1 wherein R₄ is H.

3. The emissive material of claim 1 wherein R₅ is an electron withdrawing group.

4. The emissive material of claim 1 wherein at least one of R₂ and R₄ is an electron withdrawing group.

5. The emissive material of claim 3 wherein at least one of R₂ and R₄ is an electron withdrawing group.

6. The emissive material of claim 1 wherein at least one substituent of the emissive material is an electron withdrawing group selected from halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R , where R is a hydrogen, alkyl, aryl or heteroaryl group.

7. The emissive material of claim 1 wherein R₅ is an electron donating group.

8. The emissive material of claim 1 wherein at least one substituent of the emissive material is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

9. The emissive material of claim 1 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

10. The emissive material of claim 1 wherein the metal is iridium.

11. The emissive material of claim 1 wherein the metal is platinum.

12. A composition represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂ through R₅ and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN;

m is an integer between 1 and 4 and n is an integer between 1 and 3;

is a monoanionic non carbon coordinating ligand; and

,

wherein if neither R₃ nor R₅ is an electron donating group then R′

₄ is an electron donating group.

13. The composition of claim 12, wherein neither R₃ nor R₅ is an electron donating group and wherein R′

₄ is an electron donating group.

14. The composition of claim 12, wherein R′

₄ is an electron donating group.

15. The composition of claim 12, wherein one of R₃ and R₅ is an electron donating group, and R′

₄ is an electron withdrawing group.

16. The composition of claim 12 wherein at least one substituent of the composition is an electron withdrawing group selected from halogens, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R , where R is a hydrogen, alkyl, aryl or heteroaryl group.

17. The composition of claim 12 wherein at least one substituent of the composition is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

18. The composition of claim 12 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

19. A composition represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂, R₄, and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group;

at least one of R₃ and R₅ is CN, and, where only one of R₃ and R₅ is CN, the other is selected from the group consisting of H, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R, where R is a hydrogen, alkyl, aryl or heteroaryl group, wherein m is an integer between 1 and 4 and n is an integer between 1 and 3 and X-Y is non carbon coordinating monoamonic ligand.

20. The composition of claim 19 wherein at least one of R₂ and R₄ is F.

21. The composition of claim 20 wherein R′

₄ is an electron donating group.

22. The composition of claim 20 wherein R′

₄ is NMe₂.

23. The composition of claim 19 wherein one of R₃ and R₅ is CF₃.

24. The composition of claim 23 wherein at least one of R₂ and R₄ is F.

25. The composition of claim 23 wherein R′

₄ is an electron donating group.

26. The composition of claim 23 wherein R′

₄ is NMe₂.

27. A light emitting device comprising an organic layer, the organic layer comprising a composition represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂ through R₅ and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN;

one of R₃ and R₅ is optionally an electron donating group;

m is an integer between 1 and 4 and n is an integer between 1 and 3; and

is a monoanionic non carbon coordinating ligand.

28. The light emitting device of claim 27 wherein R₃ and R₅ are both electron withdrawing groups.

29. The light emitting device of claim 27 wherein R₃ is an electron withdrawing group.

30. The light emitting device of claim 29 wherein R₂ and R₄ are electron withdrawing groups.

31. The light emitting device of claim 27 wherein R₂ and R₄ are electron withdrawing groups.

32. The light emitting device of claim 27 wherein one of R₃ and R₅ is an electron donating group.

33. The light emitting device of claim 27 wherein at least one substituent of the emissive material is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

34. The light emitting device of claim 27 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

35. The light emitting device of claim 27 wherein the metal is Pt.

36. The light emitting device of claim 27 wherein the metal is Ir.

37. The light emitting device of claim 27 wherein light emitted by the organic layer has a maximum wavelength of less than 520 nm.

38. The light emitting device of claim 27 wherein light emitted by the organic layer has a wavelength of between approximately 420 nm and approximately 480 nm.

39. A light emitting device comprising an organic layer, the organic layer comprising a composition represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂ through R₅ and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN;

one of R₃ and R₅ is optionally an electron donating group;

m is an integer between 1 and 4 and n is an integer between 1 and 3;

is a monoanionic non carbon coordinated ligand; and

,

wherein if neither R₃ nor R₅ is an electron donating group then R′

₄ is an electron donating group.

40. The light emitting device of claim 39, wherein R′

₄ is an electron donating group.

41. The light emitting device of claim 39, wherein both R₃ and R₅ are electron withdrawing groups and R′

₄ is an electron donating group.

42. The light emitting device of claim 39, wherein one of R₃ and R₅ is an electron donating group and R′

₄ is an electron withdrawing group.

43. The light emitting device of claim 39, wherein R′

₄ is an electron withdrawing group.

44. The light emitting device of claim 39 wherein at least one substituent of the composition is an electron withdrawing group selected from halogens, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R, where R is a hydrogen, alkyl, aryl or heteroaryl group.

45. The light emitting device of claim 39 wherein at least one substituent of the composition is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

46. The light emitting device of claim 39 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

47. The light emitting device of claim 39 wherein the metal is Pt.

48. The light emitting device of claim 39 wherein the metal is Ir.

49. The light emitting device of claim 39, wherein light emitted by the organic layer has a maximum wavelength of less than 520 nm.

50. The light emitting device of claim 39 wherein light emitted by the organic layer has a wavelength of between approximately 420 nm and approximately 480 nm.

51. A light emitting device comprising an organic layer, the organic layer comprising a composition represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂, R₄, and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an ailcyl group, an aryl group or a heteroaryl group;

m is an integer between 1 and 4 and n is an integer between 1 and 3; and

,

is a monoanionic non carbon coordinating ligand;

at least one of R₃ and R₅ is CN, and where only one of R₃ and R₅ is CN, the other is selected from the group consisting of H, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R, where R is a hydrogen, alkyl, aryl or heteroaryl group.

52. The light emitting device of claim 51 wherein at least one of R₂ and R₄ is F.

53. The light emitting device of claim 51 wherein one of R₃ and R₅ is CF₃.

54. The light emitting device of claim 51 wherein one of R₃ and R₅ is CF₃, and at least one of R₂ and R₄ is F.

55. A composition represented by the following structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

each of R₂ through R₅ and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN;

m is an integer between 1 and 4 and n is an integer between 1 and 3; and

,

is a monoanionic non carbon coordinating ligand,

wherein R₃ and R₅ are selected to provide a hypsochromic shift in the emission spectrum of the compound of greater than or equal to approximately 40 nm as compared with the emission spectrum of a composition with the following structure;

56. An emissive material represented by the structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

m is at least 1 n is at least 0

X-Y is an ancillary ligand;

R₂ and R₄ are both F;

each of R₃, R₅, and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN.

57. The emissive material of claim 56 wherein R₃ and R₅ are both electron withdrawing groups.

58. The emissive material of claim 56 wherein R₃ is an electron withdrawing group.

59. The emissive material of claim 56 wherein at least one substituent of the emissive material is an electron withdrawing group selected from halogens, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R, where R is a hydrogen, alkyl, aryl or heteroaryl group.

60. The emissive material of claim 56 wherein one of R₃ and R₅ is an electron donating group.

61. The emissive material of claim 56 wherein R₃ is an electron donating group.

62. The emissive material of claim 56 wherein at least one substituent of the emissive material is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

63. The emissive material of claim 56 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

64. The emissive material of claim 56 wherein the metal is iridium.

65. The emissive material of claim 56 wherein the metal is platinum.

66. The composition of claim 56 wherein if neither R₃ nor R₅ is an electron donating group then R′

₄ is an electron donating group.

67. The emissive material of claim 66 wherein R′

₄ is an electron withdrawing group.

68. The emissive material of claim 66 wherein one of R₃ and R₅ is an electron donating group, and R′

₄ is an electron withdrawing group.

69. The emissive material of claim 66 wherein at least one substituent of the emissive material is an electron withdrawing group selected from halogens, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, and aryl and heteroaryl groups substituted with halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, or PO₃R, where R is a hydrogen, alkyl, aryl or heteroaryl group.

70. The emissive material of claim 66 wherein at least one substituent of the emissive material is an electron donating group selected from alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is a hydrogen, alkyl, aryl or heteroaryl group.

71. The emissive material of claim 66 wherein the metal is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.

72. A light emitting device comprising an organic layer, the organic layer comprising a composition represented by the general structure:

wherein M is a heavy metal with an atomic weight of greater than or equal to 40;

m is at least 1 n is at least 0

X-Y is an ancillary ligand;

R₂ and R₄ are both F;

each of R₃, R₅, and R′

₃ through R′

₆ are independently selected from the group consisting of H, halogens, CN, perfluoroalkyl, trifluorovinyl, NO₂, CO₂R, C(O)R, S(O)R, SO₂R, SO₃R, P(O)R, PO₂R, PO₃R, C≡

CR, alkyl, alkenyl, aryl, heteroaryl, OR, SR, NR₂ (including cyclic-amino), and PR₂ (including cyclic-phosphino), where R is hydrogen, an alkyl group, an aryl group or a heteroaryl group, wherein at least one of R₃ and R₅ is CN.

73. The light emitting device of claim 72 wherein if neither R₃ nor R₅ is an electron donating group then R′

₄ is an electron donating group.