Organic electroluminescence device

• US 5,503,910 A
• Filed: 03/29/1994
• Issued: 04/02/1996
• Est. Priority Date: 03/29/1994
• Status: Expired due to Term

• Current Assignee: Idemitsu Kosan Company Limited
• Original Assignee: Idemitsu Kosan Company Limited
• Inventors: Matsuura, Masahide, Kusumoto, Tadashi, Higashi, Hisahiro, Tokailin, Hiroshi
• Primary Examiner(s): Ryan, Patrick J.
• Assistant Examiner(s): YAMNITZKY, MARIE ROSE
• Application Number:
  US08/219,384
• Time in Patent Office: 735 Days
• Field of Search: 428/690, 428/917, 428/212, 428/213, 313/503, 313/504, 313/506, 252/301.21, 252/301.35
• US Class Current: 428/212
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C23C 14/12 Organic material
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• CPC Class Codes: H10K 2102/103 comprising indium oxides, e.g. ITO
• CPC Class Codes: H10K 50/125 specially adapted for multicolour light emission, e.g. for emitting white light
• CPC Class Codes: H10K 71/164 using vacuum deposition
• CPC Class Codes: H10K 85/324 comprising aluminium, e.g. Alq3
• CPC Class Codes: H10K 85/60 Organic compounds having low molecular weight H10K85/10 - H10K85/50 take precedence
• CPC Class Codes: H10K 85/615 Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: H10K 85/621 Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
• CPC Class Codes: H10K 85/622 containing four rings, e.g. pyrene
• CPC Class Codes: H10K 85/631 Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
• CPC Class Codes: H10K 85/649 Aromatic compounds comprising a hetero atom
• CPC Class Codes: Y02B 20/00 Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
• CPC Class Codes: Y10S 428/917 Electroluminescent
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/2495 Thickness [relative or absolute]

Abstract

An organic electroluminescence device comprises the first light emitting layer containing an organic compound having a fluorescence peak wave length of 380 nm or longer to shorter than 480 nm in solid state and the second light emitting layer containing an organic compound having a fluorescence peak wave length of 480 nm or longer to shorter than 580 nm in solid state. One of the first light emitting layer and the second light emitting layer contains an organic compound having a fluorescence peak wave length of 580 nm or longer to 650 nm or shorter in solution state. The device has a structure in which the first light emitting layer and the second light emitting layer are laminated on the anode in this order and both of these layers emit light by application of an electric field. This device shows light emission, particularly white light emission, with high efficiency and excellent stability.

Claims

1. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorenscence peak wave length of 380 nm to shorter than 480 and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of the first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nm in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field, wherein the first organic compound is an aromatic methylidine compound represented by the general formula (I);

##STR30## wherein R¹ and R⁴ indicate each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms;

wherein said substituted groups are substituted with one or more substitutes selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, carboxyl group, styryl group, an arylcarbonyl group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, vinyl group, anilinocarbonyl group, carbamoyl group, phenyl group, nitro group, hydroxyl group and a hologen atom;

R¹ to R⁴ may be identical to or different from one another;

R¹ and R², and R³ and R⁴ may combine through a substituent in one or both to form a substituted or unsubstituted saturated or unsaturated five-membered ring or a substituted or unsubstituted saturated or unsaturated six-membered ring;

Ar indicates a substituted or unsubstituted arylene group having 6 to 20 carbon atoms which may be mono-substituted or poly-substituted with a substituent as described above;

substituents in the arylene group may combine with each other to form a substituted or unsubstituted saturated or unsaturated five-membered ring or a substituted or unsubstituted saturated or unsaturated six-membered ring; and

, when Ar is unsubstituted phenylene, R¹ to R⁴ are each a group selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted naphthyl group, biphenyl group, cyclohexyl group and an aryloxy group.

2. The organic electroluminescence device as defined in claim 1 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

3. The organic electroluminescence device as defined in claim 1 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

4. The organic electroluminescence device as defined in claim 1 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

5. The organic electroluminescence device as defined in claim 4 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

6. The organic electroluminescence device as defined in claim 4 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

7. The organic electroluminescence device as defined in claim 4 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

8. The organic electroluminescence device as defined in claim 4 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.

9. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorescence peak wave length of from 380 nm to shorter than 480 nm and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of said first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nm in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field, wherein the organic compound having a luminescence peak wave length of 380 nm to shorter than 480 nm in solid state is an aromatic methylidine compound represented by the general formula (II);

space="preserve" listing-type="equation">A--Q--B (II)

wherein A and B indicate each a monovalent group having a structure obtained by removing one hydrogen atom from a compound represented by the general formula (I);

##STR31## wherein R¹ to R⁴ indicate each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms;

wherein said substituted groups are substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, carboxyl group, styryl group, an arylcarbonyl group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, vinyl group, anilinocarbonyl group, carbamoyl group, phenyl group, nitro group, hydroxyl group and a halogen atom;

R¹ to R⁴ may be identical to or different from one another;

R¹ and R², and R³ and R⁴ may combine through a substituent in one or both to form a substituted or unsubstituted saturated or unsaturated five-membered ring or a substituted or unsubstituted saturated or unsaturated six-membered ring;

Ar indicates a substituted or unsubstituted arylene group having 6 to 20 carbon atoms which may be mono-substituted or poly-substituted with a substituent as described above;

substituents in the arylene group may combine with each other to form a substituted or unsubstituted saturated or unsaturated five-membered ring or a substituted or unsubstituted saturated or unsaturated six-membered ring; and

, when Ar is unsubstituted phenylene, R¹ to R⁴ are each a group selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted naphthyl group, biphenyl group, cyclohexyl group and an aryloxy group,

wherein A and B may be identical to or different from each other, and Q indicates a divalent group breaking the conjugation.

10. The organic electroluminescence device as defined in claim 9 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

11. The organic electroluminescence device as defined in claim 9 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

12. The organic electroluminescence device as defined in claim 9 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

13. The organic electroluminescence device as defined in claim 12 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

14. The organic electroluminescence device as defined in claim 12 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

15. The organic electroluminescence device as defined in claim 12 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

16. The organic electroluminescence device as defined in claim 12 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.

17. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorescence peak wave length of from 380 nm to shorter than 480 nm and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of said first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nm in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field,

wherein the first organic compound is an aromatic methylidine compound represented by the general formula (III);

##STR32## wherein A¹ indicates a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted divalent aromatic heterocyclic group;

A² indicates a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted monovalent aromatic heterocyclic group, R⁵ and R⁶ indicate each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, cyclohexyl group, a monovalent aromatic heterocyclic group, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and may be identical to or different from each other;

wherein said substituted groups are substituted with one or more of an alkyl group, an aryloxy group, amino group or a phenyl group which is unsubstituted or substituted with an alkyl group, an aryloxy group or an amino group;

each substitutent in R⁵ may combine with A¹ to form a saturated or unsaturated five-membered or six-membered ring;

each substituent in R⁶ may combine with A² to form a saturated or unsaturated five-membered or six-membered ring; and

Q¹ indicates a divalent group breaking the conjugation.

18. The organic electroluminescence device as defined in claim 17 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

19. The organic electroluminescence device as defined in claim 17 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

20. The organic electroluminescence device as defined in claim 17 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

21. The organic electroluminescence device as defined in claim 20 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

22. The organic electroluminescence device as defined in claim 20 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

23. The organic electroluminescence device as defined in claim 20 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

24. The organic electroluminescence device as defined in claim 20 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.

25. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorescence peak wave length of from 380 nm to shorter than 480 nm and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of said first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nm in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field, wherein the first light emitting layer and/or the second light emitting layer comprise at least one compound selected from stilbene derivatives respresented by the general formulae (IV) and (V);

##STR33## wherein Ar¹ indicates an aryl group having 6 to 20 carbon atoms;

R⁷ to R¹⁰ indicate each independently a hydrogen atom or an aryl group having 6 to 20 carbon atoms; and

D¹ to D³ indicate each independently an aryl group having 6 to 20 carbon atoms and substituted with an electron-donating group or a condensed polycyclic group having 10 to 30 carbon atoms and substituted with an electron-donating group;

therein Ar¹ and R⁷ to R¹⁰ may be each independently unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an aklkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms or an amino group containing hydrocarbon groups having 1 to 20 carbon atoms.

26. The organic electroluminescence device as defined in claim 25 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

27. The organic electroluminescence device as defined in claim 25 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

28. The organic electroluminescence device as defined in claim 25 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

29. The organic electroluminescence device as defined in claim 28 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

30. The organic electroluminescence device as defined in claim 28 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

31. The organic electroluminescence device as defined in claim 28 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

32. The organic electroluminescence device as defined in claim 28 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.

33. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorescence peak wave length of from 380 nm to shorter than 480 nm and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of said first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nm in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field, wherein at least one of the first light emitting layer and the second light emitting layer comprises at least one compound selected from distyrylarylene derivatives represented by the general formulae (VI) and (VII);

##STR34## wherein Ar² and Ar³ indicate each independently an arylene group having 6 to 20 carbon atoms;

Ar⁴ indicates an aryl group having 6 to 20 carbon atoms;

R¹¹ to R¹⁸ indicate each independently a hydrogen atom or an aryl group having 6 to 20 carbon atoms;

wherein Ar² to Ar⁴ and R¹¹ to R¹⁸ may be each independently unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms or an amino group containing hydrocarbon groups having 1 to 20 carbon atoms; and

D⁴ to D⁶ indicate each independently an aryl group having 6 to 20 carbon atoms and substituted with an electron-donating group or a condensed polycyclic group having 10 to 30 carbon atoms and substituted with an electron-donating group.

34. The organic electroluminescence device as defined in claim 33 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

35. The organic electroluminescence device as defined in claim 33 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

36. The organic electroluminescence device as defined in claim 33 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

37. The organic electroluminescence device as defined in claim 36 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

38. The organic electroluminescence device as defined in claim 36 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

39. The organic electroluminescence device as defined in claim 36 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

40. The organic electroluminescence device as defined in claim 36 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.

41. An organic electroluminescence device which comprises light emitting layers placed between a pair of electrodes at least one of which electrodes is transparent or translucent, said light emitting layers comprising a first light emitting layer containing a first organic compound having a solid state fluorescence peak wave length of from 380 nm to shorter than 480 nm and a second light emitting layer containing a second organic compound having a solid state fluorescence peak wave length of 480 nm to shorter than 580 nm, one of said first and second light emitting layers further comprising a third organic compound having a solution state fluorescence peak wave length of 580 nm to 650 nn in a concentration of 0.1 to 10 mol % with respect to said first organic compound if said third organic compound is present in the first light emitting layer or with respect to said second organic compound if said third organic compound is present in the second light emitting layer;

said device having a structure in which the first light emitting layer and the second light emitting layer are laminated on an anode in this order and both the first light emitting layer and the second light emitting layer emit light upon application of an electric field, wherein at least one of the first light emitting layer and the second light emitting layer comprises at least one compound selected from trisstyrylarylene derivatives represented by the general formulae (VIII), (IX) and (X);

##STR35## wherein Ar⁵ and Ar⁷ indicate each independently a trivalent aromatic cyclic group having 6 to 24 carbon atoms;

Ar⁸ to Ar¹⁰ indicate each independently an aryl group having 6 to 20 carbon atoms;

R¹⁹ to R³⁶ indicate each independently a hydrogen atom or an aryl group having 6 to 20 carbon atoms; and

D⁷ to D¹² indicate each independently an aryl group having 6 to 20 carbon atoms and substituted with an electron-donating group or a condensed polycyclic group having 10 to 30 carbon atoms and substituted with an electron-donating group;

therein Ar⁵ to Ar⁷ and R¹⁹ to R³⁶ may be each independently unsubstituted or substituted with an alky group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms or an amino group containing hydrocarbon groups having 1 to 20 carbon atoms.

42. The organic electroluminescence device as defined in claim 41 wherein light emitted by said device upon application of an electric field is white light as measured on the CIE chromaticity diagram.

43. The organic electroluminescence device as defined in claim 41 wherein a recombination region in which injected holes and electrons are combined to form an excited state is present in both of the first light emitting layer and the second light emitting layer.

44. The organic electroluminescence device as defined in claim 41 wherein the device has a structure of an anode/a hole transporting layer/the first light emitting layer/the second light emitting layer/a cathode.

45. The organic electroluminescence device as defined in claim 44 wherein blue or bluish light is emitted from the first light emitting layer and red or reddish light is emitted from the second light emitting layer.

46. The organic electroluminescence device as defined in claim 44 wherein thickness of the second light emitting layer is the same as or larger than that of the first light emitting layer.

47. The organic electroluminescence device as defined in claim 44 wherein the second light emitting layer has electron transporting ability larger than hole transporting ability.

48. The organic electroluminescence device as defined in claim 44 wherein the second light emitting layer consists essentially of a metal complex of 8-hydroxyquinoline or a derivative thereof.