Organic electroluminescent device

• US 10,319,949 B2
• Filed: 05/19/2015
• Issued: 06/11/2019
• Est. Priority Date: 03/26/2002
• Status: Expired due to Term

• Current Assignee: Junji Kido, Mitsubishi Heavy Industries, Ltd., ROHM Co., Ltd.
• Original Assignee: Junji Kido, Mitsubishi Heavy Industries, Ltd., ROHM Co., Ltd.
• Inventors: Kido, Junji, Matsumoto, Toshio
• Primary Examiner(s): Williams, Joseph L
• Application Number:
  US14/716,114
• Publication Number:
  US 20150249230A1
• Time in Patent Office: 1,484 Days
• CPC Class Codes: C07C 211/58 Naphthylamines; N-substituted derivatives thereof
• CPC Class Codes: C07C 211/61 with at least one of the condensed ring systems formed by three or more rings
• CPC Class Codes: C07C 2603/18 Fluorenes; Hydrogenated fluorenes
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1003 Carbocyclic compounds
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1014 bridged by heteroatoms, e.g. N, P, Si or B
• CPC Class Codes: H10K 50/125 specially adapted for multicolour light emission, e.g. for emitting white light
• CPC Class Codes: H10K 50/131 with spacer layers between the electroluminescent layers
• CPC Class Codes: H10K 50/15 Hole transporting layers
• CPC Class Codes: H10K 50/16 Electron transporting layers
• CPC Class Codes: H10K 50/17 Carrier injection layers
• CPC Class Codes: H10K 50/171 Electron injection layers
• CPC Class Codes: H10K 50/19 Tandem OLEDs
• CPC Class Codes: H10K 50/81 Anodes
• CPC Class Codes: H10K 50/82 Cathodes
• CPC Class Codes: H10K 50/85 Arrangements for extracting light from the devices
• CPC Class Codes: H10K 50/865 comprising light absorbing layers, e.g. light-blocking layers
• CPC Class Codes: H10K 71/00 Manufacture or treatment specially adapted for the organic devices covered by this subclass
• CPC Class Codes: H10K 85/60 : Organic compounds having low molecular weight H10K85/10 - H10K85/50 take precedence
• CPC Class Codes: H10K 85/624 : containing six or more rings
• CPC Class Codes: H10K 85/626 : containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
• CPC Class Codes: H10K 85/633 : comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree

Abstract

An organic electroluminescent device includes at least two light-emissive units provided between a cathode electrode and an anode electrode opposed to the cathode electrode, each of the light-emissive units including at least one light-emissive layer. The light-emissive units are partitioned from each other by at least one charge generation layer, the charge generation layer being an electrically insulating layer having a resistivity of not less than 1.0×10² Ωcm.

Claims

1. An organic electroluminescent device comprising:

at least two light-emissive units provided between a plurality of cathode electrodes arranged in a first direction and a plurality of anode electrodes arranged in a second direction which is vertical with said first direction and opposed to said cathode electrode, each of said light-emissive units including at least one light-emissive layer;

wherein said light-emissive units are partitioned from each other by at least one charge generation layer, and

wherein said charge generation layer constituting an electrically insulating layer having a resistivity of not less than 1.0×

10² Ω

cm so that said light-emissive units are configured to emit light only from a light emissive area located between crossed area of said cathode electrode and said anode electrode.

2. The organic electroluminescent device according to claim 1, wherein said electrically insulating layer having a resistivity of not less than 1.0×

10⁵ Ω

cm.

3. The organic electroluminescent device according to claim 1, wherein each of said cathode electrodes having a width and a length that is larger than the width and each of said anode electrodes having a width and a length that is larger than the width.

4. An organic electroluminescent device comprising:

at least two light-emissive units provided between a cathode electrode and an anode electrode opposed to said cathode electrode, each of said light-emissive units including at least one light-emissive layer;

wherein said light-emissive units are partitioned from each other by at least one charge generation layer,

wherein said charge generation layer constituting an electrically insulating layer having a resistivity of not less than 1.0×

10² Ω

cm and

wherein said anode electrode comprises a plurality of electrically independent anode electrode elements, said light emissive areas located only between said cathode electrode and said anode electrode elements are configured to emit light when a voltage is applied therebetween.

5. The organic electroluminescent device according to claim 4, wherein said electrically insulating layer having a resistivity of not less than 1.0×

10⁵ Ω

cm.

6. The organic electroluminescent device according to claim 4, wherein said charge generation layer comprises at least one of a laminated and mixed layer formed from two different materials, wherein a charge transfer complex including a radical cation and a radical anion is formed upon an oxidation-reduction reaction between said two materials, and a radical cation state and a radical anion state in said charge transfer complex is transferred to a direction of the cathode and direction of the anode, respectively, when a voltage is applied to said device, so that a hole is injected into the light-emissive unit which is located on a cathode side of the charge generation layer and is adjacent thereto, and an electron is injected into the light-emissive unit which is located on an anode side of the charge generation layer and is adjacent thereto.

7. The organic electroluminescent device according to claim 4, wherein said charge generation layer comprises one of a laminated and a mixed layer comprising:

an organic compound having an ionization potential of less than 5.7 eV and a hole transporting property or electron donating property; and

one of an inorganic and organic material capable of forming a charge transfer complex through the oxidation-reduction reaction thereof with said organic compound;

wherein said charge generation layer contains a charge transfer complex formed upon the oxidation-reduction reaction between said organic compound and one of an inorganic and organic material and wherein said inorganic material comprises at least one fluorine as a substituent group, and possesses at least one of an electron injection property and an electron accepting property.

8. The organic electroluminescent device according to claim 7, wherein said organic compound comprises an arylamine compound having a glass transition temperature of not lower than 90°

C., wherein said arylamine compound is represented by the following formula (I);

9. The organic electroluminescent device according to claim 8, wherein said arylamine comprises one of a NPD, 2-TNATA, spiro-TAD, and spiro-NPB.

10. The organic electroluminescent device according to claim 7, wherein said inorganic material comprises a metal oxide selected from vanadium pentaoxide or rhenium heptaoxide.

11. The organic electroluminescent device according to claim 7, wherein said inorganic material comprises a metal halide.

12. The organic electroluminescent device according to claim 7, wherein said inorganic material is deposited by one of a resistive heating vapor deposition method, an electron beam vapor deposition method and a laser beam vapor deposition method.

13. The organic electroluminescent device according to claim 7, wherein said inorganic material is deposited by a sputtering method, wherein a sputtering apparatus used in the sputtering method is a facing target sputtering system which comprises a pair of opposed targets provided at a certain distance, a reflection electrode capable of reflecting electrons towards a front peripheral area of each target, and a magnetic field generation device capable of forming a parallel magnetic field in the vicinity of the peripheral portion of each target, said magnetic field having a portion parallel to the peripheral portion of the target.

14. The organic electroluminescent device according to claim 7, wherein said inorganic material comprises at least one cyano group as a substituent group, and possesses at least one of an electron injection property and an electron accepting property.

15. The organic electroluminescent device according to claim 10, wherein said organic material comprises tetrafluoro-tetracyanoquinodimethane (4F-TCNQ).

16. The organic electroluminescent device according to claim 4, wherein said light-emissive unit comprises, as a layer located on an anode side of said charge generation layer and being adjacent thereto, an electron injection layer having a mixture including an organic compound and a metal functioning as an electron donating dopant.

17. The organic electroluminescent device according to claim 16, wherein said electron donating dopant comprises at least one metal selected from a group including an alkaline metal, an alkaline earth metal and a rare earth metal.

18. The organic electroluminescent device according to claim 14, wherein said metal of the electron donating dopant is provided in a molar ratio of 0.1 to 10 with respect to said organic compound in said electron injection layer.

19. The organic electroluminescent device according to claim 4, wherein said light-emissive unit comprises, as a layer located on an anode side of said charge generation layer and being adjacent thereto, a metal layer having a thickness of nor more than 5 nm formed from a metal selected from an alkaline metal, an alkaline earth metal and a rare earth metal;

wherein said metal constituting the layer diffuses in the adjacent electron transporting layer to react with electron transporting organic material; and

wherein, as a result of said diffusion, an electron injection layer is composed of a mixture including said electron transporting organic material and a metal functioning as an electron donating dopant is formed.

20. The organic electroluminescent device according to claim 4, wherein said light-emissive unit comprises, as a layer located on an anode side of said charge generation layer and being adjacent thereto, a layer including an organic metal complex compound including at least one metal ion selected from an alkaline metal ion, an alkaline earth metal ion and a rare earth metal ion, and a reaction generating layer which is formed by an in-situ reduction reaction when a thermally reducible metal, which can reduce a metal ion in said organic metal complex to a metal in a vacuum is deposited on the organic metal complex constituting the layer.

21. The organic electroluminescent device according to claim 20, wherein the thermally reducible metal includes at least one selected from aluminum, zirconium, silicon, titanium and tungsten.

22. The organic electroluminescent device according to claim 4, wherein said light-emissive unit comprises a structure, as a layer located on an anode side of said charge generation layer and being adjacent thereto, in which a layer of a mixture including an organic compound and an electron donating dopant is formed, thereafter, a reaction generating layer is generated by an in-situ reduction reaction when a thermally reducible metal, which can reduce an alkaline metal ion, an alkaline earth metal ion and a rare earth metal ion to a metal in a vacuum, is deposited on an organic metal complex com pound containing at least one metal ion selected from an alkaline metal ion, an alkaline earth metal ion and a rare earth metal ion.

23. The organic electroluminescent device according to claim 4, wherein said light-emissive unit comprises a structure, as a layer located on an anode side of said charge generation layer and being adjacent thereto, in which a layer of a mixture including an organic compound and an electron donating dopant is formed, thereafter, a reaction generating layer is generated by an in-situ reduction reaction when a thermally reducible metal, which can reduce an alkaline metal ion, an alkaline earth metal ion and a rare earth metal ion to a metal in a vacuum, is deposited on an inorganic compound containing at least one metal ion selected from an alkaline metal ion, an alkaline earth metal ion and a rare earth metal ion.

24. The organic electroluminescent device according to claim 4, in which said light-emissive unit comprises, as a layer located on an anode side of said charge generation layer and being adjacent thereto, a hole injection layer comprising a mixture of an organic compound and an electron accepting compound having a property capable of oxidizing said organic compound in terms of Lewis acid chemistry.

25. The organic electroluminescent device according to claim 24, wherein the electron accepting compound having a property capable of oxidizing the organic compound in said hole injection layer in terms of Lewis acid chemistry is provided in a molar ratio of 0.01 to 10 with respect to the organic compound.

26. The organic electroluminescent device according to claim 4, in which said light-emissive unit comprises, as a layer located on a cathode side of said charge generation layer and being adjacent thereto, a hole injection layer including an electron accepting compound and having a thickness of not more than 30 nm.

27. The organic electroluminescent device according to claim 4, in which said light-emissive units each have different emission spectrums;

and wherein said organic electroluminescent device is configured to emit white light due to superimposing of different lights from each light-emissive unit.

28. The organic electroluminescent device according to claim 4, wherein, in each of said light-emissive units, an optical path length from a light-emissive site to a light-reflective metal electrode is an odd-numbered times a quarter wavelength of light.

29. The organic electroluminescent device according to claim 4, wherein all the layers including said light-emissive units, said charge generation layer, and an electrode layer are formed on a substrate by heating a vaporizable material in a vacuum to deposit one of a vaporized and sublimed material on the substrate, wherein upon depositing said one of vaporized and sublimed material on the substrate, a substrate is transported in a direction of a planar surface

thereof:

a deposition area being open in a lower surface of the substrate;

a container is provided, in a

lower position of the transporting substrate, including a vaporizable material having a deposition width which can cover the deposition area extending in a direction perpendicular to the transportation direction of the substrate; and

said container is heated to thereby one of vaporize and sublime so as to deposit the vaporizable material provided in the container.

30. The organic electroluminescent device according to claim 4, wherein a combined thickness of said light-emissive units and said charge generation layers, sandwiched between the cathode and anode, is greater than 1,000 nm.

31. The organic electroluminescent device according to claim 4, wherein light can be passed in only one direction which is one of an anode electrode direction and a cathode electrode direction, from a light generation site in the organic electroluminescent device, wherein light advancing in a direction opposite to said only one direction is absorbed by a light-absorbing medium, and wherein, in each of said light-emissive units, a light interference effect is removed so that an adjustment of an optical path length from a light-emissive site of said light-emissive layers to a light-reflective metal electrode is substantially not necessary.