WO2014081206A1 - Novel organic electroluminescence compounds and organic electroluminescence device containing the same - Google Patents

Novel organic electroluminescence compounds and organic electroluminescence device containing the same Download PDF

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WO2014081206A1
WO2014081206A1 PCT/KR2013/010598 KR2013010598W WO2014081206A1 WO 2014081206 A1 WO2014081206 A1 WO 2014081206A1 KR 2013010598 W KR2013010598 W KR 2013010598W WO 2014081206 A1 WO2014081206 A1 WO 2014081206A1
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substituted
unsubstituted
group
alkyl
aryl
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PCT/KR2013/010598
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French (fr)
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Chi-Sik Kim
Seon-Woo Lee
Young-Kwang Kim
Kyung-Joo Lee
Kyoung-Jin Park
Hyuck-Joo Kwon
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to JP2015542962A priority Critical patent/JP2016503585A/en
Priority to CN201380058239.8A priority patent/CN104781253B/en
Publication of WO2014081206A1 publication Critical patent/WO2014081206A1/en

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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1011—Condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer

Definitions

  • the present invention relates to novel organic electroluminescent compounds and organic electroluminescent device containing the same.
  • An electroluminescence device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • a luminescent material can be used in combination with a host material as a light emitting material to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as a light emitting material, their selection is important.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
  • Japanese Patent Appln. Laying-Open Nos. 2007-194241 and 2009-194042 disclose compounds in which two carbazoles are linked via an aryl, heteroaryl or fluorene group, as compounds for an organic EL device.
  • organic EL devices comprising the compounds disclosed in the above references are still not satisfactory in terms of power efficiency, luminous efficiency, quantum efficiency, lifespan, etc.
  • the objective of the present invention is to provide an organic electroluminescent compound which has higher luminous efficiency, power efficiency, and a longer operational lifespan than the conventional materials; and an organic electroluminescent device having high efficiency and a long lifespan, using said compounds.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • Ar 1 represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
  • a 1 to A 5 each independently represent CR or N, with a proviso that at least one of Ar 1 to Ar 5 represent N;
  • R represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group;
  • R 1 to R 4 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group,
  • a and c each independently represent an integer of 1 to 4; where each of a or c is 2 or more, each of R 1 and each of R 3 may be same or different;
  • b and d each independently represent an integer of 1 to 3; where each of b or d is 2 or more, each of R 2 and each of R 4 may be same or different; and
  • the organic electroluminescent compound according to the present invention has high luminous efficiency, power efficiency, and a long operational lifespan.
  • an organic electroluminescent device using the compound according to the present invention provides excellent current efficiency and has lower driving voltage, which results in higher power efficiency and enhanced power consumption.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group, preferably represents a substituted or unsubstituted (C6-C30)arylene group, and more preferably represents a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl.
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group, preferably represents a single bond, or a substituted or unsubstituted (C6-C30)arylene group, and more preferably represents a single bond or an unsubstituted (C6-C20)arylene group.
  • Ar 1 represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, preferably represents a substituted or unsubstituted (C6-C30)aryl group, and more preferably represents a (C6-C20)aryl group unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, or a cyano; or an unsubstituted 5- to 20-membered heteroaryl group.
  • a 1 to A 5 each independently represent CR or N, with a proviso that at least one of Ar 1 to Ar 5 represent N.
  • R represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group, preferably represents hydrogen, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, and more preferably represents hydrogen; a (C6-C20)aryl group unsubstituted or substituted with deuterium, a (C1-C6)alkyl, a (C3-C20)cycloalkyl, a (C6-C20)aryl, a 5- to 20-membered heteroaryl, or a tri(C1-C6)alkylsilyl; or an unsubsti
  • R 1 to R 4 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group,
  • a and c each independently represent an integer of 1 to 4, preferably an integer of 1 to 2; where each of a or c is 2 or more, each of R 1 and each of R 3 may be same or different.
  • b and d each independently represent an integer of 1 to 3, preferably an integer of 1 to 2; where each of b or d is 2 or more, each of R 2 and each of R 4 may be same or different.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group
  • L 2 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene group
  • Ar 1 represents a substituted or unsubstituted (C6-C30)aryl group
  • a 1 to A 5 each independently represent CR or N, with a proviso that at least one of Ar 1 to Ar 5 represent N
  • R represents hydrogen, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group
  • R 1 to R 4 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted di(C6-C30)arylamino
  • L 1 represents a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl
  • L 2 represents a single bond or an unsubstituted (C6-C20)arylene group
  • Ar 1 represents a (C6-C20)aryl group unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, or a cyano; or an unsubstituted 5- to 20-membered heteroaryl group
  • a 1 to A 5 each independently represent CR or N, with a proviso that at least one of Ar 1 to Ar 5 represent N
  • R represents hydrogen; a (C6-C20)aryl group unsubstituted or substituted with deuterium, a (C1-C6)alkyl, a (C3-C20)cycloalkyl, a (C6-C20)aryl, a 5-
  • Formula 1 may be represented by the following formulae (1-1) to (1-4):
  • L 1 , L 2 , Ar 1 , A 1 to A 5 , R 1 to R 4 , a, b, c, and d are as defined in formula 1.
  • the structure may represent pyridine, pyrimidine, triazine, pyrazine or pyridazine.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 15, and includes phenyl, bi
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • the representative compounds of the present invention include the following compounds:
  • the compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
  • L 1 , L 2 , Ar 1 , A 1 to A 5 , R 1 to R 4 , and a to d are as defined in formula 1 above, and Hal represents a halogen.
  • an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • Said organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes.
  • Said organic layer comprises at least one compound of formula 1 according to the present invention.
  • the organic layer comprises a light-emitting layer, and at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
  • the compound represented by formula 1 can be comprised in the light-emitting layer. Where used in the light-emitting layer, the compound represented by formula 1 can be comprised as a host material. Preferably, the light-emitting layer can further comprise at least one dopant, and if needed, a compound other than the compound represented by formula 1 can be comprised additionally as a second host material.
  • the second host material can be from any of the known phosphorescent dopants.
  • the phosphorescent dopant selected from the group consisting of the compounds of formulae 2 to 6 below is preferable in view of luminous efficiency.
  • X represents O or S
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, or R 25 R 26 R 27 Si-;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl;
  • preferable examples of the second host material are as follows:
  • the dopant comprised in the organic electroluminescent device according to the present invention may be selected from the group consisting of the compounds of formulae 7 to 9 below.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with halogen(s); a substituted or unsubstituted (C3-C30)cycloalkyl; a cyano; or a substituted or unsubstituted (C1-C30)alkoxy; adjacent substituents of R 120 to R 123 may be linked to each other to form a fused ring, e.g. quinoline;
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R 124 to R 127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R 100 may be same or different; and
  • n is an integer of 1 to 3.
  • the dopant materials include the following:
  • a material used for an organic electroluminescent device comprises the compound according to the present invention as a host material.
  • said material may additionally comprise a second host material, wherein the ratio of the first host material to the second host material can be in the range of 1:99 to 99:1.
  • the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes.
  • Said organic layer comprises the material used for the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • a surface layer is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it is easy to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it is easy to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • An OLED device was produced using the compound according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound H-3 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material
  • compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed a green emission having a luminance of 930 cd/m 2 and a current density of 2.28 mA/cm 2 at a driving voltage of 2.6 V, and a power efficiency of 49.31 m/W.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-3 as a host, and using compound D-102 as a dopant of the light emitting material.
  • the produced OLED device showed a green emission having a luminance of 2420 cd/m 2 and a current density of 5.76 mA/cm 2 at a driving voltage of 2.7 V, and a power efficiency of 48.91 m/W.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-56 as a host, and using compound D-1 as a dopant of the light emitting material.
  • the produced OLED device showed a green emission having a luminance of 1110 cd/m 2 and a current density of 3.34 mA/cm 2 at a driving voltage of 2.7 V, and a power efficiency of 38.71 m/W.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-11 as a host, and using compound D-1 as a dopant of the light emitting material.
  • the produced OLED device showed a green emission having a luminance of 770 cd/m 2 and a current density of 2.56 mA/cm 2 at a driving voltage of 2.6 V, and a power efficiency of 36.31 m/W.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-63 as a host, and using compound D-1 as a dopant of the light emitting material.
  • the produced OLED device showed a green emission having a luminance of 1970 cd/m 2 and a current density of 5.38 mA/cm 2 at a driving voltage of 3.0 V, and a power efficiency of 38.31 m/W.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-85 as a host, and using compound D-1 as a dopant of the light emitting material.
  • the produced OLED device showed a green emission having a luminance of 1240 cd/m 2 and a current density of 2.86 mA/cm 2 at a driving voltage of 2.6 V, and a power efficiency of 52.41 m/W.
  • Comparative Example 1 Production of an OLED device using
  • An OLED device was produced in the same manner as in Device Example 1, except for depositing the light emitting layer having a thickness of 30 nm on the hole transport layer using 4,4'-N,N'-dicarbazole-biphenyl as a host, and compound D-86 as a dopant; and depositing aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate to form a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed a green emission having a luminance of 3000 cd/m 2 and a current density of 8.57 mA/cm 2 at a driving voltage of 5.8 V, and a power efficiency of 18.961 m/W.
  • Comparative Example 2 Production of an OLED device using
  • An OLED device was produced in the same manner as in Device Example 1, except for depositing the light emitting layer having a thickness of 30 nm on the hole transport layer using 4,4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl as a host, and compound D-86 as a dopant.
  • the produced OLED device showed a green emission having a luminance of 1320 cd/m 2 and a current density of 11.66 mA/cm 2 at a driving voltage of 5.9 V, and a power efficiency of 6.031 m/W.
  • the organic electroluminescence compound according to the present invention provides higher luminous efficiency compared with conventional materials.
  • an OLED device using the organic electroluminescence compound according to the present invention as a light-emitting host material has lower driving voltage to result in higher power efficiency, and enhanced power consumption, and provides improved current efficiency.

Abstract

The present invention relates to a novel organic electroluminescence compound and an organic electroluminescence device comprising the same. The organic electroluminescence compound according to the present invention provides higher luminous efficiency compared with conventional materials. In addition, an OLED device using the organic electroluminescence compound according to the present invention as a light-emitting host material has lower driving voltage, which results in higher power efficiency and enhanced power consumption, and provides improved current efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENCE COMPOUNDS AND ORGANIC ELECTROLUMINESCENCE DEVICE CONTAINING THE SAME
The present invention relates to novel organic electroluminescent compounds and organic electroluminescent device containing the same.
An electroluminescence device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
A luminescent material (dopant) can be used in combination with a host material as a light emitting material to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as a light emitting material, their selection is important.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent substances. Recently, Pioneer (Japan) et al. developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc. as host materials, which were known as hole blocking layer materials.
Though these phosphorous host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc. were used as a hole injection and transport material.
However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
Japanese Patent Appln. Laying-Open Nos. 2007-194241 and 2009-194042 disclose compounds in which two carbazoles are linked via an aryl, heteroaryl or fluorene group, as compounds for an organic EL device.
However, organic EL devices comprising the compounds disclosed in the above references are still not satisfactory in terms of power efficiency, luminous efficiency, quantum efficiency, lifespan, etc.
The objective of the present invention is to provide an organic electroluminescent compound which has higher luminous efficiency, power efficiency, and a longer operational lifespan than the conventional materials; and an organic electroluminescent device having high efficiency and a long lifespan, using said compounds.
The present inventors found that the above objective can be achieved by a compound in which two carbazoles are linked via an aryl or heteroaryl group, and a nitrogen containing aromatic ring is bonded to a nitrogen atom of one carbazole, represented by the following formula 1:
Figure PCTKR2013010598-appb-I000001
wherein
L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
Ar1 represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N;
R represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group;
R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur;
a and c each independently represent an integer of 1 to 4; where each of a or c is 2 or more, each of R1 and each of R3 may be same or different;
b and d each independently represent an integer of 1 to 3; where each of b or d is 2 or more, each of R2 and each of R4 may be same or different; and
the heteroarylene group and the heteroaryl group each independently contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescent compound according to the present invention has high luminous efficiency, power efficiency, and a long operational lifespan. In addition, an organic electroluminescent device using the compound according to the present invention provides excellent current efficiency and has lower driving voltage, which results in higher power efficiency and enhanced power consumption.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The compound represented by the above formula 1 will be described in detail.
In formula 1 above, L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group, preferably represents a substituted or unsubstituted (C6-C30)arylene group, and more preferably represents a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl.
L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group, preferably represents a single bond, or a substituted or unsubstituted (C6-C30)arylene group, and more preferably represents a single bond or an unsubstituted (C6-C20)arylene group.
Ar1 represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, preferably represents a substituted or unsubstituted (C6-C30)aryl group, and more preferably represents a (C6-C20)aryl group unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, or a cyano; or an unsubstituted 5- to 20-membered heteroaryl group.
A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N.
R represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group, preferably represents hydrogen, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, and more preferably represents hydrogen; a (C6-C20)aryl group unsubstituted or substituted with deuterium, a (C1-C6)alkyl, a (C3-C20)cycloalkyl, a (C6-C20)aryl, a 5- to 20-membered heteroaryl, or a tri(C1-C6)alkylsilyl; or an unsubstituted 5- to 20-membered heteroaryl group.
R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, preferably each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted di(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring, and more preferably each independently represent hydrogen, an unsubstituted (C1-C6)alkyl group, an unsubstituted (C6-C20)aryl group, or an unsubstituted di(C6-C20)arylamino group; or are linked to an adjacent substituent(s) to form a monocyclic, 3- to 20- membered, aromatic ring.
a and c each independently represent an integer of 1 to 4, preferably an integer of 1 to 2; where each of a or c is 2 or more, each of R1 and each of R3 may be same or different.
b and d each independently represent an integer of 1 to 3, preferably an integer of 1 to 2; where each of b or d is 2 or more, each of R2 and each of R4 may be same or different.
The heteroarylene group and the heteroaryl group each independently contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
According to one embodiment of the present invention, in formula 1, above, L1 represents a substituted or unsubstituted (C6-C30)arylene group; L2 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene group; Ar1 represents a substituted or unsubstituted (C6-C30)aryl group; A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N; R represents hydrogen, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; R1 to R4 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted di(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring; a and c each independently represent an integer of 1 to 2; and b and d each independently represent an integer of 1 to 2.
According to another embodiment of the present invention, in formula 1, above, L1 represents a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl; L2 represents a single bond or an unsubstituted (C6-C20)arylene group; Ar1 represents a (C6-C20)aryl group unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, or a cyano; or an unsubstituted 5- to 20-membered heteroaryl group; A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N; R represents hydrogen; a (C6-C20)aryl group unsubstituted or substituted with deuterium, a (C1-C6)alkyl, a (C3-C20)cycloalkyl, a (C6-C20)aryl, a 5- to 20-membered heteroaryl, or a tri(C1-C6)alkylsilyl; or an unsubstituted 5- to 20-membered heteroaryl group; R1 to R4 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl group, an unsubstituted (C6-C20)aryl group, or an unsubstituted di(C6-C20)arylamino group; or are linked to an adjacent substituent(s) to form a monocyclic, 3- to 20- membered, aromatic ring; a and c each independently represent an integer of 1 to 2; and b and d each independently represent an integer of 1 to 2.
Formula 1 may be represented by the following formulae (1-1) to (1-4):
Figure PCTKR2013010598-appb-I000002
Figure PCTKR2013010598-appb-I000003
Figure PCTKR2013010598-appb-I000004
Figure PCTKR2013010598-appb-I000005
wherein L1, L2, Ar1, A1 to A5, R1 to R4, a, b, c, and d are as defined in formula 1.
The structure,
Figure PCTKR2013010598-appb-I000006
may represent pyridine, pyrimidine, triazine, pyrazine or pyridazine.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “5- to 30-membered heteroaryl(ene)” is an aryl having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 5 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 5 to 15 ring backbone atoms; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “Halogen” includes F, Cl, Br and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
The substituents of the substituted alkyl, the substituted alkoxy, the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted alkylamino, the substituted arylamino, the substituted alkylarylamino, the substituted cycloalkyl, the substituted aryl(ene), and the substituted heteroaryl(ene) in L1, L2, Ar1, R, and R1 to R4 in the above formula 1 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 5- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a 5- to 30-membered heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono or di(C1-C30)alkylamino, a mono or di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl, and preferably each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a (C1-C30)alkyl, a (C3-C30)cycloalkyl, a 5- to 30-membered heteroaryl, a (C6-C30)aryl, and a tri(C1-C30)alkylsilyl.
The representative compounds of the present invention include the following compounds:
Figure PCTKR2013010598-appb-I000007
Figure PCTKR2013010598-appb-I000008
Figure PCTKR2013010598-appb-I000009
Figure PCTKR2013010598-appb-I000010
Figure PCTKR2013010598-appb-I000011
Figure PCTKR2013010598-appb-I000012
Figure PCTKR2013010598-appb-I000013
Figure PCTKR2013010598-appb-I000014
Figure PCTKR2013010598-appb-I000015
Figure PCTKR2013010598-appb-I000016
Figure PCTKR2013010598-appb-I000017
Figure PCTKR2013010598-appb-I000018
Figure PCTKR2013010598-appb-I000019
Figure PCTKR2013010598-appb-I000020
Figure PCTKR2013010598-appb-I000021
Figure PCTKR2013010598-appb-I000022
Figure PCTKR2013010598-appb-I000023
Figure PCTKR2013010598-appb-I000024
Figure PCTKR2013010598-appb-I000025
Figure PCTKR2013010598-appb-I000026
Figure PCTKR2013010598-appb-I000027
The compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2013010598-appb-I000028
wherein L1, L2, Ar1, A1 to A5, R1 to R4, and a to d are as defined in formula 1 above, and Hal represents a halogen.
In another embodiment of the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
Said organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes. Said organic layer comprises at least one compound of formula 1 according to the present invention.
One of the first and second electrodes is an anode, and the other is a cathode. The organic layer comprises a light-emitting layer, and at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
The compound represented by formula 1 can be comprised in the light-emitting layer. Where used in the light-emitting layer, the compound represented by formula 1 can be comprised as a host material. Preferably, the light-emitting layer can further comprise at least one dopant, and if needed, a compound other than the compound represented by formula 1 can be comprised additionally as a second host material.
The second host material can be from any of the known phosphorescent dopants. Specifically, the phosphorescent dopant selected from the group consisting of the compounds of formulae 2 to 6 below is preferable in view of luminous efficiency.
Figure PCTKR2013010598-appb-I000029
Figure PCTKR2013010598-appb-I000030
Figure PCTKR2013010598-appb-I000031
Figure PCTKR2013010598-appb-I000032
Figure PCTKR2013010598-appb-I000033
wherein Cz represents the following structure;
Figure PCTKR2013010598-appb-I000034
X represents O or S;
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted 5- to 30-membered heteroaryl, or R25R26R27Si-; R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 5- to 30-membered heteroarylene; M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl; Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist; R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted 5- to 30-membered heteroaryl, and R32 and R33 may be same or different; h and i each independently represent an integer of 1 to 3; j, k, l and m each independently represent an integer of 0 to 4; and where h, i, j, k, l or m is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23 or each of R24 may be same or different.
Specifically, preferable examples of the second host material are as follows:
Figure PCTKR2013010598-appb-I000035
Figure PCTKR2013010598-appb-I000036
Figure PCTKR2013010598-appb-I000037
Figure PCTKR2013010598-appb-I000038
Figure PCTKR2013010598-appb-I000039
Figure PCTKR2013010598-appb-I000040
Figure PCTKR2013010598-appb-I000041
Figure PCTKR2013010598-appb-I000042
Figure PCTKR2013010598-appb-I000043
Figure PCTKR2013010598-appb-I000044
Figure PCTKR2013010598-appb-I000045
Figure PCTKR2013010598-appb-I000046
Figure PCTKR2013010598-appb-I000047
Figure PCTKR2013010598-appb-I000048
Figure PCTKR2013010598-appb-I000049
Figure PCTKR2013010598-appb-I000050
The dopant comprised in the organic electroluminescent device according to the present invention may be selected from the group consisting of the compounds of formulae 7 to 9 below.
Figure PCTKR2013010598-appb-I000051
Figure PCTKR2013010598-appb-I000052
Figure PCTKR2013010598-appb-I000053
wherein L is selected from the following structures:
Figure PCTKR2013010598-appb-I000054
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with halogen(s); a substituted or unsubstituted (C3-C30)cycloalkyl; a cyano; or a substituted or unsubstituted (C1-C30)alkoxy; adjacent substituents of R120 to R123 may be linked to each other to form a fused ring, e.g. quinoline;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R124 to R127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl;
f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R100 may be same or different; and
n is an integer of 1 to 3.
Specifically, the dopant materials include the following:
Figure PCTKR2013010598-appb-I000055
Figure PCTKR2013010598-appb-I000056
Figure PCTKR2013010598-appb-I000057
Figure PCTKR2013010598-appb-I000058
Figure PCTKR2013010598-appb-I000059
Figure PCTKR2013010598-appb-I000060
Figure PCTKR2013010598-appb-I000061
Figure PCTKR2013010598-appb-I000062
Figure PCTKR2013010598-appb-I000063
Figure PCTKR2013010598-appb-I000064
Figure PCTKR2013010598-appb-I000065
Figure PCTKR2013010598-appb-I000066
Figure PCTKR2013010598-appb-I000067
Figure PCTKR2013010598-appb-I000068
Figure PCTKR2013010598-appb-I000069
Figure PCTKR2013010598-appb-I000070
Figure PCTKR2013010598-appb-I000071
In another embodiment of the present invention, a material used for an organic electroluminescent device is provided. The material comprises the compound according to the present invention as a host material. When the compound according to the present invention is comprised as a host material, said material may additionally comprise a second host material, wherein the ratio of the first host material to the second host material can be in the range of 1:99 to 99:1.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes. Said organic layer comprises the material used for the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it is easy to inject and transport electrons from the mixed region to an electroluminescent medium. Further, the hole transport compound is oxidized to a cation, and thus it is easy to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound H-3
Figure PCTKR2013010598-appb-I000072
Preparation of compound 1-1
After adding 9-phenyl-9H-carbazol-3-yl boronic acid (30 g, 104 mmol), 1-bromo-4-iodobenzene (22.7 g, 80 mmol), tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (2.8 g, 2.4 mmol), Na2CO3 (22 g, 200 mmol), toluene 400 mL, ethanol (EtOH) 100 mL, and H2O 100 mL in a flask, the mixture was stirred under reflux for 5 hours. After completing the reaction, the mixture was extracted with dichloromethane (DCM) and H2O, and the DCM layer was dried with MgSO4, and filtered. The obtained solid was separated with a column to obtain compound 1-1 (17.9 g, 45 %).
Preparation of compound 1-2
After dissolving compound 1-1 (17.9 g, 44.8 mmol) in tetrahydrofuran (THF) 200 mL, the mixture was cooled to -78°C, 2.5 M n-butyl lithium (23 mL, 58.3 mmol) was slowly added to the mixture, and the mixture was stirred for 1 hour. Next, isopropyl borate (15.5 mL, 67.2 mmol) was added to the mixture, and the mixture was slowly heated and stirred at room temperature for 17 hours. After completing the reaction, the mixture was extracted with ethylacetate (EA) and H2O, and the EA layer was dried with MgSO4, and concentrated to obtain compound 1-2 (5.02 g, 31 %).
Preparation of compound 1-3
After adding compound 1-2 (5 g, 13.7 mmol), 3-bromocarbazole (3.72 g, 15.1 mmol), Pd(PPh3)4 (791 mg, 0.7 mmol), K2CO3 (3.8 g, 27.4 mmol), toluene 80 mL, EtOH 30 mL, and H2O 30 mL in a flask, the mixture was stirred under reflux for 5 hours. After completing the reaction, the mixture was extracted with DCM and H2O, and the DCM layer was dried with MgSO4, and filtered. The obtained solid was separated with a column to obtain compound 1-3 (3.4 g, 53 %).
Preparation of compound H-3
After adding compound 1-3 (3.4 g, 7 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.2 g, 8.4 mmol), dimethylaminopyridine (DMAP) (427 mg, 3.5 mmol), K2CO3 (2.4 g, 17.5 mmol), and dimethylformamide (DMF) 80 mL in a flask, the mixture was stirred under reflux for 3 hours. After completing the reaction, methanol (MeOH) was added to the mixture to produce a solid, and the solid was filtered. Next, the obtained solid was separated with a column to obtain compound H-3 (2.7 g, 53 %).
The detailed data of the compound prepared in Example 1, and the compounds that could be prepared by the same method as in Example 1 are shown in Table 1 below.
[Table 1]
Figure PCTKR2013010598-appb-I000073
Figure PCTKR2013010598-appb-I000074
Device Example 1: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced using the compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound H-3 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed a green emission having a luminance of 930 cd/m2 and a current density of 2.28 mA/cm2 at a driving voltage of 2.6 V, and a power efficiency of 49.31 m/W.
Device Example 2: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-3 as a host, and using compound D-102 as a dopant of the light emitting material.
The produced OLED device showed a green emission having a luminance of 2420 cd/m2 and a current density of 5.76 mA/cm2 at a driving voltage of 2.7 V, and a power efficiency of 48.91 m/W.
Device Example 3: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-56 as a host, and using compound D-1 as a dopant of the light emitting material.
The produced OLED device showed a green emission having a luminance of 1110 cd/m2 and a current density of 3.34 mA/cm2 at a driving voltage of 2.7 V, and a power efficiency of 38.71 m/W.
Device Example 4: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-11 as a host, and using compound D-1 as a dopant of the light emitting material.
The produced OLED device showed a green emission having a luminance of 770 cd/m2 and a current density of 2.56 mA/cm2 at a driving voltage of 2.6 V, and a power efficiency of 36.31 m/W.
Device Example 5: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-63 as a host, and using compound D-1 as a dopant of the light emitting material.
The produced OLED device showed a green emission having a luminance of 1970 cd/m2 and a current density of 5.38 mA/cm2 at a driving voltage of 3.0 V, and a power efficiency of 38.31 m/W.
Device Example 6: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-85 as a host, and using compound D-1 as a dopant of the light emitting material.
The produced OLED device showed a green emission having a luminance of 1240 cd/m2 and a current density of 2.86 mA/cm2 at a driving voltage of 2.6 V, and a power efficiency of 52.41 m/W.
Comparative Example 1: Production of an OLED device using
conventional light emitting material
An OLED device was produced in the same manner as in Device Example 1, except for depositing the light emitting layer having a thickness of 30 nm on the hole transport layer using 4,4'-N,N'-dicarbazole-biphenyl as a host, and compound D-86 as a dopant; and depositing aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate to form a hole blocking layer having a thickness of 10 nm.
The produced OLED device showed a green emission having a luminance of 3000 cd/m2 and a current density of 8.57 mA/cm2 at a driving voltage of 5.8 V, and a power efficiency of 18.961 m/W.
Comparative Example 2: Production of an OLED device using
conventional light emitting material
An OLED device was produced in the same manner as in Device Example 1, except for depositing the light emitting layer having a thickness of 30 nm on the hole transport layer using 4,4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl as a host, and compound D-86 as a dopant.
The produced OLED device showed a green emission having a luminance of 1320 cd/m2 and a current density of 11.66 mA/cm2 at a driving voltage of 5.9 V, and a power efficiency of 6.031 m/W.
The organic electroluminescence compound according to the present invention provides higher luminous efficiency compared with conventional materials. In addition, an OLED device using the organic electroluminescence compound according to the present invention as a light-emitting host material has lower driving voltage to result in higher power efficiency, and enhanced power consumption, and provides improved current efficiency.

Claims (8)

  1. An organic electroluminescence compound represented by the following formula 1:
    Figure PCTKR2013010598-appb-I000075
    wherein
    L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
    L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
    Ar1 represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
    A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N;
    R represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group;
    R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur;
    a and c each independently represent an integer of 1 to 4; where each of a or c is 2 or more, each of R1 and each of R3 may be same or different;
    b and d each independently represent an integer of 1 to 3; where each of b or d is 2 or more, each of R2 and each of R4 may be same or different; and
    the heteroarylene group and the heteroaryl group each independently contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescence compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted alkoxy, the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted alkylamino, the substituted arylamino, the substituted alkylarylamino, the substituted cycloalkyl, the substituted aryl(ene) and the substituted heteroaryl(ene) in L1, L2, Ar1, R, and R1 to R4 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 5- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a 5- to 30-membered heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di(C1-C30)alkylamino, a mono- or di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
  3. The organic electroluminescence compound according to claim 1, wherein L1 represents a substituted or unsubstituted (C6-C30)arylene group;
    L2 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene group;
    Ar1 represents a substituted or unsubstituted (C6-C30)aryl group;
    A1 to A5 each independently represent CR or N, with a proviso that at least one of Ar1 to Ar5 represent N;
    R represents hydrogen, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
    R1 to R4 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted di(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, 3- to 30- membered, alicyclic or aromatic ring;
    a and c each independently represent an integer of 1 to 2; and
    b and d each independently represent an integer of 1 to 2.
  4. The organic electroluminescence compound according to claim 1, wherein L1 represents a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl;
    L2 represents a single bond or an unsubstituted (C6-C20)arylene group;
    Ar1 represents a (C6-C20)aryl group unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, or a cyano; or an unsubstituted 5- to 20-membered heteroaryl group;
    A1 to A5 each independently represent CR or N, with a proviso that at least one of A1 to A5 represent N;
    R represents hydrogen; a (C6-C20)aryl group unsubstituted or substituted with deuterium, a (C1-C6)alkyl, a (C3-C20)cycloalkyl, a (C6-C20)aryl, a 5- to 20-membered heteroaryl, or a tri(C1-C6)alkylsilyl; or an unsubstituted 5- to 20-membered heteroaryl group;
    R1 to R4 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl group, an unsubstituted (C6-C20)aryl group, or an unsubstituted di(C6-C20)arylamino group; or are linked to an adjacent substituent(s) to form a monocyclic, 3- to 20- membered, aromatic ring;
    a and c each independently represent an integer of 1 to 2; and
    b and d each independently represent an integer of 1 to 2.
  5. The organic electroluminescence compound according to claim 1, wherein formula 1 is represented by the following formulae (1-1) to (1-4):
    Figure PCTKR2013010598-appb-I000076
    Figure PCTKR2013010598-appb-I000077
    Figure PCTKR2013010598-appb-I000078
    Figure PCTKR2013010598-appb-I000079
    wherein
    L1, L2, Ar1, A1 to A5, R1 to R4, a, b, c, and d are as defined in claim 1.
  6. The organic electroluminescence compound according to claim 1, wherein the structure,
    Figure PCTKR2013010598-appb-I000080
    represents pyridine, pyrimidine, triazine, pyrazine or pyridazine.
  7. The organic electroluminescence compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013010598-appb-I000081
    Figure PCTKR2013010598-appb-I000082
    Figure PCTKR2013010598-appb-I000083
    Figure PCTKR2013010598-appb-I000084
    Figure PCTKR2013010598-appb-I000085
    Figure PCTKR2013010598-appb-I000086
    Figure PCTKR2013010598-appb-I000087
    Figure PCTKR2013010598-appb-I000088
    Figure PCTKR2013010598-appb-I000089
    Figure PCTKR2013010598-appb-I000090
    Figure PCTKR2013010598-appb-I000091
    Figure PCTKR2013010598-appb-I000092
    Figure PCTKR2013010598-appb-I000093
    Figure PCTKR2013010598-appb-I000094
    Figure PCTKR2013010598-appb-I000095
    Figure PCTKR2013010598-appb-I000096
    Figure PCTKR2013010598-appb-I000097
    Figure PCTKR2013010598-appb-I000098
    Figure PCTKR2013010598-appb-I000099
    Figure PCTKR2013010598-appb-I000100
    Figure PCTKR2013010598-appb-I000101
  8. An organic electroluminescence device comprising the organic electroluminescence compound according to claim 1.
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