WO2014185694A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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WO2014185694A1
WO2014185694A1 PCT/KR2014/004286 KR2014004286W WO2014185694A1 WO 2014185694 A1 WO2014185694 A1 WO 2014185694A1 KR 2014004286 W KR2014004286 W KR 2014004286W WO 2014185694 A1 WO2014185694 A1 WO 2014185694A1
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group
substituted
unsubstituted
organic electroluminescent
independently represent
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PCT/KR2014/004286
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French (fr)
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Young-Kwang Kim
Nam-Kyun Kim
Chi-Sik Kim
Young-Jun Cho
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to CN201480024612.2A priority Critical patent/CN105392789B/en
Publication of WO2014185694A1 publication Critical patent/WO2014185694A1/en

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    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/16—Peri-condensed systems
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • 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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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing 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 [see Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminescent efficiency of an organic EL device is a light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials.
  • 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 mixed system of a dopant/host material can be used as a light-emitting material to improve color purity, luminescent efficiency and stability. If the dopant/host material system is used, the selection of the host material is important because the host material greatly influences on efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as a phosphorescent host material.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • 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
  • the organic EL device comprising the materials has low quantum efficiency and a short operating lifespan, because, when the organic EL device is driven at a high current, thermal stress is generated between an anode and a hole injection layer, thereby rapidly reducing the operating lifespan of the device. Furthermore, movement of holes is great in organic materials used in a hole injection layer, and thus the hole-electron charge balance is broken and quantum efficiency (cd/A) is reduced.
  • Korean Patent Application Laid-open No. 2011-0066763 discloses indoloacridine-based compounds as compounds for an organic EL device.
  • the organic EL device comprising the compounds has high driving voltage and comprises a hole blocking layer thereby increasing the voltage needs of the device.
  • the present inventors have found that by using phosphorescent host compounds having excellent electron transport efficiency in a light-emitting layer of an organic EL device, the hole-electron charge balance is well established in a light-emitting layer, the driving voltage of the device is reduced, and the power efficiency of the device is enhanced. Furthermore, an organic EL device comprising the host material does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
  • the objective of the present invention is to provide an organic electroluminescent compound having high current transport efficiency, and an organic electroluminescent device having low driving voltage and enhanced power efficiency by comprising the organic electroluminescent compound in a light-emitting layer.
  • L 1 to L 3 each independently represent a single bond, a substituted or unsubstituted 3- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30)arylene group, or (C1-C30)alkylene group;
  • a 1 to A 3 each independently represent the following structure:
  • X 1 and X 2 each independently represent CR 3 or N;
  • Y represents -O-, -S- or -NR 12 -;
  • R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or R 1 and R 2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom
  • R 3 to R 7 and R 12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR 13 R 14 , -SiR 15 R 16 R 17 , -SR 18 , -OR 19 , a cyano group, a nitro group or a hydroxyl group;
  • R 10 and R 11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
  • R 13 to R 19 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each of R 4 , each of R 6 , or each of R 7 is the same or different;
  • b is an integer of 1;
  • l, m and n each independently represent 0 or 1.
  • the organic electroluminescent compound according to the present invention has high electron transport efficiency, which can prevent crystallization during the formation of the device; is effective in forming a layer(s) to improve the current property of the device, and thus reduces the driving voltage of the device; and has the advantages of providing an organic EL device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
  • the present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
  • L 1 to L 3 each independently represent a single bond, or a substituted or unsubstituted (C6-C30)arylene group;
  • R 1 and R 2 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; or R 1 and R 2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
  • R 3 to R 7 and R 12 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, or -SiR 15 R 16 R 17 ; and
  • R 10 and R 11 each independently represent hydrogen, or
  • the compound of formula 1 of the present invention is preferably represented by the following formula 2:
  • L 1 to L 3 , A 1 to A 3 , X 1 and X 2 , Y, R 3 to R 7 , R 10 to R 19 , a, b, c, d, l, m and n are as defined in formula 1;
  • e and f are as defined for a, c and d in formula 1;
  • R 8 and R 9 are as defined for R 4 to R 7 in formula 1;
  • a 4 is as defined for A 1 to A 3 in formula 1;
  • L 4 is as defined for L 1 to L 3 in formula 1.
  • (C1-C30)alkyl(ene) is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, 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 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • 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.
  • organic electroluminescent compounds according to the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme:
  • the present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise 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 an electron blocking layer.
  • the light-emitting layers can include the organic electroluminescent compound of the present invention.
  • the organic electroluminescent compounds of the present invention can be included as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one other compounds as host materials, in addition to the organic electroluminescent compound of the present invention, and may further include at least one dopant.
  • the organic electroluminescent compound of the present invention is included as the host material (a first host material) in the light-emitting layer, other compounds may be included as a second host material.
  • the first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
  • the second host material which is other compounds in addition to the organic electroluminescent compound of the present invention, can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 3 to 5 in view of luminescent efficiency:
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R 25 R 26 R 27 Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
  • M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )- or -C(R 32 )(R 33 )-; and Y 1 and Y 2 are not simultaneously present;
  • R 31 to R 33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R 32 and R 33 may be the 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.
  • each (Cz-L 4 ), each (Cz), each R 21 , each R 22 , each R 23 or each R 24 is the same or different.
  • the second host material includes the following:
  • TPS represents triphenylsilyl
  • the dopants applied to the organic electroluminescent device of the present invention are preferably one or more phosphorescent dopants.
  • the phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably ortho metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant may be selected from the group consisting of the compounds represented by the following formulae 6 to 8:
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group
  • R 101 to R 109 and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group
  • R 120 to R 123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or
  • the phosphorescent dopant material includes the following:
  • the present invention further provides the composition for the organic electroluminescent device.
  • the composition comprises the compounds of the present invention as a host material.
  • the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes, wherein the organic layer comprises a light-emitting layer and the light-emitting layer may comprise the composition for the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the organic electroluminescent compounds of formula 1, 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 the metal.
  • the organic layer may further comprise a light-emitting layer and a charge-generating layer.
  • the organic electroluminescent device of 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, besides the compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
  • a surface layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • the surface layer provides operating stability for the organic electroluminescent device.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the 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 may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to a light-emitting medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to a light-emitting 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 organic electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc.
  • wet film-forming methods such as spin coating, dip coating, flow coating methods, etc.
  • a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • suitable solvents such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
  • An organic light-emitting diode (OLED) device comprising the organic electroluminescent compound according to the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an 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.
  • ITO indium tin oxide
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalene-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the 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’-diamino biphenyl was introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • Compound H-2 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell.
  • the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 15 wt%, based on the total weight 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(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% 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 green emission having a luminance of 1640 cd/m 2 and a current density of 3.84 mA/cm 2 at 2.6 V.
  • Comparative Example 1 Production of an OLED device by using
  • An OLED device was produced in the same manner as in Device Example 1, except that 4,4’-N,N’-dicarbazole-biphenyl was used as a host and compound D-86 was used as a dopant in a light-emitting material; a light-emitting layer having a thickness of 30 nm was deposited on a hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed green emission having a luminance of 3000 cd/m 2 and a current density of 8.56 mA/cm 2 at 5.8 V.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-2 as a host was introduced into one cell of the vacuum vapor depositing apparatus, compound D-88 as a dopant was introduced into another cell, and the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 4 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed red emission having a luminance of 1570 cd/m 2 and a current density of 19.0 mA/cm 2 at 4.1 V.
  • Comparative Example 2 Production of an OLED device by
  • An OLED device was produced in the same manner as in Device Example 1, except that 4,4’-N,N’-dicarbazole-biphenyl was used as a host and compound D-88 was used as a dopant in a light-emitting material; a light-emitting layer having a thickness of 30 nm was deposited on a hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 and a current density of 20.0 mA/cm 2 at 8.2 V.
  • the organic electroluminescent compound according to the present invention has high electron transport efficiency, which can prevent crystallization during the formation of the device; is effective in forming a layer(s) to improve the current property of the device, and thus reduces the driving voltage of the device; and has the advantages of providing an OLED device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has high electron transport efficiency, which can prevent crystallization during the formation of the device; is effective in forming a layer(s) to improve the current property of the device, and thus reduces the driving voltage of the device; and has the advantages of providing an OLED device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing 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 [see Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminescent efficiency of an organic EL device is a light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials. Until now, 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 mixed system of a dopant/host material can be used as a light-emitting material to improve color purity, luminescent efficiency and stability. If the dopant/host material system is used, the selection of the host material is important because the host material greatly influences on efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as a phosphorescent host material. Pioneer (Japan) et al., currently developed a high performance organic EL device by employing bathocuproine (BCP), aluminum(III) bis(2-methyl-8-quinolinato)(4-phenylphenolate) (BAlq), etc., which were used in a hole blocking layer, as host materials.
Although these phosphorescent host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperatures 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 voltage. An organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) and has a higher driving voltage than one comprising fluorescent host materials. Thus, the organic EL device using conventional phosphorescent materials has no advantage in terms of power efficiency (lm/W). (3) Furthermore, the operating lifespan and luminous efficiency of the organic EL device are not satisfactory.
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., have been used as hole injection and transport materials in the organic EL device. However, the organic EL device comprising the materials has low quantum efficiency and a short operating lifespan, because, when the organic EL device is driven at a high current, thermal stress is generated between an anode and a hole injection layer, thereby rapidly reducing the operating lifespan of the device. Furthermore, movement of holes is great in organic materials used in a hole injection layer, and thus the hole-electron charge balance is broken and quantum efficiency (cd/A) is reduced.
Korean Patent Application Laid-open No. 2011-0066763 discloses indoloacridine-based compounds as compounds for an organic EL device. However, the organic EL device comprising the compounds has high driving voltage and comprises a hole blocking layer thereby increasing the voltage needs of the device.
The present inventors have found that by using phosphorescent host compounds having excellent electron transport efficiency in a light-emitting layer of an organic EL device, the hole-electron charge balance is well established in a light-emitting layer, the driving voltage of the device is reduced, and the power efficiency of the device is enhanced. Furthermore, an organic EL device comprising the host material does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
The objective of the present invention is to provide an organic electroluminescent compound having high current transport efficiency, and an organic electroluminescent device having low driving voltage and enhanced power efficiency by comprising the organic electroluminescent compound in a light-emitting layer.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014004286-appb-I000001
wherein
L1 to L3 each independently represent a single bond, a substituted or unsubstituted 3- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30)arylene group, or (C1-C30)alkylene group;
A1 to A3 each independently represent the following structure:
Figure PCTKR2014004286-appb-I000002
X1 and X2 each independently represent CR3 or N;
Y represents -O-, -S- or -NR12-;
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or R1 and R2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R3 to R7 and R12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR13R14, -SiR15R16R17, -SR18, -OR19, a cyano group, a nitro group or a hydroxyl group;
R10 and R11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
R13 to R19 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
the heteroaryl(ene) group and the heterocycloalkyl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each of R4, each of R6, or each of R7 is the same or different;
b is an integer of 1; and
l, m and n each independently represent 0 or 1.
The organic electroluminescent compound according to the present invention has high electron transport efficiency, which can prevent crystallization during the formation of the device; is effective in forming a layer(s) to improve the current property of the device, and thus reduces the driving voltage of the device; and has the advantages of providing an organic EL device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.
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 represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
In the compound of formula 1 of the present invention, preferably, L1 to L3 each independently represent a single bond, or a substituted or unsubstituted (C6-C30)arylene group; R1 and R2 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; or R1 and R2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring; R3 to R7 and R12 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, or -SiR15R16R17; and R10 and R11 each independently represent hydrogen, or a substituted or unsubstituted (C6-C30)aryl group.
The compound of formula 1 of the present invention is preferably represented by the following formula 2:
Figure PCTKR2014004286-appb-I000003
wherein
L1 to L3, A1 to A3, X1 and X2, Y, R3 to R7, R10 to R19, a, b, c, d, l, m and n are as defined in formula 1;
e and f are as defined for a, c and d in formula 1;
R8 and R9 are as defined for R4 to R7 in formula 1;
A4 is as defined for A1 to A3 in formula 1; and
L4 is as defined for L1 to L3 in formula 1.
Herein, “(C1-C30)alkyl(ene)” is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, 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. “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and 3 to 7, preferably 5 to 7 ring backbone atoms, and includes tetrahydrofurane, pyrrolidine, thiolan, tetrahydropyran, 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 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “3- to 30-membered heteroaryl(ene)” is an aryl group 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 3 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 3 to 20, more preferably 3 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. “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. Substituents of the substituted (C1-C30)alkyl group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 3- to 30-membered heteroaryl(ene) group and the substituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring in L1 to L4 and R1 to R19 of formulae 1 and 2 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 3- to 30-membered heteroaryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30) alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
The organic electroluminescent compounds according to the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014004286-appb-I000004
Figure PCTKR2014004286-appb-I000005
Figure PCTKR2014004286-appb-I000006
Figure PCTKR2014004286-appb-I000007
Figure PCTKR2014004286-appb-I000008
Figure PCTKR2014004286-appb-I000009
Figure PCTKR2014004286-appb-I000010
Figure PCTKR2014004286-appb-I000011
Figure PCTKR2014004286-appb-I000012
Figure PCTKR2014004286-appb-I000013
Figure PCTKR2014004286-appb-I000014
Figure PCTKR2014004286-appb-I000015
Figure PCTKR2014004286-appb-I000016
Figure PCTKR2014004286-appb-I000017
Figure PCTKR2014004286-appb-I000018
The organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme:
Figure PCTKR2014004286-appb-I000019
The present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material. The material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
One of the first electrodes and the second electrodes can be an anode and the other can be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise 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 an electron blocking layer.
The light-emitting layers can include the organic electroluminescent compound of the present invention. When used in the light-emitting layer, the organic electroluminescent compounds of the present invention can be included as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one other compounds as host materials, in addition to the organic electroluminescent compound of the present invention, and may further include at least one dopant.
If the organic electroluminescent compound of the present invention is included as the host material (a first host material) in the light-emitting layer, other compounds may be included as a second host material. The first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
The second host material, which is other compounds in addition to the organic electroluminescent compound of the present invention, can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 3 to 5 in view of luminescent efficiency:
Figure PCTKR2014004286-appb-I000020
Figure PCTKR2014004286-appb-I000021
Figure PCTKR2014004286-appb-I000022
wherein
Cz represents the following structure:
Figure PCTKR2014004286-appb-I000023
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R25R26R27Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-; and Y1 and Y2 are not simultaneously present;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R32 and R33 may be the 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;
where h, i, j, k, l or m is an integer of 2 or more, each (Cz-L4), each (Cz), each R21, each R22, each R23 or each R24 is the same or different.
Specifically, the second host material includes the following:
Figure PCTKR2014004286-appb-I000024
Figure PCTKR2014004286-appb-I000025
Figure PCTKR2014004286-appb-I000026
Figure PCTKR2014004286-appb-I000027
Figure PCTKR2014004286-appb-I000028
Figure PCTKR2014004286-appb-I000029
Figure PCTKR2014004286-appb-I000030
Figure PCTKR2014004286-appb-I000031
Figure PCTKR2014004286-appb-I000032
Figure PCTKR2014004286-appb-I000033
Figure PCTKR2014004286-appb-I000034
Figure PCTKR2014004286-appb-I000035
Figure PCTKR2014004286-appb-I000036
Figure PCTKR2014004286-appb-I000037
Figure PCTKR2014004286-appb-I000038
Figure PCTKR2014004286-appb-I000039
Figure PCTKR2014004286-appb-I000040
wherein TPS represents triphenylsilyl.
The dopants applied to the organic electroluminescent device of the present invention are preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably ortho metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopant may be selected from the group consisting of the compounds represented by the following formulae 6 to 8:
Figure PCTKR2014004286-appb-I000041
Figure PCTKR2014004286-appb-I000042
Figure PCTKR2014004286-appb-I000043
wherein
L is selected from the following structures:
Figure PCTKR2014004286-appb-I000044
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; R101 to R109 and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group; R120 to R123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline; R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; when R124 to R127 are aryl groups, they are linked to an adjacent substituent(s) to form a fused ring, for example, fluorene; R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, or a (C6-C30)aryl group; f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each R100 may be the same or different; and n represents an integer of 1 to 3.
The phosphorescent dopant material includes the following:
Figure PCTKR2014004286-appb-I000045
Figure PCTKR2014004286-appb-I000046
Figure PCTKR2014004286-appb-I000047
Figure PCTKR2014004286-appb-I000048
Figure PCTKR2014004286-appb-I000049
Figure PCTKR2014004286-appb-I000050
Figure PCTKR2014004286-appb-I000051
Figure PCTKR2014004286-appb-I000052
Figure PCTKR2014004286-appb-I000053
Figure PCTKR2014004286-appb-I000054
Figure PCTKR2014004286-appb-I000055
Figure PCTKR2014004286-appb-I000056
Figure PCTKR2014004286-appb-I000057
Figure PCTKR2014004286-appb-I000058
Figure PCTKR2014004286-appb-I000059
Figure PCTKR2014004286-appb-I000060
Figure PCTKR2014004286-appb-I000061
Figure PCTKR2014004286-appb-I000062
Figure PCTKR2014004286-appb-I000063
Figure PCTKR2014004286-appb-I000064
Figure PCTKR2014004286-appb-I000065
The present invention further provides the composition for the organic electroluminescent device. The composition comprises the compounds of the present invention as a host material.
Furthermore, the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes, wherein the organic layer comprises a light-emitting layer and the light-emitting layer may comprise the composition for the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the organic electroluminescent compounds of formula 1, 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 the metal. Furthermore, the organic layer may further comprise a light-emitting layer and a charge-generating layer.
In addition, the organic electroluminescent device of 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, besides the compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
Preferably, in the organic electroluminescent device according to the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
Preferably, 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 may be 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 becomes easier to inject and transport electrons from the mixed region to a light-emitting medium. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to a light-emitting 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 organic electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer constituting the organic electroluminescent device according to the present invention, dry film-forming methods, such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods, such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples:
Example 1: Preparation of compound H-2
Figure PCTKR2014004286-appb-I000066
Preparation of compound H-2-2
Compound H-2-1 (60.0 g, 263.0 mmol), 2-bromonitrobenzene (44.2 g, 219.0 mmol), tetrakis(triphenylphosphine)palladium(O) [Pd(PPh3)4] (7.6 g, 6.57 mmol), K2CO3 (60.5 g, 438.0 mmol), toluene (900.0 mL), ethanol (EtOH) (220.0mL) and H2O (220.0 mL) were reflux stirred in a 2L round-bottom flask (RBF). After 5 hours, the mixture was extracted with dichloromethane (DCM) and H2O, and the DCM layer was dried over MgSO4 and was filtered. The obtained solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2-2 (74.8 g, 93 %).
Preparation of compound H-2-3
Compound H-2-2 (74.8 g, 245.0 mmol), triethylphosphite [P(OEt)3] (500.0 mL) and 1,2-dichlorobenzene (1,2-DCB) (200.0 mL) were reflux stirred in a 1L RBF. After 13 hours, the solvent was distilled, and the solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2-3 (38.0 g, 56 %).
Preparation of compound H-2-4
Compound H-2-3 (27.0 g, 98.7 mmol), 1,2-dibromobenzene (46.6 g, 197.5 mmol), Cu powder (3.1 g, 49.35 mmol), K2CO3 (27.3 g, 197.5 mmol) and 1,2-DCB (500.0 mL) were reflux stirred in a 1L RBF. After 23 hours, the solvent was distilled, and the obtained solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2-4 (28.19 g, 67 %).
Preparation of compound H-2-5
Compound H-2-4 (28.19 g, 66.0 mmol) and tetrahydrofuran (THF) (300.0 mL) in a 1L RBF were cooled to -78 °C. After adding 2.5 M n-buthyl lithium (34.2 mL, 85.5 mmol), 2-bromo-9-fluorenone (22.2 g, 85.5 mmol) was added 2 hours later. After 18 hours, the mixture was extracted with methylene chloride (MC) and H2O, and the MC layer was dried over MgSO4. The MC layer was filtered and was concentrated to obtain compound H-2-5 (35.3 g, 91 %).
Preparation of compound H-2-6
Compound H-2-5 (35.3 g, 60.0 mmol), hydrochloric acid (80.0 mL) and acetic acid (600.0 mL) were reflux stirred in a 1L RBF. After 14 hours, the resulting solid was filtered, the filtered solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2-6 (27.9 g, 78 %).
Preparation of compound H-2-7
Compound H-2-6 (28.0 g, 47.2 mmol), bis(pinacolato)diborane (13.2 g, 52.0 mmol), potassium acetate (KOAc) (7.7 g, 94.4 mmol) and 1,4-dioxane (500.0 mL) were reflux stirred in a 1L RBF. After 3 hours, the mixture was extracted with DCM and H2O, and the DCM layer was dried over MgSO4 and was filtered. The obtained solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2-7 (9.0 g, 31 %).
Preparation of compound H-2
Compound H-2-7 (8.3 g, 13.0 mmol), compound H-3-2 (5.2 g, 19.5 mmol), Pd(PPh3)4 (450.0 mg, 0.39 mmol), K2CO3 (3.6 g, 26.0 mmol), toluene (100.0 mL) and H2O (13.0 mL) were reflux stirred in a 250 mL RBF. After 3 hours, the mixture was extracted with DCM and H2O, and the DCM layer was dried over MgSO4 and was filtered. The obtained solid was dissolved in CHCl3 and was separated through column chromatography on silica gel to obtain compound H-2 (2.5 g, 26 %).
Device Example 1: Production of an OLED device by using the
organic electroluminescent compound according to the present invention
An organic light-emitting diode (OLED) device comprising the organic electroluminescent compound according to the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an 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-(naphthalene-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the 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’-diamino biphenyl was introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Compound H-2 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell. The two materials were evaporated at different rates and the dopant was deposited in a doping amount of 15 wt%, based on the total weight 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(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% 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 green emission having a luminance of 1640 cd/m2 and a current density of 3.84 mA/cm2 at 2.6 V.
Comparative Example 1: Production of an OLED device by using
conventional light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that 4,4’-N,N’-dicarbazole-biphenyl was used as a host and compound D-86 was used as a dopant in a light-emitting material; a light-emitting layer having a thickness of 30 nm was deposited on a hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
The produced OLED device showed green emission having a luminance of 3000 cd/m2 and a current density of 8.56 mA/cm2 at 5.8 V.
Device Example 2: Production of an OLED device by 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 that compound H-2 as a host was introduced into one cell of the vacuum vapor depositing apparatus, compound D-88 as a dopant was introduced into another cell, and the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 4 wt%, based on the total weight 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(naphthalene-2-yl)anthracene-2-yl)phenyl)1-phenyl-1H-benzo[d]imidiazole was introduced into one cell, lithium quinolate was introduced into another cell, and the two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
The produced OLED device showed red emission having a luminance of 1570 cd/m2 and a current density of 19.0 mA/cm2 at 4.1 V.
Comparative Example 2: Production of an OLED device by
using conventional light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that 4,4’-N,N’-dicarbazole-biphenyl was used as a host and compound D-88 was used as a dopant in a light-emitting material; a light-emitting layer having a thickness of 30 nm was deposited on a hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
The produced OLED device showed red emission having a luminance of 1000 cd/m2 and a current density of 20.0 mA/cm2 at 8.2 V.
The organic electroluminescent compound according to the present invention has high electron transport efficiency, which can prevent crystallization during the formation of the device; is effective in forming a layer(s) to improve the current property of the device, and thus reduces the driving voltage of the device; and has the advantages of providing an OLED device having advanced power efficiency. While organic electroluminescent devices comprising conventional organic electroluminescent compounds need hole blocking layers, the organic electroluminescent device comprising the organic electroluminescent compound of the present invention does not have to comprise a hole blocking layer, and thus can decrease the voltage needs of the device.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014004286-appb-I000067
    wherein
    L1 to L3 each independently represent a single bond, a substituted or unsubstituted 3- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30)arylene group, or (C1-C30)alkylene group;
    A1 to A3 each independently represent the following structure:
    Figure PCTKR2014004286-appb-I000068
    X1 and X2 each independently represent CR3 or N;
    Y represents -O-, -S- or -NR12-;
    R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or R1 and R2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    R3 to R7 and R12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR13R14, -SiR15R16R17, -SR18, -OR19, a cyano group, a nitro group or a hydroxyl group;
    R10 and R11 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
    R13 to R19 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    the heteroaryl(ene) group and the heterocycloalkyl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
    a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each of R4, each of R6, or each of R7 is the same or different;
    b is an integer of 1; and
    l, m and n each independently represent 0 or 1.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2014004286-appb-I000069
    wherein
    L1 to L3, A1 to A3, X1 and X2, Y, R3 to R7, R10 to R19, a, b, c, d, l, m and n are as defined in claim 1;
    e and f are as defined for a, c and d in claim 1;
    R8 and R9 are as defined for R4 to R7 in claim 1;
    A4 is as defined for A1 to A3 in claim 1; and
    L4 is as defined for L1 to L3 in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 3- to 30-membered heteroaryl(ene) group, and the substituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring in L1 to L4 and R1 to R19 are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group unsubstituted or substituted with a 3- to 30-membered heteroaryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
  4. The organic electroluminescent compound according to claim 1, wherein L1 to L3 each independently represent a single bond, or a substituted or unsubstituted (C6-C30)arylene group; R1 and R2 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; or R1 and R2 are fused to form a substituted or unsubstituted mono- or polycyclic, (C3-C30) alicyclic or aromatic ring; R3 to R7 and R12 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, or -SiR15R16R17; and R10 and R11 each independently represent hydrogen, or a substituted or unsubstituted (C6-C30)aryl group.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of the following compounds:
    Figure PCTKR2014004286-appb-I000070
    Figure PCTKR2014004286-appb-I000071
    Figure PCTKR2014004286-appb-I000072
    Figure PCTKR2014004286-appb-I000073
    Figure PCTKR2014004286-appb-I000074
    Figure PCTKR2014004286-appb-I000075
    Figure PCTKR2014004286-appb-I000076
    Figure PCTKR2014004286-appb-I000077
    Figure PCTKR2014004286-appb-I000078
    Figure PCTKR2014004286-appb-I000079
    Figure PCTKR2014004286-appb-I000080
    Figure PCTKR2014004286-appb-I000081
    Figure PCTKR2014004286-appb-I000082
    Figure PCTKR2014004286-appb-I000083
    Figure PCTKR2014004286-appb-I000084
  6. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2014/004286 2013-05-14 2014-05-13 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same WO2014185694A1 (en)

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