WO2017026643A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2017026643A1
WO2017026643A1 PCT/KR2016/006594 KR2016006594W WO2017026643A1 WO 2017026643 A1 WO2017026643 A1 WO 2017026643A1 KR 2016006594 W KR2016006594 W KR 2016006594W WO 2017026643 A1 WO2017026643 A1 WO 2017026643A1
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substituted
unsubstituted
alkyl
aryl
arylsilyl
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PCT/KR2016/006594
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French (fr)
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Young-Kwang Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Definitions

  • the present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent (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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the organic EL device(OLED) converts electric energy into light when electricity is applied to an organic light-emitting material(s).
  • the organic EL device has a structure comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode.
  • the organic layer of the organic EL device comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (comprising a host material and a dopant material), an electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc.
  • materials for forming the organic layer can be classified as a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc.
  • a voltage is applied to the organic EL device, holes and electrons are injected from an anode and a cathode, respectively, to the light-emitting layer.
  • Excitons having high energy are formed by recombinations between the holes and the electrons, the energy puts the organic light-emitting compound in an excited state, and the decay of the excited state results in a relaxation of the energy level into a ground state, accompanied by light-emission.
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • the light-emitting material needs to have high quantum efficiency, high electron mobility, and high hole mobility.
  • the light-emitting layer formed by the light-emitting material needs to be uniform and stable.
  • the light-emitting materials can be classified as a blue-, green-, or red-emitting material, and can additionally include a yellow- or orange-emitting material.
  • the light-emitting material can be classified according to its function, as a host material and a dopant material. Recently, the development of OLED providing high efficiency and a long lifespan is urgent.
  • a host material which plays a role as a solvent in a solid state and transfers energy, should have high purity, and an appropriate molecular weight for being deposited under a vacuum.
  • a host material should have high glass transition temperature and high thermal decomposition temperature to ensure thermal stability; high electrochemical stability to have a long lifespan; ease of preparation for amorphous thin film; and good adhesion to materials of adjacent layers.
  • a host material should not move to an adjacent layer.
  • Korean Patent Application Laying-Open No. 10-2015-0021861 discloses aromatic derivatives having a fused ring structure as light-emitting layer materials.
  • aromatic derivatives having a fused ring structure as light-emitting layer materials.
  • organic electroluminescent compounds which are effective in improving light emission efficiency and thermal stability of an organic electroluminescent device.
  • the objective of the present disclosure is to provide an organic electroluminescent compound, which is effective in preparing an organic electroluminescent device having a remarkably improved lifespan.
  • X represents -O-, -S- or -NR 9 -;
  • La represents a single bond, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
  • Ma represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
  • a and B each independently, represent a substituted or unsubstituted phenyl, or a substituted or unsubstituted naphthyl;
  • R 1 to R 9 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-
  • the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
  • the organic electroluminescent compounds of the present disclosure when they are used in a light-emitting layer, can provide the remarkably improved lifespan of the organic electroluminescent device, compared to the conventional organic light-emitting compound.
  • the present disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • X, La, Ma and R 1 to R 9 are as defined in formula 1 above;
  • R 10 to R 15 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-
  • the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
  • La may represent, preferably, a single bond, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl; and more preferably, a single bond, an unsubstituted (C6-C12)aryl, or an unsubstituted triazinyl or pyridyl.
  • Ma may represent, preferably, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C12)aryl, or phenyl, terphenyl, triazinyl, pyridyl, quinolinyl, quinazolinyl, pyrimidinyl or quinoxalinyl unsubstituted or substituted with a (C6-C20) aryl.
  • R 1 to R 9 each independently, may represent preferably, hydrogen, deuterium, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted (3 to 20-membered)heteroaryl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C1-C20)alkoxy, a substituted or unsubstituted tri(C1-C20)alkylsilyl, a substituted or unsubstituted di(C1-C20)alkyl(C6-C20)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C20)arylsilyl, a substituted or unsubstituted tri(C6-C20)ary
  • (C1-C30)alkyl indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • (C1-C30)alkoxy indicates a linear or branched alkoxy having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, etc.
  • (C3-C30)cycloalkyl indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferabley 3 to 20, more preferably 3 to 7 ring backbone carbon atoms.
  • the cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (3 to 7-membered)heterocycloalkyl indicates a cycloalkyl having 3 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes pyrrolidine, thiolan, tetrahydropyran, etc.
  • (C6-C30)aryl(ene) indicates a monocyclic ring-type or a fused ring-type radical derived from aromatic hydrocarbon having 6 to 30, preferabley 6 to 20, more preferably 6 to 15 ring backbone carbon atoms.
  • the aryl includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • (3 to 30-membered)heteroaryl(ene) indicates an aryl group having 3 to 30, preferabley 3 to 20, more preferably 3 to 15 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; 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 such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazoly
  • 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, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C6-C30)aryl, the substituted (3 to 30-membered)heteroaryl, and the substituted (C3-C30) mono- or polycyclic alicyclic or aromatic ring each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)al
  • organic electroluminescent compounds of formula 1 of the present disclosure include the following, but are not limited thereto:
  • organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art.
  • the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the organic electroluminescent compound alone of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised in an organic electroluminescent material, in addition to the compound of the present disclosure.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise 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 a hole injection layer, a hole transport layer, an electron transport layer, an electron buffering layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound of formula 1 of the present disclosure may be comprised in the light-emitting layer as a host material.
  • the light-emitting layer may further comprise at least one dopant, and if needed, a compound other than the organic electroluminescent compound of formula 1 of the present disclosure may be comprised additionally as a second host material.
  • a material for preparing an organic electroluminescent device comprises a first host material and a second host material, wherein the first host material comprises the organic electroluminescent compound of the present disclosure.
  • the weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
  • the second host material may be from any of the known phosphorescent host materials.
  • the second host material may be selected from the group consisting of the phosphorescent hosts of formulae 3 to 6 below.
  • a 1 and A 2 each independently, represent a substituted or unsubstituted (C6-C30)aryl; preferably, each independently, represent a substituted or unsubstituted (C6-C18)aryl; more preferably, each independently, represent a (C6-C18)aryl substituted or unsubstituted with a cyano, a (C1-C6)alkyl, a (C6-C12)aryl or a tri(C6-C12)arylsily; and still more preferably, each independently, represent phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl or fluoranthenyl.
  • X 1 to X 16 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30) alkenyl, a substituted or unsubstituted (C2-C30) alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substitute
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene, preferably, a substituted or unsubstituted (C6-C15)arylene, and more preferably, a (C6-C15)arylene substituted or unsubstituted with a cyano, a (C1-C6)alkyl or a tri(C6-C12)arylsilyl.
  • L 1 may be represented by any one of the following formulae 7 to 19.
  • Xi to Xp each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted
  • the second host material preferably includes the following:
  • the organic electroluminescent device of the present disclosure comprises an anode, a cathode, and at least one light-emitting layer disposed between the anode and cathode, wherein the light-emitting layer comprises a host material and a phosphorescent dopant material; the host material consists of two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by formula 1 and a second host compound is the compound represented by any of formulae 3 to 6.
  • the light-emitting layer indicates a layer from which light is emitted, which may be a single layer, and also may be multiple layers stacked by two or more layers. It is preferable that a doping amount of the dopant compound is less than 20 wt% based on the total amount of the host compound and the dopant compound.
  • the dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the compounds represented by the following formulae 101 to 103 may be used as the dopant to be comprised in the organic electroluminescent device of the present disclosure.
  • 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 substituted or unsubstituted (C1-C30)alky, a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 106 to R 109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • R 120 to R 123 may be linked to an adjacent substituent(s) to
  • 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;
  • R 124 to R 127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 208 to R 211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • r and s each independently, represent an integer of 1 to 3; when r or s is an integer of 2 or more, each of R 100 may be the same or different; and
  • e represents an integer of 1 to 3.
  • the phosphorescent dopant includes the following:
  • the organic electroluminescent device of the present disclosure comprises organic electroluminescent compounds of formula 1, and may further comprise 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 compound 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 the 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 disclosure 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 of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • 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 of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • a surface layer may be 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.
  • 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 a 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 an electroluminescent 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 the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • 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 light-emitting 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, and 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.
  • first host compound and a second host compound of the present disclosure as a host
  • OLED device was produced by using the organic electroluminescent compound of the present disclosure as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ / ⁇ ) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile(compound HI-1) 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 above introduced material, thereby forming a first hole injection layer having a thickness of 5nm on the ITO substrate.
  • N,N'-bis(naphthalen-1-yl)-N,N’-bis(phenyl)-benzidine(compound HI-2) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 95 nm on the first hole injection layer.
  • N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine(compound HT-1) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the second hole injection layer.
  • a light-emitting layer was formed thereon as follows.
  • 2,4,6-tris(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine(compound ET-1) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated, thereby forming an electron transport layer having a thickness of 35 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to prepare OLED device.
  • OLED was produced in the same manner as in Device Example 1-1, except for using compound A-1 as a sole host of a light-emitting layer.
  • OLED was produced in the same manner as in Device Example 1-1, except for using compound B-1 as a host of a light-emitting layer.
  • OLED was produced in the same manner as in Device Example 1-2, except for using compound B-1 as a sole host of a light-emitting layer.
  • a driving voltage at 10mA/cm 2 of a current density and the time taken for luminance at 10,000nits to be reduced from 100% to 95%(T95 lifespan) of the organic electroluminescent device produced in device examples 1-1 and 1-2, and comparative examples 1-1 and 1-2 are shown in Table 1 below.
  • the organic electroluminescent device of the present disclosure shows excellence in a lifespan by using the specific host, compared to the conventional organic electroluminescent device.

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Abstract

The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound of the present disclosure is effective in preparing an organic electroluminescent device having a remarkably improved lifespan.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent (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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The organic EL device(OLED) converts electric energy into light when electricity is applied to an organic light-emitting material(s). Generally, the organic EL device has a structure comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer of the organic EL device comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (comprising a host material and a dopant material), an electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. Depending on its function, materials for forming the organic layer can be classified as a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc. When a voltage is applied to the organic EL device, holes and electrons are injected from an anode and a cathode, respectively, to the light-emitting layer. Excitons having high energy are formed by recombinations between the holes and the electrons, the energy puts the organic light-emitting compound in an excited state, and the decay of the excited state results in a relaxation of the energy level into a ground state, accompanied by light-emission.
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. The light-emitting material needs to have high quantum efficiency, high electron mobility, and high hole mobility. Furthermore, the light-emitting layer formed by the light-emitting material needs to be uniform and stable. Depending on the colors visualized by light-emission, the light-emitting materials can be classified as a blue-, green-, or red-emitting material, and can additionally include a yellow- or orange-emitting material. Furthermore, the light-emitting material can be classified according to its function, as a host material and a dopant material. Recently, the development of OLED providing high efficiency and a long lifespan is urgent. In particular, considering EL requirements for a middle or large-sized OLED panel, materials showing better performance than conventional ones must be urgently developed. In order to achieve the development, a host material which plays a role as a solvent in a solid state and transfers energy, should have high purity, and an appropriate molecular weight for being deposited under a vacuum. In addition, a host material should have high glass transition temperature and high thermal decomposition temperature to ensure thermal stability; high electrochemical stability to have a long lifespan; ease of preparation for amorphous thin film; and good adhesion to materials of adjacent layers. Furthermore, a host material should not move to an adjacent layer.
Korean Patent Application Laying-Open No. 10-2015-0021861 discloses aromatic derivatives having a fused ring structure as light-emitting layer materials. However, there has been a need for new organic electroluminescent compounds which are effective in improving light emission efficiency and thermal stability of an organic electroluminescent device.
As a result of a study for finding new compounds that can provide an organic electroluminescent device with superior performance compared to the conventional organic light-emitting compounds, the present inventors found that compounds of the present disclosure can provide an organic electroluminescent device having an improved lifespan.
The objective of the present disclosure is to provide an organic electroluminescent compound, which is effective in preparing an organic electroluminescent device having a remarkably improved lifespan.
As a result of an earnest study for solving the above-described problems, the present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1 and have come to complete the present disclosure.
Figure PCTKR2016006594-appb-I000001
wherein
X represents -O-, -S- or -NR9-;
La represents a single bond, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
Ma represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
A and B, each independently, represent a substituted or unsubstituted phenyl, or a substituted or unsubstituted naphthyl;
R1 to R9, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
The organic electroluminescent compounds of the present disclosure, when they are used in a light-emitting layer, can provide the remarkably improved lifespan of the organic electroluminescent device, compared to the conventional organic light-emitting compound.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the disclosure, and is not meant in any way to restrict the scope of the disclosure.
The present disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
The compound of formula 1 of the present disclosure may be represented by the following formula 2:
Figure PCTKR2016006594-appb-I000002
wherein
X, La, Ma and R1 to R9 are as defined in formula 1 above;
R10 to R15, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
In formula 1, La may represent, preferably, a single bond, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl; and more preferably, a single bond, an unsubstituted (C6-C12)aryl, or an unsubstituted triazinyl or pyridyl.
In formula 1, Ma may represent, preferably, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C12)aryl, or phenyl, terphenyl, triazinyl, pyridyl, quinolinyl, quinazolinyl, pyrimidinyl or quinoxalinyl unsubstituted or substituted with a (C6-C20) aryl.
In formula 1, R1 to R9, each independently, may represent preferably, hydrogen, deuterium, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted (3 to 20-membered)heteroaryl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C1-C20)alkoxy, a substituted or unsubstituted tri(C1-C20)alkylsilyl, a substituted or unsubstituted di(C1-C20)alkyl(C6-C20)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C20)arylsilyl, a substituted or unsubstituted tri(C6-C20)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C20)alkylamino, a substituted or unsubstituted mono- or di-(C6-C20)arylamino, or a substituted or unsubstituted (C1-C20)alkyl(C6-C20)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C20), mono- or polycyclic, 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 contains at least one hetero atom selected from B, N, O, S, Si and P.
Herein, “(C1-C30)alkyl” indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. Herein, “(C1-C30)alkoxy” indicates a linear or branched alkoxy having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, etc. Herein, “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferabley 3 to 20, more preferably 3 to 7 ring backbone carbon atoms. The cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Herein, “(3 to 7-membered)heterocycloalkyl” indicates a cycloalkyl having 3 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes pyrrolidine, thiolan, tetrahydropyran, etc. Herein, “(C6-C30)aryl(ene)” indicates a monocyclic ring-type or a fused ring-type radical derived from aromatic hydrocarbon having 6 to 30, preferabley 6 to 20, more preferably 6 to 15 ring backbone carbon atoms. The aryl includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. Herein, “(3 to 30-membered)heteroaryl(ene)” indicates an aryl group having 3 to 30, preferabley 3 to 20, more preferably 3 to 15 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; 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 such as 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 such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Furthermore, “halogen” includes F, Cl, Br, and I.
Furthermore, 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. In formulae 1 and 2, the substituents of the substituted (C1-C30)alkyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C6-C30)aryl, the substituted (3 to 30-membered)heteroaryl, and the substituted (C3-C30) mono- or polycyclic alicyclic or aromatic ring, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, 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 substituted or unsubstituted with a (C6-C30)aryl, a (C6-C30)aryl substituted or unsubstituted 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.
More specifically, organic electroluminescent compounds of formula 1 of the present disclosure include the following, but are not limited thereto:
Figure PCTKR2016006594-appb-I000003
Figure PCTKR2016006594-appb-I000004
Figure PCTKR2016006594-appb-I000005
Figure PCTKR2016006594-appb-I000006
Figure PCTKR2016006594-appb-I000007
Figure PCTKR2016006594-appb-I000008
Figure PCTKR2016006594-appb-I000009
Figure PCTKR2016006594-appb-I000010
Figure PCTKR2016006594-appb-I000011
Figure PCTKR2016006594-appb-I000012
Figure PCTKR2016006594-appb-I000013
Figure PCTKR2016006594-appb-I000014
The organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art.
Furthermore, the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The material may consist of the organic electroluminescent compound alone of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised in an organic electroluminescent material, in addition to the compound of the present disclosure.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron buffering layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound of formula 1 of the present disclosure may be comprised in the light-emitting layer as a host material. Preferably, the light-emitting layer may further comprise at least one dopant, and if needed, a compound other than the organic electroluminescent compound of formula 1 of the present disclosure may be comprised additionally as a second host material.
According to another aspect of the present disclosure, a material for preparing an organic electroluminescent device is provided. The material comprises a first host material and a second host material, wherein the first host material comprises the organic electroluminescent compound of the present disclosure. The weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
The second host material may be from any of the known phosphorescent host materials. Preferably, the second host material may be selected from the group consisting of the phosphorescent hosts of formulae 3 to 6 below.
Figure PCTKR2016006594-appb-I000015
Figure PCTKR2016006594-appb-I000016
wherein
A1 and A2, each independently, represent a substituted or unsubstituted (C6-C30)aryl; preferably, each independently, represent a substituted or unsubstituted (C6-C18)aryl; more preferably, each independently, represent a (C6-C18)aryl substituted or unsubstituted with a cyano, a (C1-C6)alkyl, a (C6-C12)aryl or a tri(C6-C12)arylsily; and still more preferably, each independently, represent phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl or fluoranthenyl.
X1 to X16, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30) alkenyl, a substituted or unsubstituted (C2-C30) alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably, each independently, represent hydrogen, a cyano, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted (5 to 20-membered)heteroaryl, or a substituted or unsubstituted tri(C6-C12)arylsilyl; more preferably, each independently, represent hydrogen, a cyano, a (C6-C20)aryl substituted or unsubstituted with a cyano, an unsubstituted (5 to 20-membered)heteroaryl, or an unsubstituted tri(C6-C12)arylsilyl.
L1 represents a substituted or unsubstituted (C6-C30)arylene, preferably, a substituted or unsubstituted (C6-C15)arylene, and more preferably, a (C6-C15)arylene substituted or unsubstituted with a cyano, a (C1-C6)alkyl or a tri(C6-C12)arylsilyl.
Furthermore, L1 may be represented by any one of the following formulae 7 to 19.
Figure PCTKR2016006594-appb-I000017
Figure PCTKR2016006594-appb-I000018
Figure PCTKR2016006594-appb-I000019
Figure PCTKR2016006594-appb-I000020
Figure PCTKR2016006594-appb-I000021
wherein
Xi to Xp, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, 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; and
Figure PCTKR2016006594-appb-I000022
represents a bonding site.
Specifically, the second host material preferably includes the following:
Figure PCTKR2016006594-appb-I000023
Figure PCTKR2016006594-appb-I000024
Figure PCTKR2016006594-appb-I000025
Figure PCTKR2016006594-appb-I000026
Figure PCTKR2016006594-appb-I000027
Figure PCTKR2016006594-appb-I000028
Figure PCTKR2016006594-appb-I000029
Figure PCTKR2016006594-appb-I000030
Figure PCTKR2016006594-appb-I000031
Figure PCTKR2016006594-appb-I000032
Figure PCTKR2016006594-appb-I000033
Figure PCTKR2016006594-appb-I000034
Figure PCTKR2016006594-appb-I000035
Figure PCTKR2016006594-appb-I000036
Figure PCTKR2016006594-appb-I000037
Figure PCTKR2016006594-appb-I000038
Figure PCTKR2016006594-appb-I000039
According to one embodiment of the present disclosure, the organic electroluminescent device of the present disclosure comprises an anode, a cathode, and at least one light-emitting layer disposed between the anode and cathode, wherein the light-emitting layer comprises a host material and a phosphorescent dopant material; the host material consists of two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by formula 1 and a second host compound is the compound represented by any of formulae 3 to 6.
The light-emitting layer indicates a layer from which light is emitted, which may be a single layer, and also may be multiple layers stacked by two or more layers. It is preferable that a doping amount of the dopant compound is less than 20 wt% based on the total amount of the host compound and the dopant compound.
The dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The compounds represented by the following formulae 101 to 103 may be used as the dopant to be comprised in the organic electroluminescent device of the present disclosure.
Figure PCTKR2016006594-appb-I000040
Figure PCTKR2016006594-appb-I000041
Figure PCTKR2016006594-appb-I000042
wherein L is selected from the following structures:
Figure PCTKR2016006594-appb-I000043
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 substituted or unsubstituted (C1-C30)alky, a cyano, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C3-C30)cycloalkyl; R106 to R109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl; R120 to R123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a quinoline unsubstituted or substituted with an alkyl or aryl;
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; R124 to R127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; R208 to R211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
r and s, each independently, represent an integer of 1 to 3; when r or s is an integer of 2 or more, each of R100 may be the same or different; and
e represents an integer of 1 to 3.
Specifically, the phosphorescent dopant includes the following:
Figure PCTKR2016006594-appb-I000044
Figure PCTKR2016006594-appb-I000045
Figure PCTKR2016006594-appb-I000046
Figure PCTKR2016006594-appb-I000047
Figure PCTKR2016006594-appb-I000048
Figure PCTKR2016006594-appb-I000049
Figure PCTKR2016006594-appb-I000050
Figure PCTKR2016006594-appb-I000051
Figure PCTKR2016006594-appb-I000052
Figure PCTKR2016006594-appb-I000053
Figure PCTKR2016006594-appb-I000054
Figure PCTKR2016006594-appb-I000055
Figure PCTKR2016006594-appb-I000056
Figure PCTKR2016006594-appb-I000057
Figure PCTKR2016006594-appb-I000058
Figure PCTKR2016006594-appb-I000059
Figure PCTKR2016006594-appb-I000060
Figure PCTKR2016006594-appb-I000061
Figure PCTKR2016006594-appb-I000062
Figure PCTKR2016006594-appb-I000063
Figure PCTKR2016006594-appb-I000064
Figure PCTKR2016006594-appb-I000065
Figure PCTKR2016006594-appb-I000066
Figure PCTKR2016006594-appb-I000067
Figure PCTKR2016006594-appb-I000068
The organic electroluminescent device of the present disclosure comprises organic electroluminescent compounds of formula 1, and may further comprise 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 disclosure, the organic layer may further comprise, in addition to the compound 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 the 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.
In addition, the organic electroluminescent device of the present disclosure 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 of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be 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, 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.
In the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a 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 an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier 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 light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, 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, and 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.
Example 1: Preparation of compound A-1
Figure PCTKR2016006594-appb-I000069
Figure PCTKR2016006594-appb-I000070
Figure PCTKR2016006594-appb-I000071
1) Preparation of compound 1-1
After adding and dissolving compound B-1(50g, 267mmol), bis(pinacolato)diboron(88g, 347mmol), bis(triphenylphosphine)palladium(II) dichloride(Pd(PPh3)Cl2)(9g, 13.35mmol), KOAc(65g, 667mmol) and 1,4-dioxane(1.3L) into a flask, the mixture was reacted at 130℃. After completing the reaction, the organic layer was extracted with ethyl acetate. The remaining moisture was removed from the obtained organic layer with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-1(38g, yield: 61%).
2) Preparation of compound 1-2
After adding and dissolving compound B-2(100g, 423mmol), (2-chlorophenyl)boronic acid(73g, 466mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh3)4)(24g, 21mmol), Na2CO3(89g, 846mmol), water(423mL) and toluene(1.6L) into a flask, the mixture was under reflux at 120℃ for 4 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-2(74.6g, yield: 66%).
3) Preparation of compound 1-3
After adding and dissolving compound 1-1(38g, 162mmol), compound 1-2(43g, 162mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh3)4)(9.4g, 8mmol), 2M K2CO3 aqueous solution(202mL), toluene(810mL) and EtOH(202mL) into a flask, the mixture was under reflux at 120℃ for 2 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-3(25g, yield: 52%).
4) Preparation of compound 1-4
After adding compound 1-3(25g, 85mmol) and dichloromethane(DCM)(848mL) into a flask, the mixture was cooled to 0°C. After adding tribromoborane(BBr3)(12mL, 127mmol), the mixture was reacted for 13 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-4(24g, yield: 100%).
5) Preparation of compound 1-5
After adding and dissolving compound 1-4(24g, 85mmol), tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3)(4g, 4.2mmol), s-Phos(3.5g, 8.5mmol), NaOt-Bu(21g, 214mmol) and o-xylene(570mL) into a flask, the mixture was under reflux at 160℃ for 14 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-5(16.6g, yield: 80%).
6) Preparation of compound 1-6
After dissolving compound 1-5(25.6g, 105mmol) in THF(525mL), the mixture was cooled to -78℃. After adding 2.5M n-butyllithium(54mL, 136mmol) was added and the mixture was stirred for 3 hours. Then, 1,2-dibromoethane(13.6mL, 157.5mmol) was added, and the mixture was reacted. After completing the reaction, the organic layer was extracted with dichloromethane, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-6(27g, yield: 80%).
7) Preparation of compound 1-7
After adding compound 1-6(27g, 84mmol), 2-chloroaniline(13mL, 125mmol), palladium(II) acetate(Pd(OAc)2)(754mg, 3.36mmol), tri-tert-butylphosphine(P(t-Bu)3)(1.7ml, 6.72mmol), NaOtBu(20g, 210mmol) and o-xylene(840mL) into a flask, the mixture was under reflux for 3 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-7(1.1g, yield: 35%).
8) Preparation of compound 1-8
After adding compound 1-7(10g, 27mmol), palladium(II) acetate (Pd(OAc)2)(607mg, 2.7mmol), tricyclohexylphosphine tetrafluoroborate(PCy3HBF4)(2g, 5.4mmol), cesium carbonate(18g, 54mmol) and o-xylene(270mL) into a flask, the mixture was under reflux for 16 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound 1-8(7.9g, yield: 88%).
9) Preparation of compound A-1
After adding compound 1-8(3g, 9mmol), compound B-3(4.5g, 12mmol) palladium(II) acetate(Pd(OAc)2)(101mg, 0.45mmol), s-Phos(369mg, 0.9mmol), NaOt-Bu(2.2g, 22.5mmol) and o-xylene(45mL) into a flask, the mixture was under reflux for 2 hours. After completing the reaction, the organic layer was extracted with ethyl acetate, and the remaining moisture was removed with magnesium sulfate. Then, the organic layer was dried. The remaining product was subjected to column chromatography to obtain compound A-1(3.6g, yield: 62%).
Figure PCTKR2016006594-appb-I000072
Compound: A-1, a white solid, Mp 288°C, 1H NMR (CDCl3, TMS) δ 6.01-6.02(dd, 1H), 7.02-7.05(t, 1H), 7.07-7.10(t, 1H), 7.34-7.36(t, 1H), 7.45-7.49(m, 3H), 7.51-7.58(m, 4H), 7.58-7.61(m, 4H), 7.62-7.65(m, 2H), 7.75-7.76(d, 1H), 7.95(m, 2H), 8.02-8.03(d, 1H), 8.14-8.16(d, 1H), 8.81-8.83(dd, 4H), 9.08(m, 2H), 13C NMR (CDCl3, TMS) δ 110.3, 117.0, 119.9, 120.4, 120.8, 122.1, 123.6, 125.4, 126.5, 126.6, 127.7, 128.1, 128.7, 128.9, 129.0, 129.3, 129.4, 130.2, 130.9, 131.3, 132.6, 133.4, 135.0, 136.2, 136.5, 137.7, 141.9, 142.8, 146.1, 160.1, 170.9, 171.8
[Device Example 1-1] OLED device produced by a co-evaporation of a
first host compound and a second host compound of the present disclosure as a host
OLED device was produced by using the organic electroluminescent compound of the present disclosure as follows. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/□) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile(compound HI-1) 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 above introduced material, thereby forming a first hole injection layer having a thickness of 5nm on the ITO substrate. N,N'-bis(naphthalen-1-yl)-N,N’-bis(phenyl)-benzidine(compound HI-2) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 95 nm on the first hole injection layer. N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine(compound HT-1) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the second hole injection layer. After forming a hole injection layer and a hole transport layer, a light-emitting layer was formed thereon as follows. Compounds A-1 and H1-1 as a host material were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and compound D-74 as a dopant compound was introduced into another cell. The two host compounds were then evaporated at the same rate of 1:1, while the dopant was evaporated at a different rate from the host compounds, so that the dopant was deposited in a doping amount of 12 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. 2,4,6-tris(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine(compound ET-1) was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated, thereby forming an electron transport layer having a thickness of 35 nm on the light-emitting layer. After depositing lithium quinolate (EI-1) as an electron injection layer having a thickness of 2 nm, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to prepare OLED device.
Figure PCTKR2016006594-appb-I000073
[Device Example 1-2] OLED device produced by an evaporation of compound
A-1 as a sole host compond
OLED was produced in the same manner as in Device Example 1-1, except for using compound A-1 as a sole host of a light-emitting layer.
[Comparative Device Example 1-1] OLED device produced by an evaporation
of B-1 as a first host compond
OLED was produced in the same manner as in Device Example 1-1, except for using compound B-1 as a host of a light-emitting layer.
[Comparative Device Example 1-2] OLED device produced by an evaporation
of B-1 as a sole host
OLED was produced in the same manner as in Device Example 1-2, except for using compound B-1 as a sole host of a light-emitting layer.
Figure PCTKR2016006594-appb-I000074
A driving voltage at 10mA/cm2 of a current density and the time taken for luminance at 10,000nits to be reduced from 100% to 95%(T95 lifespan) of the organic electroluminescent device produced in device examples 1-1 and 1-2, and comparative examples 1-1 and 1-2 are shown in Table 1 below.
Figure PCTKR2016006594-appb-I000075
The organic electroluminescent device of the present disclosure shows excellence in a lifespan by using the specific host, compared to the conventional organic electroluminescent device.

Claims (9)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2016006594-appb-I000076
    wherein
    X represents -O-, -S- or -NR9-;
    La represents a single bond, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
    Ma represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3 to 30-membered)heteroaryl;
    A and B, each independently, represent a substituted or unsubstituted phenyl, or a substituted or unsubstituted naphthyl;
    R1 to R9, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
    the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2016006594-appb-I000077
    wherein
    X, La, Ma and R1 to R9 are as defined in claim 1;
    R10 to R15, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
    the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
  3. The organic electroluminescent compound according to claim 1, wherein in formula 1, La represents a single bond, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl, and Ma represents a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (3 to 20-membered)heteroaryl.
  4. The organic electroluminescent compound according to claim 1, wherein in formula 1, La represents a single bond, an unsubstituted (C6-C12)aryl, or an unsubstituted triazinyl or pyridyl, and Ma represents a substituted or unsubstituted (C6-C12)aryl, or phenyl, terphenyl, triazinyl, pyridyl, quinolinyl, quinazolinyl, pyrimidinyl or quinoxalinyl unsubstituted or substituted with a (C6-C20)aryl.
  5. The organic electroluminescent compound according to claim 1, wherein in formula 1, R1 to R9, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted (3 to 20-membered)heteroaryl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C1-C20)alkoxy, a substituted or unsubstituted tri(C1-C20)alkylsilyl, a substituted or unsubstituted di(C1-C20)alkyl(C6-C20)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C20)arylsilyl, a substituted or unsubstituted tri(C6-C20)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C20)alkylamino, a substituted or unsubstituted mono- or di-(C6-C20)arylamino, or a substituted or unsubstituted (C1-C20)alkyl(C6-C20)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C20), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si and P.
  6. The organic electroluminescent compound according to claim 1, wherein in formula 1, the substituent for the substituted (C1-C30)alkyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C6-C30)aryl, the substituted (3 to 30-membered)heteroaryl, and the substituted (C3-C30) mono- or polycyclic alicyclic or aromatic ring, each independently, is at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, 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 substituted or unsubstituted with a (C6-C30)aryl, a (C6-C30)aryl substituted or unsubstituted 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.
  7. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2016006594-appb-I000078
    Figure PCTKR2016006594-appb-I000079
    Figure PCTKR2016006594-appb-I000080
    Figure PCTKR2016006594-appb-I000081
    Figure PCTKR2016006594-appb-I000082
    Figure PCTKR2016006594-appb-I000083
    Figure PCTKR2016006594-appb-I000084
    Figure PCTKR2016006594-appb-I000085
    Figure PCTKR2016006594-appb-I000086
    Figure PCTKR2016006594-appb-I000087
    Figure PCTKR2016006594-appb-I000088
    Figure PCTKR2016006594-appb-I000089
  8. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
  9. The organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer disposed between the anode and cathode, wherein the light-emitting layer comprises a host material and a phosphorescent dopant material; the host material consists of two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by formula 1 according to claim 1 and a second host compound is the compound represented by any of formulae 3 to 6.
    Figure PCTKR2016006594-appb-I000090
    Figure PCTKR2016006594-appb-I000091
    wherein
    A1 and A2, each independently, represent a substituted or unsubstituted (C6-C30)aryl;
    X1 to X16, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30) alkenyl, a substituted or unsubstituted (C2-C30) alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted (3 to 30-membered)heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and
    L1 represents a substituted or unsubstituted (C6-C30)arylene.
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