WO2014088290A1 - 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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WO2014088290A1
WO2014088290A1 PCT/KR2013/011108 KR2013011108W WO2014088290A1 WO 2014088290 A1 WO2014088290 A1 WO 2014088290A1 KR 2013011108 W KR2013011108 W KR 2013011108W WO 2014088290 A1 WO2014088290 A1 WO 2014088290A1
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substituted
unsubstituted
aryl
membered
alkyl
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PCT/KR2013/011108
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French (fr)
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Hyun-Ju Kang
Doo-Hyeon Moon
Hee-Ryong Kang
Seok-Keun Yoon
Nam-Kyun Kim
Seon-Woo Lee
Hyuck-Joo Kwon
Kyung-Joo Lee
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to CN201380059780.0A priority Critical patent/CN104797571A/en
Publication of WO2014088290A1 publication Critical patent/WO2014088290A1/en

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Definitions

  • the present invention relates to organic electroluminescent compounds 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 most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as the light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Korean Patent Application Laying-Open Nos. 2011-0013220, 2005-0100694 and 2007-0073868 disclose compounds for an organic EL device, in which an aryl or nitrogen-containing heteroaryl is connected to the nitrogen atom of benzocarbazole or dibenzocarbazole backbone.
  • the above references fail to specifically disclose the compounds for an organic EL device, in which a phenyl and a nitrogen-containing heteroaryl are connected to the carbon atom and nitrogen atom of benzocarbazole, respectively.
  • the objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device having a long lifespan and being operated at a low driving voltage to enhance current and power efficiency.
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene;
  • Ar 1 to Ar 4 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 (C1-C30)alkylamino, a substituted or unsubstituted (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
  • an organic electroluminescent device can have a long lifespan and be operated at a low driving voltage to enhance current and power efficiency.
  • the present invention provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • Alkenyl includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • Alkynyl includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • aryl(ene) indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, 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.
  • the substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkylamino, the substituted arylamino and the substituted alkylarylamino in L 1 , Ar 1 to Ar 4 , A ring and R 1 to R 3 of formula 1 above, each independently, are at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C1-C30)alkoxy, a (C6-C30)aryl, a (3- to 30-membered) heteroaryl unsubstituted or substituted with a (C6-C
  • the compound of formula 1 can be represented by the following formula 1a or 1b:
  • L 1 , Ar 1 to Ar 4 , A ring, X 1 , X 2 , X 3 , R 2 , R 3 , l, m and n are as defined in formula 1 above.
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene; preferably, a single bond, or a substituted or unsubstituted (C6-C21)arylene; more preferably, a single bond, or an unsubstituted (C6-C21)arylene; and even more preferably a single bond or phenylene.
  • Ar 1 to Ar 4 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 (C1-C30)alkylamino, a substituted or unsubstituted (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 (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring; and preferably, hydrogen, an unsubstituted (C1-C6)alkyl, a substituted or unsubsti
  • Ar 1 , Ar 3 and Ar 4 each independently, represent hydrogen, or an unsubstituted (C6-C12)aryl;
  • Ar 2 represents hydrogen, a (C1-C4)alkyl, a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s), or an unsubstituted (5- to 18-membered) heteroaryl.
  • Ar 1 represents hydrogen, phenyl or naphthyl
  • Ar 2 represents hydrogen, a (C1-C4)alkyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl substituted with a (C1-C4)alkyl(s), or benzofluorenyl substituted with a (C1-C4)alkyl(s)
  • Ar 3 represents hydrogen
  • Ar 4 represents hydrogen or phenyl.
  • a ring represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; preferably a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl; more preferably, a (C6-C12)aryl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s); and, even more preferably, phenyl, biphenyl, naphthyl, quinolyl, isoquinolyl, naphthyridinyl, phenanthrenyl, phenanthridinyl, benzoquinolyl, benzoquinazolyl, benzoisoquinolyl, phenanthrolinyl, pyridyl, pyrimidiny
  • X 1 to X 3 represent -CR 1 -, -CR 2 - and -CR 3 - respectively
  • a ring represents a nitrogen-containing (3- to 30-membered) heteroaryl, preferably a nitrogen-containing (5- to 21-membered) heteroaryl, and more preferably a nitrogen-containing (5- to 15-membered) heteroaryl.
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (C13-C30) spirofluorenyl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; and preferably, hydrogen, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (C15-C25)spirofluorenyl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl.
  • R 1 to R 3 each independently, represent hydrogen; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s) or a (C6-C12)aryl(s); a (C15-C25)spirofluorenyl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s).
  • R 1 to R 3 each independently, represent hydrogen; phenyl; biphenyl; terphenyl; naphthyl; naphthylphenyl; phenyl substituted with a (C1-C4)alkyl(s); fluorenyl; fluorenyl substituted with a (C1-C4)alkyl(s) or phenyl(s); spirobifluorenyl; spiro[cyclopentan-1,9’-fluoren]yl; spiro[cyclohexan-1,9’-fluoren]yl; dibenzofuranyl; dibenzothiophenyl; or carbazolyl substituted with phenyl(s).
  • R 1 represents hydrogen
  • R 2 represents hydrogen or phenyl
  • R 3 represents hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted with a (C1-C4)alkyl(s), dibenzofuranyl, dibenzothiophenyl, or carbazolyl substituted with phenyl(s).
  • L 1 represents a single bond, or a substituted or unsubstituted (C6-C21)arylene;
  • Ar 1 to Ar 4 each independently, represent hydrogen, an unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C21)aryl, or an unsubstituted (5- to 21-membered) heteroaryl;
  • a ring represents a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl;
  • X 1 represents -N- or -CR 1 -;
  • X 2 represents -N- or -CR 2 -;
  • X 3 represents -N- or -CR 3 -; where X 1 to X 3 represent -CR 1 -, -CR 2 - and -CR 3 - respectively,
  • a ring represents a nitrogen-containing (5
  • L 1 represents a single bond, or an unsubstituted (C6-C12)arylene
  • Ar 1 , Ar 3 and Ar 4 each independently, represent hydrogen or an unsubstituted (C6-C12)aryl
  • Ar 2 represents hydrogen; a (C1-C4)alkyl; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s); or an unsubstituted (5- to 18-membered) heteroaryl
  • a ring represents a (C6-C12)aryl; or a (5- to 15-membered) unsubstituted or substituted with a (C6-C12)aryl(s)
  • X 1 represents -N- or -CR 1 -
  • X 2 represents -N- or -CR 2 -
  • X 3 represents -N- or -CR 3 -; where X 1 to X 3
  • Organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
  • the compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1 or 2.
  • the present invention 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 of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
  • the organic electroluminescent device 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 injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic layer may comprise a light-emitting layer in which the organic electroluminescent compound of formula 1 may be comprised as a host material.
  • a phosphorescent dopant which is used for an organic electroluminescent device together with the host material according to the present invention, may be selected from the compounds represented by the following formula 2:
  • M 1 is selected from the group consisting of Ir, Pt, Pd and Os;
  • L 101 , L 102 and L 103 are each independently selected from the following structures:
  • R 201 to R 203 each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl(s), or a halogen;
  • R 204 to R 219 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF 5 , a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a
  • R 220 to R 223 each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl(s);
  • R 224 and R 225 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a halogen, or may be linked to each other to form a (C5-C30), mono- or polycyclic, alicyclic or aromatic ring;
  • R 226 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- or 30-membered) heteroaryl or a halogen;
  • R 227 to R 229 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl or a halogen;
  • R 230 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • f and g each independently, represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R 230 may be the same or different;
  • R 231 to R 242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C1-C30)alkoxy, a halogen, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C5-C30)cycloalkyl, or may be linked to an adjacent substituent(s) via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R 207 or R 208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
  • the dopants of formula 2 are preferred, but are not limited thereto:
  • the organic electroluminescent device of the present invention may further comprise, in addition to the organic electroluminescent compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the organic electroluminescent 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 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device 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 known in the field, besides the compound of the present invention.
  • 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 electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer in any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • Compound 3-1 was obtained in the same manner as the preparations of compounds 2 to 7 of Example 1, except for using 1-bromonaphthalene as compound 1 instead of 1-bromo-4-phenylnaphthalene.
  • reaction mixture was extracted with methylene chloride (MC), was dried with MgSO 4 , was distilled under reduced pressure, and then was recrystallized with ethyl acetate(EA) and methanol to obtain compound C-65 (3.5 g, 22%).
  • OLED device was produced using the compound of the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound C-12 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-7 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 4 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-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rate, so that they 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.
  • an Al cathode having a thickness of 150 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the material used for producing the OLED device were those purified by vacuum sublimation at 10 -6 torr.
  • the produced OLED device showed red emission having a luminance of 980 cd/m 2 and a current density of 5.9 mA/cm 2 at a driving voltage of 3.4 V.
  • the time taken to be reduced to 90 % of the luminance at 5,000 nit was 160 hours or more.
  • OLED devices were produced in the same manner as in Device Example 1, except for using those of Table 2 below as a host material and a dopant.
  • An OLED device was produced in the same manner as in Device Example 1, except that 4,4'-N,N'-dicarbazole-biphenyl(CBP) as a host material and compound D-11 as a dopant were used to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was used to form a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed red emission having a luminance of 1,000 cd/m 2 and a current density of 20.0 mA/cm 2 at a driving voltage of 8.2 V. The time taken to be reduced to 90 % of the luminance at 5,000 nit was 10 hours or more.
  • the organic electroluminescent compounds according to the present invention can provide an organic electroluminescent device having long lifespan and enhanced current and power efficiency at lowered driving voltages.
  • the OLED device using conventional organic electroluminescent compounds needed a hole blocking layer, the hole blocking layer is not necessary in the OLED device using the compounds according to the present invention.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. Using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have a long lifespan, a low driving voltage, high current efficiency and high power efficiency.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to organic electroluminescent compounds 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 most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as the light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc., as host materials, which were known as hole blocking materials.
Although these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order to be improved.
Korean Patent Application Laying-Open Nos. 2011-0013220, 2005-0100694 and 2007-0073868 disclose compounds for an organic EL device, in which an aryl or nitrogen-containing heteroaryl is connected to the nitrogen atom of benzocarbazole or dibenzocarbazole backbone. However, the above references fail to specifically disclose the compounds for an organic EL device, in which a phenyl and a nitrogen-containing heteroaryl are connected to the carbon atom and nitrogen atom of benzocarbazole, respectively.
The objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device having a long lifespan and being operated at a low driving voltage to enhance current and power efficiency.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2013011108-appb-I000001
wherein
L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene; Ar1 to Ar4, 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 (C1-C30)alkylamino, a substituted or unsubstituted (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 (3- to 30-membered), 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; A ring represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; X1 represents -N- or -CR1-; X2 represents -N- or -CR2-; X3 represents -N- or -CR3-; where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (3- to 30-membered) heteroaryl; R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (C13-C30) spirofluorenyl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; l represents 0 or 1; m represents an integer of 0 to 5; n represents an integer of 0 to 2; where m or n is an integer of 2 or more, each of Ar1 or Ar2 may be the same or different; and the heteroaryl(ene) contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
By using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have a long lifespan and be operated at a low driving voltage to enhance current and power efficiency.
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 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 invention is described in detail.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “Alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “Alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(5- to 7-membered) heterocycloalkyl” indicates a cycloalkyl having 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Furthermore, “aryl(ene)” indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “(3- to 30-membered) heteroaryl(ene)” indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, P(=O), 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.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkylamino, the substituted arylamino and the substituted alkylarylamino in L1, Ar1 to Ar4, A ring and R1 to R3 of formula 1 above, each independently, are at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C1-C30)alkoxy, a (C6-C30)aryl, a (3- to 30-membered) heteroaryl unsubstituted or substituted with a (C6-C30)aryl(s), a (C3-C30)cycloalkyl, a (5- to 7-membered) heterocycloalkyl, 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, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a cyano, a di(C1-C30)alkylamino, a di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, a (C1-C30)alkyl(C6-C30)aryl, a carboxyl, a nitro and a hydroxyl; and preferably, at least one selected from the group consisting of a (C1-C6)alkyl and a (C6-C21)aryl.
Preferably, the compound of formula 1 can be represented by the following formula 1a or 1b:
Figure PCTKR2013011108-appb-I000002
Figure PCTKR2013011108-appb-I000003
wherein
L1, Ar1 to Ar4, A ring, X1, X2, X3, R2, R3, l, m and n are as defined in formula 1 above.
According to one aspect of the present invention, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene; preferably, a single bond, or a substituted or unsubstituted (C6-C21)arylene; more preferably, a single bond, or an unsubstituted (C6-C21)arylene; and even more preferably a single bond or phenylene.
Ar1 to Ar4, 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 (C1-C30)alkylamino, a substituted or unsubstituted (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 (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring; and preferably, hydrogen, an unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C21)aryl, or an unsubstituted (5- to 21-membered) heteroaryl. More preferably, Ar1, Ar3 and Ar4, each independently, represent hydrogen, or an unsubstituted (C6-C12)aryl; Ar2 represents hydrogen, a (C1-C4)alkyl, a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s), or an unsubstituted (5- to 18-membered) heteroaryl. Even more preferably, Ar1 represents hydrogen, phenyl or naphthyl; Ar2 represents hydrogen, a (C1-C4)alkyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl substituted with a (C1-C4)alkyl(s), or benzofluorenyl substituted with a (C1-C4)alkyl(s); Ar3 represents hydrogen; and Ar4 represents hydrogen or phenyl.
A ring represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; preferably a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl; more preferably, a (C6-C12)aryl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s); and, even more preferably, phenyl, biphenyl, naphthyl, quinolyl, isoquinolyl, naphthyridinyl, phenanthrenyl, phenanthridinyl, benzoquinolyl, benzoquinazolyl, benzoisoquinolyl, phenanthrolinyl, pyridyl, pyrimidinyl, or phenyl-substituted pyridyl.
X1 represents -N- or -CR1-; X2 represents -N- or -CR2-; and X3 represents -N- or -CR3-. Where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (3- to 30-membered) heteroaryl, preferably a nitrogen-containing (5- to 21-membered) heteroaryl, and more preferably a nitrogen-containing (5- to 15-membered) heteroaryl.
R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (C13-C30) spirofluorenyl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl; and preferably, hydrogen, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (C15-C25)spirofluorenyl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl. More preferably, R1 to R3, each independently, represent hydrogen; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s) or a (C6-C12)aryl(s); a (C15-C25)spirofluorenyl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s). Even more preferably, R1 to R3, each independently, represent hydrogen; phenyl; biphenyl; terphenyl; naphthyl; naphthylphenyl; phenyl substituted with a (C1-C4)alkyl(s); fluorenyl; fluorenyl substituted with a (C1-C4)alkyl(s) or phenyl(s); spirobifluorenyl; spiro[cyclopentan-1,9’-fluoren]yl; spiro[cyclohexan-1,9’-fluoren]yl; dibenzofuranyl; dibenzothiophenyl; or carbazolyl substituted with phenyl(s). Specifically, R1 represents hydrogen; R2 represents hydrogen or phenyl; and R3 represents hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted with a (C1-C4)alkyl(s), dibenzofuranyl, dibenzothiophenyl, or carbazolyl substituted with phenyl(s).
l represents 0 or 1; m represents an integer of 0 to 5, preferably an integer of 0 to 2; n represents an integer of 0 to 2, preferably 0 or 1; where m or n is an integer of 2 or more, each of Ar1 or Ar2 may be the same or different.
According to one embodiment of the present invention, in formula 1 above, L1 represents a single bond, or a substituted or unsubstituted (C6-C21)arylene; Ar1 to Ar4, each independently, represent hydrogen, an unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C21)aryl, or an unsubstituted (5- to 21-membered) heteroaryl; A ring represents a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl; X1 represents -N- or -CR1-; X2 represents -N- or -CR2-; X3 represents -N- or -CR3-; where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (5- to 21-membered) heteroaryl; R1 to R3, each independently, represent hydrogen, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (C15-C25) spirofluorenyl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl; l represents 0 or 1; m represents an integer of 0 to 2; n represents 0 or 1; and where m is 2, each of Ar2 may be the same or different.
According to another embodiment of the present invention, in formula 1 above, L1 represents a single bond, or an unsubstituted (C6-C12)arylene; Ar1, Ar3 and Ar4, each independently, represent hydrogen or an unsubstituted (C6-C12)aryl; Ar2 represents hydrogen; a (C1-C4)alkyl; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s); or an unsubstituted (5- to 18-membered) heteroaryl; A ring represents a (C6-C12)aryl; or a (5- to 15-membered) unsubstituted or substituted with a (C6-C12)aryl(s); X1 represents -N- or -CR1-; X2 represents -N- or -CR2-; X3 represents -N- or -CR3-; where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (5- to 15-membered) heteroaryl; R1 to R3, each independently, represent hydrogen; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s) or a (C6-C12)aryl(s); a (C15-C25)spirofluorenyl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s); l represents 0 or 1; m represents an integer of 0 to 2; n represents 0 or 1; and where m is 2, each of Ar2 may be the same or different.
Organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
Figure PCTKR2013011108-appb-I000004
Figure PCTKR2013011108-appb-I000005
Figure PCTKR2013011108-appb-I000006
Figure PCTKR2013011108-appb-I000007
Figure PCTKR2013011108-appb-I000008
Figure PCTKR2013011108-appb-I000009
Figure PCTKR2013011108-appb-I000010
Figure PCTKR2013011108-appb-I000011
Figure PCTKR2013011108-appb-I000012
Figure PCTKR2013011108-appb-I000013
Figure PCTKR2013011108-appb-I000014
Figure PCTKR2013011108-appb-I000015
Figure PCTKR2013011108-appb-I000016
Figure PCTKR2013011108-appb-I000017
The compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1 or 2.
[Reaction Scheme 1]
Figure PCTKR2013011108-appb-I000018
[Reaction Scheme 2]
Figure PCTKR2013011108-appb-I000019
The present invention 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 of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
The organic electroluminescent device 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 injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
Furthermore, the organic layer may comprise a light-emitting layer in which the organic electroluminescent compound of formula 1 may be comprised as a host material.
In addition, a phosphorescent dopant, which is used for an organic electroluminescent device together with the host material according to the present invention, may be selected from the compounds represented by the following formula 2:
Figure PCTKR2013011108-appb-I000020
wherein M1 is selected from the group consisting of Ir, Pt, Pd and Os; L101, L102 and L103 are each independently selected from the following structures:
Figure PCTKR2013011108-appb-I000021
Figure PCTKR2013011108-appb-I000022
Figure PCTKR2013011108-appb-I000023
Figure PCTKR2013011108-appb-I000024
Figure PCTKR2013011108-appb-I000025
R201 to R203, each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl(s), or a halogen;
R204 to R219, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF5, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a cyano or a halogen, or may be linked to an adjacent substituent(s) to form a (C5-C30), mono- or polycyclic, alicyclic or aromatic ring;
R220 to R223, each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl(s);
R224 and R225, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a halogen, or may be linked to each other to form a (C5-C30), mono- or polycyclic, alicyclic or aromatic ring;
R226 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- or 30-membered) heteroaryl or a halogen;
R227 to R229, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl or a halogen;
R230 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
f and g, each independently, represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R230 may be the same or different;
Q represents
Figure PCTKR2013011108-appb-I000026
,
Figure PCTKR2013011108-appb-I000027
Figure PCTKR2013011108-appb-I000028
; R231 to R242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C1-C30)alkoxy, a halogen, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C5-C30)cycloalkyl, or may be linked to an adjacent substituent(s) via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R207 or R208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
Specifically, the dopants of formula 2 are preferred, but are not limited thereto:
Figure PCTKR2013011108-appb-I000029
Figure PCTKR2013011108-appb-I000030
Figure PCTKR2013011108-appb-I000031
Figure PCTKR2013011108-appb-I000032
Figure PCTKR2013011108-appb-I000033
Figure PCTKR2013011108-appb-I000034
Figure PCTKR2013011108-appb-I000035
Figure PCTKR2013011108-appb-I000036
Figure PCTKR2013011108-appb-I000037
Figure PCTKR2013011108-appb-I000038
Figure PCTKR2013011108-appb-I000039
Figure PCTKR2013011108-appb-I000040
Figure PCTKR2013011108-appb-I000041
Figure PCTKR2013011108-appb-I000042
Figure PCTKR2013011108-appb-I000043
Figure PCTKR2013011108-appb-I000044
Figure PCTKR2013011108-appb-I000045
Figure PCTKR2013011108-appb-I000046
Figure PCTKR2013011108-appb-I000047
Figure PCTKR2013011108-appb-I000048
Figure PCTKR2013011108-appb-I000049
The organic electroluminescent device of the present invention may further comprise, in addition to the organic electroluminescent compound of formula 1, 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 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 said 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 invention may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present invention.
In the organic electroluminescent device of the present invention, 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 invention, 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 electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, 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 in any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
Hereinafter, the compound of the present invention, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-12
Preparation of compound 2 [(4-phenylnaphthalen-1-yl)boronic acid]
Figure PCTKR2013011108-appb-I000050
After dissolving 1-bromo-4-phenylnaphthalene (compound 1) (50 g, 176 mmol) in anhydrous tetrahydrofuran(THF) (1L) of a flask, the mixture was stirred at -78°C and n-BuLi (2.5 M in hexane, 132 mL) was dropped slowly thereto. The reaction mixture was stirred for 1 hour at room temperature. After the reaction mixture was cooled to -78°C, triisopropylborate (61 mL, 264 mmol) was dropped slowly thereto. The reaction mixture was then stirred for 3 hours at room temperature. When the reaction was completed, the mixture was extracted with ethyl acetate. The extracted organic layer was dried with MgSO4, and was solidified with hexane to obtain compound 2 (30 g, 68 %).
Preparation of compound 4 [1-(4-bromo-2-nitrophenyl)-4- phenylnaphthalene ]
Figure PCTKR2013011108-appb-I000051
After dissolving 1,4-dibromo-2-nitrobenzene (compound 3) (14.2 g, 50.38 mmol), compound 2 (15 g, 60.46 mmol), and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (1.7 g, 1.51 mmol) in 2 M Na2CO3 (125 mL), toluene (250 mL) and ethanol (125 mL) of a flask, the mixture was refluxed for 5 hours at 120°C. After the reaction mixture was extracted with ethyl acetate, the organic layer was dried with MgSO4, and was purified with column chromatography to obtain compound 4 (13 g, 64 %).
Preparation of compound 5 [1-(3-nitro[1,1'-biphenyl]-4-yl)-4- phenylnaphthalene ]
Figure PCTKR2013011108-appb-I000052
Compound 5 (12 g, 98%) was obtained in the same manner as the preparation of compound 4, by using compound 4 (13 g, 33.87 mmol) and phenyl boronic acid (3.9 g, 32.26 mmol).
Preparation of compound 7 [5,9- diphenyl -7H- benzo [c]carbazole]
Figure PCTKR2013011108-appb-I000053
After dissolving compound 5 (12 g, 32 mmol) in triethyl phosphate (130 mL), the mixture was refluxed for 6 hours at 150°C, and then was triturated with methanol to obtain compound 7 (6.8 g, 62%).
Preparation of compound C-12 [5,9-diphenyl-7-(4-phenylquinazolin-2-yl)-7H-benzo[c]carbazole]
Figure PCTKR2013011108-appb-I000054
After dissolving 2-chloro-4-phenylquinazoline (compound 9) (4 g, 10.83 mmol) and compound 7 (3.2 g, 12.99 mmol) in dimethylformamide (DMF) (55 mL), NaH (0.4 g, 16.4 mmol, 60% in mineral oil) was added thereto. The mixture was stirred for 12 hours at room temperature. Methanol and distilled water were added to the mixture. The resultant solid was filtered under reduced pressure and was purified with column chromatography to obtain compound C-12 (2 g, 33 %).
UV: 384 nm, PL: 515 nm, melting point: 178℃
MS/EIMS found 573.7; calculated 573.23
[Examples 2-24]
The following compounds were prepared in a similar manner as Example 1 above.
Figure PCTKR2013011108-appb-I000055
Figure PCTKR2013011108-appb-I000056
Figure PCTKR2013011108-appb-I000057
Figure PCTKR2013011108-appb-I000058
Figure PCTKR2013011108-appb-I000059
Figure PCTKR2013011108-appb-I000060
Example 25: Preparation of compound C-56
Figure PCTKR2013011108-appb-I000061
Preparation of compound C-56 [5,9-diphenyl-7-(2-phenylquinolin-7-yl)-7H-benzo[c]carbazole]
After dissolving 7-chloro-2-phenylquinoline (3 g, 11.91 mmol) and compound 7 (4 g, 10.83 mmol) in dimethylformamide (DMF) (60 mL), NaH (0.4 g, 16.4 mmol, 60% in mineral oil) was added thereto. The mixture was stirred for 12 hours at room temperature. Methanol and distilled water were added to the mixture. The resultant solid was filtered under reduced pressure, and was purified with column chromatography to obtain compound C-56 (2 g, 33 %).
The characteristics of compounds of Examples 1 to 25 are shown in Table 1 below.
[Table 1]
Figure PCTKR2013011108-appb-I000062
Figure PCTKR2013011108-appb-I000063
Example 26: Preparation of compound C-66
Figure PCTKR2013011108-appb-I000064
Figure PCTKR2013011108-appb-I000065
Preparation of compound 2-5
Compound 2-5 (12 g, 76%) was obtained in the same manner as the preparation of compound 7 of Example 1.
Preparation of compound 2-6
A mixture of compound 2-5 (12 g), 1-bromo-4-iodobenzene (8 g), CuI (500 mg), ethylene diamine(EDA) (4 mL), and toluene (100 mL) was stirred under reflux for 13 hours in a 250 mL-sized round bottom flask. After cooling to room temperature, the reaction mixture was subjected to a work-up procedure, and then was purified with column chromatography to obtain compound 2-6 (14 g, 87%).
Preparation of compound 2-7
A mixture of compound 2-6 (14 g), B2(Pin)2 (15 g), bis(triphenylphosphine)palladium(II) dichloride (PdCl2(PPh3)2) (1.2 mg), potassium acetate (KOAc2) (10 g) and 1,4-dioxane (100 mL) was stirred under reflux for 13 hours in a 250 mL-sized round bottom flask. After cooling to room temperature, the reaction mixture was subjected to a work-up procedure, and then was purified with column chromatography to obtain compound 2-7 (15 g, 82%).
Preparation of compound 2-9
A mixture of compound 2-8 (50 g), phenylboronic acid (26 g), Pd(PPh3)4 (3 g), K2CO3 (26 g), ethanol(EtOH) (50 mL), purified water (100 mL), and toluene (400 mL) was stirred under reflux for 4 hours in a round bottom flask. After cooling to room temperature, the reaction mixture was subjected to a work-up procedure, and then was purified with column chromatography to obtain compound 2-9 (25 g).
Preparation of compound C-66
A mixture of compound 2-7 (11 g), compound 2-9 (4 g), Pd(PPh3)4 (1 g), K2CO3 (5 g), EtOH (30 mL), purified water (60 mL), and toluene (200 mL) was stirred under reflux for 20 hours in a round bottom flask. After cooling to room temperature, the reaction mixture was subjected to a work-up procedure, and then was purified with column chromatography to obtain compound C-66 (1.5 g).
Example 27: Preparation of compound C-65
Figure PCTKR2013011108-appb-I000066
Compound 3-1 was obtained in the same manner as the preparations of compounds 2 to 7 of Example 1, except for using 1-bromonaphthalene as compound 1 instead of 1-bromo-4-phenylnaphthalene. A mixture of compound 2-9 (6.8 g, 28.41 mmol), compound 3-1 (10 g, 34.09 mmol), K2CO3 (4.7 g, 34.09 mmol), 4-dimethylaminopyridine (2.1 g, 17.05 mmol) and DMF (170 mL) was stirred under reflux for 5 hours. The reaction mixture was cooled to room temperature, and then distilled water was added thereto. The reaction mixture was extracted with methylene chloride (MC), was dried with MgSO4, was distilled under reduced pressure, and then was recrystallized with ethyl acetate(EA) and methanol to obtain compound C-65 (3.5 g, 22%).
[Device Example 1] Production of an OLED device using the compound of the present invention
OLED device was produced using the compound of the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound C-12 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-7 was introduced into another cell as a dopant. The two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 4 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-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate, so that they 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. 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the material used for producing the OLED device were those purified by vacuum sublimation at 10-6 torr. The produced OLED device showed red emission having a luminance of 980 cd/m2 and a current density of 5.9 mA/cm2 at a driving voltage of 3.4 V. The time taken to be reduced to 90 % of the luminance at 5,000 nit was 160 hours or more.
[Device Examples 2 to 27] Production of an OLED device using the compound of the present invention
OLED devices were produced in the same manner as in Device Example 1, except for using those of Table 2 below as a host material and a dopant.
[Comparative Device Example 1] Production of an OLED device by using conventional compounds
An OLED device was produced in the same manner as in Device Example 1, except that 4,4'-N,N'-dicarbazole-biphenyl(CBP) as a host material and compound D-11 as a dopant were used to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was used to form a hole blocking layer having a thickness of 10 nm. The produced OLED device showed red emission having a luminance of 1,000 cd/m2 and a current density of 20.0 mA/cm2 at a driving voltage of 8.2 V. The time taken to be reduced to 90 % of the luminance at 5,000 nit was 10 hours or more.
The results of the device examples and the comparative device example are shown in Table 2 below.
[Table 2]
Figure PCTKR2013011108-appb-I000067
Figure PCTKR2013011108-appb-I000068
The organic electroluminescent compounds according to the present invention can provide an organic electroluminescent device having long lifespan and enhanced current and power efficiency at lowered driving voltages. In addition, while the OLED device using conventional organic electroluminescent compounds needed a hole blocking layer, the hole blocking layer is not necessary in the OLED device using the compounds according to the present invention.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013011108-appb-I000069
    wherein
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene;
    Ar1 to Ar4, 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 (C1-C30)alkylamino, a substituted or unsubstituted (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 (3- to 30-membered), 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;
    A ring represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl;
    X1 represents -N- or -CR1-;
    X2 represents -N- or -CR2-;
    X3 represents -N- or -CR3-;
    where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (3- to 30-membered) heteroaryl;
    R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted
    (C6-C30)aryl, a substituted or unsubstituted (C13-C30) spirofluorenyl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl;
    l represents 0 or 1;
    m represents an integer of 0 to 5;
    n represents an integer of 0 to 2;
    where m or n is an integer of 2 or more, each of Ar1 or Ar2 may be the same or different; and
    the heteroaryl(ene) contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 1a or 1b:
    Figure PCTKR2013011108-appb-I000070
    Figure PCTKR2013011108-appb-I000071
    wherein
    L1, Ar1 to Ar4, A ring, X1, X2, X3, R2, R3, l, m and n are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkylamino, the substituted arylamino and the substituted alkylarylamino in L1, Ar1 to Ar4, A ring and R1 to R3, each independently, are at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a (C1-C30)alkoxy, a (C6-C30)aryl, a (3- to 30-membered) heteroaryl unsubstituted or substituted with a (C6-C30)aryl(s), a (C3-C30)cycloalkyl, a (5- to 7-membered) heterocycloalkyl, 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, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a cyano, a di(C1-C30)alkylamino, a di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, a (C1-C30)alkyl(C6-C30)aryl, a carboxyl, a nitro and a hydroxyl.
  4. The organic electroluminescent compound according to claim 1, wherein L1 represents a single bond, or a substituted or unsubstituted (C6-C21)arylene;
    Ar1 to Ar4, each independently, represent hydrogen, an unsubstituted (C1-C6)alkyl, a substituted or unsubstituted (C6-C21)aryl, or an unsubstituted (5- to 21-membered) heteroaryl;
    A ring represents a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl;
    X1 represents -N- or -CR1-;
    X2 represents -N- or -CR2-;
    X3 represents -N- or -CR3-;
    where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (5- to 21-membered) heteroaryl;
    R1 to R3, each independently, represent hydrogen, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (C15-C25) spirofluorenyl, or a substituted or unsubstituted (5- to 21-membered) heteroaryl;
    l represents 0 or 1;
    m represents an integer of 0 to 2;
    n represents 0 or 1; and
    where m is 2, each of Ar2 may be the same or different.
  5. The organic electroluminescent compound according to claim 1, wherein L1 represents a single bond, or an unsubstituted (C6-C12)arylene;
    Ar1, Ar3 and Ar4, each independently, represent hydrogen or an unsubstituted (C6-C12)aryl;
    Ar2 represents hydrogen; a (C1-C4)alkyl; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s); or an unsubstituted (5- to 18-membered) heteroaryl;
    A ring represents a (C6-C12)aryl; or a (5- to 15-membered) unsubstituted or substituted with a (C6-C12)aryl(s);
    X1 represents -N- or -CR1-;
    X2 represents -N- or -CR2-;
    X3 represents -N- or -CR3-;
    where X1 to X3 represent -CR1-, -CR2- and -CR3- respectively, A ring represents a nitrogen-containing (5- to 15-membered) heteroaryl;
    R1 to R3, each independently, represent hydrogen; a (C6-C18)aryl unsubstituted or substituted with a (C1-C4)alkyl(s) or a (C6-C12)aryl(s); a (C15-C25)spirofluorenyl; or a (5- to 15-membered) heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s);
    l represents 0 or 1;
    m represents an integer of 0 to 2;
    n represents 0 or 1; and
    where m is 2, each of Ar2 may be the same or different.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013011108-appb-I000072
    Figure PCTKR2013011108-appb-I000073
    Figure PCTKR2013011108-appb-I000074
    Figure PCTKR2013011108-appb-I000075
    Figure PCTKR2013011108-appb-I000076
    Figure PCTKR2013011108-appb-I000077
    Figure PCTKR2013011108-appb-I000078
    Figure PCTKR2013011108-appb-I000079
    Figure PCTKR2013011108-appb-I000080
    Figure PCTKR2013011108-appb-I000081
    Figure PCTKR2013011108-appb-I000082
    Figure PCTKR2013011108-appb-I000083
    Figure PCTKR2013011108-appb-I000084
    Figure PCTKR2013011108-appb-I000085
  7. An organic electroluminescent device comprising the compound according to claim 1.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015093878A1 (en) * 2013-12-18 2015-06-25 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound, and multi-component host material and organic electroluminescent device comprising the same
JP2015124206A (en) * 2013-12-27 2015-07-06 株式会社半導体エネルギー研究所 Organic compound, light emitting element, display module, illumination module, light emitting device, display device, electronic device and illumination device
WO2016052962A1 (en) * 2014-09-29 2016-04-07 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
CN105794010A (en) * 2013-12-18 2016-07-20 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound, and multi-component host material and organic electroluminescent device comprising the same
WO2016198144A1 (en) 2015-06-10 2016-12-15 Merck Patent Gmbh Materials for organic electroluminescent devices
CN106715441A (en) * 2014-09-29 2017-05-24 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2017109722A1 (en) * 2015-12-21 2017-06-29 Idemitsu Kosan Co., Ltd. Nitrogen-containing heterocyclic compounds and organic electroluminescence devices containing them
EP3418285A1 (en) 2017-06-20 2018-12-26 Idemitsu Kosan Co., Ltd. Composition comprising a substituted ir complex and a phenylquinazoline bridged with a heteroatom
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EP3608319A1 (en) 2018-08-07 2020-02-12 Idemitsu Kosan Co., Ltd. Condensed aza cycles as organic light emitting device and materials for use in same
US11447496B2 (en) 2016-11-23 2022-09-20 Guangzhou Chinaray Optoelectronic Materials Ltd. Nitrogen-containing fused heterocyclic ring compound and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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KR102273047B1 (en) * 2014-06-30 2021-07-06 삼성디스플레이 주식회사 Organic light-emitting device
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Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010107244A2 (en) * 2009-03-20 2010-09-23 Dow Advanced Display Materials, Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010110553A2 (en) * 2009-03-23 2010-09-30 Dow Advanced Display Materials, Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114264A2 (en) * 2009-03-31 2010-10-07 Dow Advanced Display Materials,Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
EP2284920A1 (en) * 2008-05-08 2011-02-16 Nippon Steel Chemical Co., Ltd. Compound for organic electric field light-emitting element and organic electric field light-emitting element
WO2011019156A1 (en) * 2009-08-10 2011-02-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011055911A1 (en) * 2009-11-04 2011-05-12 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011099718A1 (en) * 2010-02-11 2011-08-18 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20120021203A (en) * 2010-08-31 2012-03-08 롬엔드하스전자재료코리아유한회사 Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2012036482A1 (en) * 2010-09-17 2012-03-22 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012050347A1 (en) * 2010-10-13 2012-04-19 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2012067425A1 (en) * 2010-11-16 2012-05-24 Rohm And Haas Electronic Materials Korea Ltd. Novel compound for organic electronic material and organic electroluminescent device using the same
US20120217485A1 (en) * 2009-07-31 2012-08-30 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012165844A1 (en) * 2011-05-30 2012-12-06 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2013002509A2 (en) * 2011-06-27 2013-01-03 주식회사 엘지화학 Novel compound and organic light-emitting device using same
WO2013009013A2 (en) * 2011-07-08 2013-01-17 주식회사 엘지화학 Novel compound and organic electronic device using same
WO2013154325A1 (en) * 2012-04-10 2013-10-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device containing the same
KR20130117726A (en) * 2012-04-18 2013-10-28 에스에프씨 주식회사 Heterocyclic com pounds and organic light-emitting diode including the same

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2284920A1 (en) * 2008-05-08 2011-02-16 Nippon Steel Chemical Co., Ltd. Compound for organic electric field light-emitting element and organic electric field light-emitting element
WO2010107244A2 (en) * 2009-03-20 2010-09-23 Dow Advanced Display Materials, Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010110553A2 (en) * 2009-03-23 2010-09-30 Dow Advanced Display Materials, Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114264A2 (en) * 2009-03-31 2010-10-07 Dow Advanced Display Materials,Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
US20120217485A1 (en) * 2009-07-31 2012-08-30 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011019156A1 (en) * 2009-08-10 2011-02-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011055911A1 (en) * 2009-11-04 2011-05-12 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011099718A1 (en) * 2010-02-11 2011-08-18 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20120021203A (en) * 2010-08-31 2012-03-08 롬엔드하스전자재료코리아유한회사 Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2012036482A1 (en) * 2010-09-17 2012-03-22 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012050347A1 (en) * 2010-10-13 2012-04-19 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2012067425A1 (en) * 2010-11-16 2012-05-24 Rohm And Haas Electronic Materials Korea Ltd. Novel compound for organic electronic material and organic electroluminescent device using the same
WO2012165844A1 (en) * 2011-05-30 2012-12-06 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2013002509A2 (en) * 2011-06-27 2013-01-03 주식회사 엘지화학 Novel compound and organic light-emitting device using same
WO2013009013A2 (en) * 2011-07-08 2013-01-17 주식회사 엘지화학 Novel compound and organic electronic device using same
WO2013154325A1 (en) * 2012-04-10 2013-10-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device containing the same
KR20130117726A (en) * 2012-04-18 2013-10-28 에스에프씨 주식회사 Heterocyclic com pounds and organic light-emitting diode including the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 2013:1701931 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105794010A (en) * 2013-12-18 2016-07-20 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound, and multi-component host material and organic electroluminescent device comprising the same
WO2015093878A1 (en) * 2013-12-18 2015-06-25 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound, and multi-component host material and organic electroluminescent device comprising the same
CN105794010B (en) * 2013-12-18 2020-12-25 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and multi-component host materials and organic electroluminescent devices comprising the same
JP2015124206A (en) * 2013-12-27 2015-07-06 株式会社半導体エネルギー研究所 Organic compound, light emitting element, display module, illumination module, light emitting device, display device, electronic device and illumination device
US9997724B2 (en) 2014-09-29 2018-06-12 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2016052962A1 (en) * 2014-09-29 2016-04-07 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
CN106715441A (en) * 2014-09-29 2017-05-24 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2016198144A1 (en) 2015-06-10 2016-12-15 Merck Patent Gmbh Materials for organic electroluminescent devices
WO2017109722A1 (en) * 2015-12-21 2017-06-29 Idemitsu Kosan Co., Ltd. Nitrogen-containing heterocyclic compounds and organic electroluminescence devices containing them
JP2018516850A (en) * 2015-12-21 2018-06-28 出光興産株式会社 Phenylquinazoline bridged with heteroatoms
WO2017109727A1 (en) 2015-12-21 2017-06-29 Idemitsu Kosan Co., Ltd. Hetero-condensed phenylquinazolines and their use in electronic devices
US11447496B2 (en) 2016-11-23 2022-09-20 Guangzhou Chinaray Optoelectronic Materials Ltd. Nitrogen-containing fused heterocyclic ring compound and application thereof
EP3418285A1 (en) 2017-06-20 2018-12-26 Idemitsu Kosan Co., Ltd. Composition comprising a substituted ir complex and a phenylquinazoline bridged with a heteroatom
EP3466954A1 (en) 2017-10-04 2019-04-10 Idemitsu Kosan Co., Ltd. Fused phenylquinazolines bridged with a heteroatom
EP3608319A1 (en) 2018-08-07 2020-02-12 Idemitsu Kosan Co., Ltd. Condensed aza cycles as organic light emitting device and materials for use in same

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