WO2014088352A1 - 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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WO2014088352A1
WO2014088352A1 PCT/KR2013/011237 KR2013011237W WO2014088352A1 WO 2014088352 A1 WO2014088352 A1 WO 2014088352A1 KR 2013011237 W KR2013011237 W KR 2013011237W WO 2014088352 A1 WO2014088352 A1 WO 2014088352A1
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substituted
unsubstituted
membered
alkyl
aryl
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PCT/KR2013/011237
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French (fr)
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Doo-Hyeon Moon
Soo-Jin Yang
Hee-Choon Ahn
Ji-Song JUN
Kyung-Joo Lee
Tae-Jin Lee
Hyuck-Joo Kwon
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2014088352A1 publication Critical patent/WO2014088352A1/en

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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
  • Korean Patent No. 10-1153910 and Japanese Patent Appln. Laying-Open No. 2008-133225 disclose compounds in which a diarylamine is bonded to a carbon atom of a benzene ring of an indole backbone via a linker such as an arylene, etc., as hole transport materials for an organic EL device.
  • the objective of the present invention is to provide an organic electroluminescent compound which has excellent current efficiency and luminous efficiency.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
  • L 2 and L 3 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl;
  • R 1 to R 5 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30- membered) heteroaryl, -
  • R 2 and R 3 may be bonded to each other to form a double bond; provided that R 5 is not -NR 11 R 12 ;
  • R 11 to R 20 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl; or
  • a represents an integer of 1 to 4; where a is an integer of 2 or more, each of R 5 may be the same or different;
  • the heterocycloalkyl group contains at least one hetero atom selected from O, S and N.
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device which has excellent current efficiency and luminous efficiency.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • the electroluminescent compound represented by the above formula 1 will be described in detail.
  • 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, 2-methylpent-2-ynyl, etc.; “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(3- to 7- membered) heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms including at least one heteroatom
  • the compound represented by formula 1 is represented by the following formula 2.
  • L 1 to L 3 , Ar 1 , Ar 2 , R 1 , R 4 , R 5 , and a are as defined in formula 1.
  • 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.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene, preferably represents a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene, and more preferably represents a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene.
  • L 2 and L 3 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene, preferably each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene, and more preferably each independently represent a single bond, a (C6-C18)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl, and more preferably each independently represent a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C18)aryl, a (5- to 15- membered) heteroaryl or a di(C6-C10)arylamino; or a (5- to 7- membered) heteroaryl unsubstituted or substituted with a (C6-C10)aryl or a (5- to 7- membered) heteroaryl.
  • R 1 to R 5 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30- membered) heteroaryl, -
  • R 2 and R 3 may be bonded to each other to form a double bond; provided that R 5 is not -NR 11 R 12 .
  • R 11 to R 20 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl; or
  • L 1 represents a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene
  • L 2 and L 3 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl
  • R 1 to R 5 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; or
  • L 1 represents a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene
  • L 2 and L 3 each independently represent a single bond, a (C6-C18)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene
  • Ar 1 and Ar 2 each independently represent a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C18)aryl, a (5- to 15- membered) heteroaryl or a di(C6-C10)arylamino; or a (5- to 7- membered) heteroaryl unsubstituted or substituted with a (C6-C10)aryl
  • the specific compounds of the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction schemes 1 and 2.
  • L 1 to L 3 , Ar 1 , Ar 2 , R 1 to R 5 , and a are as defined in formula 1 above, and Hal represents a halogen.
  • 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 above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • Said organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes.
  • Said organic layer may comprise at least one organic electroluminescent compound of formula 1 according to the present invention.
  • the organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • Said hole transport layer may be comprised of two or more hole transport layers, and when there are two or more hole transport layers, the efficiency and the lifespan of the organic electroluminescent device may be improved.
  • the organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound according to the present invention may comprise at least one compound other than the organic electroluminescent compound according to the present invention as a host material, and can further comprise at least one dopant.
  • the organic electroluminescent compound according to the present invention is comprised as a host material (first host material)
  • the other compound may be comprised as a second host material.
  • the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • Another host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts.
  • the phosphorescent host selected from the group consisting of the compounds of formulae 3 to 5 below is preferable in view of luminous efficiency.
  • R 21 to R 24 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 (3- to 30- membered) heteroaryl, or R 25 R 26 R 27 Si-;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30- membered) heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30- membered) heteroaryl;
  • preferable examples of said host material are as follows:
  • the dopant is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from compounds represented by the following formulae 6 to 8.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a substituted or unsubstituted (C3-C30)cycloalkyl; a cyano; or a substituted or unsubstituted (C1-C30)alkoxy; adjacent substituents of R 120 to R 123 may be linked to each other to form a fused ring, e.g. quinoline;
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R 124 to R 127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R 100 may be the same or different; and
  • n is an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • composition for an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport layer.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes.
  • Said organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition used for the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • said organic layer may form an organic electroluminescent device emitting 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 organic electroluminescent compound according to the present invention.
  • a surface layer is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it 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; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, 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.
  • Compound 2-1 (31 g, 66%) was obtained by the same synthetic method for preparing compound 1-1 in Example 1, except using 2,3,4,9-tetrahydrocarbazole (20 g, 170 mmol) instead of 1 H -indole.
  • An OLED device was produced using the light emitting material according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • compound C-23 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-7,9'-diphenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, compound E-1 as below was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed a green emission having a luminance of 3660 cd/m 2 and a current density of 7.7 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for forming a hole transport layer having a thickness of 20 nm by using compound C-52 , introducing 9-phenyl-3-(4-(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)phenyl)-9H-carbazole into one cell of the vacuum vapor depositing apparatus, introducing compound D-78 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 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.
  • the produced OLED device showed a red emission having a luminance of 1500 cd/m 2 and a current density of 10.8 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound C-92 for a hole transport layer.
  • the produced OLED device showed a green emission having a luminance of 2800 cd/m 2 and a current density of 5.8 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 2, except for using compound C-86 for a hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 2600 cd/m 2 and a current density of 19.7 mA/cm 2 .
  • Comparative Example 1 Luminous characteristic of an OLED device
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as below in a thickness of 20 nm for the hole transport layer.
  • the produced OLED device showed a green emission having a luminance of 8730 cd/m 2 and a current density of 21.4 mA/cm 2 .
  • Comparative Example 2 Luminous characteristic of an OLED device
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound R-2 as below in a thickness of 20 nm for the hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 4800 cd/m 2 and a current density of 59.3 mA/cm 2 .
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device which has excellent current efficiency and luminous efficiency.

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Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound according to the present invention, an organic electroluminescent device having excellent current efficiency and luminous efficiency can be produced.

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 device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host 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 layer materials.
Though 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 an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc. were used as a hole injection and transport material.
However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
Korean Patent No. 10-1153910 and Japanese Patent Appln. Laying-Open No. 2008-133225 disclose compounds in which a diarylamine is bonded to a carbon atom of a benzene ring of an indole backbone via a linker such as an arylene, etc., as hole transport materials for an organic EL device.
However, the above references do not disclose compounds in which a diarylamine or a diheteroarylamine is bonded to a nitrogen atom of an indole backbone via a linker such as an arylene, etc.
The objective of the present invention is to provide an organic electroluminescent compound which has excellent current efficiency and luminous efficiency.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2013011237-appb-I000001
wherein
L1 represents a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
L2 and L3 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl;
R1 to R5 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30- membered) heteroaryl, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic, substituted or unsubstituted (3- to 30- membered) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R2 and R3 may be bonded to each other to form a double bond; provided that R5 is not -NR11R12;
R11 to R20 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
a represents an integer of 1 to 4; where a is an integer of 2 or more, each of R5 may be the same or different;
the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P; and
the heterocycloalkyl group contains at least one hetero atom selected from O, S and N.
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device which has excellent current efficiency and luminous 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 relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The electroluminescent compound represented by the above formula 1 will be 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, 2-methylpent-2-ynyl, etc.; “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(3- to 7- membered) heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms including at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.; “aryl(ene)” is 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)” is an aryl having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P; is 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 including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, bipyridyl, pyrazinyl, pyrimidyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indolinyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “Halogen” includes F, Cl, Br and I.
According to one embodiment of the present invention, the compound represented by formula 1 is represented by the following formula 2.
Figure PCTKR2013011237-appb-I000002
wherein L1 to L3, Ar1, Ar2, R1, R4, R5, and a are as defined in formula 1.
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 (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7- membered) heterocycloalkyl, the substituted (C6-C30)aryl(ene), and the substituted (3- to 30- membered) heteroaryl(ene) groups in L1 to L3, Ar1, Ar2, R1 to R5, and R11 to R20 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7- membered) heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30- membered) heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30- membered) heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono or di(C1-C30)alkylamino, a mono or di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl, and preferably each independently are at least one selected from the group consisting of a (C1-C30)alkyl, a (3- to 30- membered) heteroaryl, a (C6-C30)aryl, and a di(C6-C30)arylamino.
In formula 1 above, L1 represents a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene, preferably represents a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene, and more preferably represents a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene.
L2 and L3 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene, preferably each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene, and more preferably each independently represent a single bond, a (C6-C18)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene.
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl, preferably each independently represent a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl, and more preferably each independently represent a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C18)aryl, a (5- to 15- membered) heteroaryl or a di(C6-C10)arylamino; or a (5- to 7- membered) heteroaryl unsubstituted or substituted with a (C6-C10)aryl or a (5- to 7- membered) heteroaryl.
R1 to R5 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30- membered) heteroaryl, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic, substituted or unsubstituted (3- to 30- membered) 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 substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a monocyclic, substituted or unsubstituted (5- to 20- membered) alicyclic ring, and more preferably each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 15- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a cyclopentyl or cyclohexyl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl.
R2 and R3 may be bonded to each other to form a double bond; provided that R5 is not -NR11R12.
R11 to R20 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur.
According to one embodiment of the present invention, in formula 1 above, L1 represents a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene; L2 and L3 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene; Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; and R1 to R5 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a monocyclic, substituted or unsubstituted (5- to 20- membered) alicyclic ring; and R2 and R3 may be bonded to each other to form a double bond.
According to another embodiment of the present invention, in formula 1 above, L1 represents a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene; L2 and L3 each independently represent a single bond, a (C6-C18)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene; Ar1 and Ar2 each independently represent a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C18)aryl, a (5- to 15- membered) heteroaryl or a di(C6-C10)arylamino; or a (5- to 7- membered) heteroaryl unsubstituted or substituted with a (C6-C10)aryl or a (5- to 7- membered) heteroaryl; and R1 to R5 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 15- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a cyclopentyl or cyclohexyl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; and R2 and R3 may be bonded to each other to form a double bond.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2013011237-appb-I000003
Figure PCTKR2013011237-appb-I000004
Figure PCTKR2013011237-appb-I000005
Figure PCTKR2013011237-appb-I000006
Figure PCTKR2013011237-appb-I000007
Figure PCTKR2013011237-appb-I000008
Figure PCTKR2013011237-appb-I000009
Figure PCTKR2013011237-appb-I000010
Figure PCTKR2013011237-appb-I000011
Figure PCTKR2013011237-appb-I000012
Figure PCTKR2013011237-appb-I000013
Figure PCTKR2013011237-appb-I000014
Figure PCTKR2013011237-appb-I000015
Figure PCTKR2013011237-appb-I000016
Figure PCTKR2013011237-appb-I000017
Figure PCTKR2013011237-appb-I000018
Figure PCTKR2013011237-appb-I000019
Figure PCTKR2013011237-appb-I000020
Figure PCTKR2013011237-appb-I000021
Figure PCTKR2013011237-appb-I000022
Figure PCTKR2013011237-appb-I000023
Figure PCTKR2013011237-appb-I000024
Figure PCTKR2013011237-appb-I000025
Figure PCTKR2013011237-appb-I000026
Figure PCTKR2013011237-appb-I000027
Figure PCTKR2013011237-appb-I000028
Figure PCTKR2013011237-appb-I000029
Figure PCTKR2013011237-appb-I000030
Figure PCTKR2013011237-appb-I000031
Figure PCTKR2013011237-appb-I000032
Figure PCTKR2013011237-appb-I000033
Figure PCTKR2013011237-appb-I000034
Figure PCTKR2013011237-appb-I000035
Figure PCTKR2013011237-appb-I000036
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction schemes 1 and 2.
[Reaction Scheme 1]
Figure PCTKR2013011237-appb-I000037
[Reaction Scheme 2]
Figure PCTKR2013011237-appb-I000038
wherein L1 to L3, Ar1, Ar2, R1 to R5, and a are as defined in formula 1 above, and Hal represents a halogen.
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 above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
Said organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes. Said organic layer may comprise at least one organic electroluminescent compound of formula 1 according to the present invention.
One of the first and second electrodes is an anode, and the other is a cathode. The organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
Said hole transport layer may be comprised of two or more hole transport layers, and when there are two or more hole transport layers, the efficiency and the lifespan of the organic electroluminescent device may be improved.
The organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound according to the present invention may comprise at least one compound other than the organic electroluminescent compound according to the present invention as a host material, and can further comprise at least one dopant.
Where the organic electroluminescent compound according to the present invention is comprised as a host material (first host material), the other compound may be comprised as a second host material. Herein, the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
Another host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 3 to 5 below is preferable in view of luminous efficiency.
Figure PCTKR2013011237-appb-I000039
wherein Cz represents the following structure;
Figure PCTKR2013011237-appb-I000040
R21 to R24 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 (3- to 30- membered) heteroaryl, or R25R26R27Si-; R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30- membered) heteroarylene; M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30- membered) heteroaryl; Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist; R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30- membered) heteroaryl, and R32 and R33 may be the same or different; h and i each independently represent an integer of 1 to 3; j, k, l and m each independently represent an integer of 0 to 4; and where h, i, j, k, l or m is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23 or each of R24 may be the same or different.
Specifically, preferable examples of said host material are as follows:
Figure PCTKR2013011237-appb-I000041
Figure PCTKR2013011237-appb-I000042
Figure PCTKR2013011237-appb-I000043
Figure PCTKR2013011237-appb-I000044
Figure PCTKR2013011237-appb-I000045
Figure PCTKR2013011237-appb-I000046
Figure PCTKR2013011237-appb-I000047
Figure PCTKR2013011237-appb-I000048
Figure PCTKR2013011237-appb-I000049
Figure PCTKR2013011237-appb-I000050
Figure PCTKR2013011237-appb-I000051
Figure PCTKR2013011237-appb-I000052
Figure PCTKR2013011237-appb-I000053
The dopant is preferably at least one phosphorescent dopant. The phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 6 to 8.
Figure PCTKR2013011237-appb-I000054
Figure PCTKR2013011237-appb-I000055
Figure PCTKR2013011237-appb-I000056
wherein L is selected from the following structures:
Figure PCTKR2013011237-appb-I000057
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a substituted or unsubstituted (C3-C30)cycloalkyl; a cyano; or a substituted or unsubstituted (C1-C30)alkoxy; adjacent substituents of R120 to R123 may be linked to each other to form a fused ring, e.g. quinoline;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R124 to R127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl;
o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R100 may be the same or different; and
n is an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2013011237-appb-I000058
Figure PCTKR2013011237-appb-I000059
Figure PCTKR2013011237-appb-I000060
Figure PCTKR2013011237-appb-I000061
Figure PCTKR2013011237-appb-I000062
Figure PCTKR2013011237-appb-I000063
Figure PCTKR2013011237-appb-I000064
Figure PCTKR2013011237-appb-I000065
Figure PCTKR2013011237-appb-I000066
Figure PCTKR2013011237-appb-I000067
Figure PCTKR2013011237-appb-I000068
Figure PCTKR2013011237-appb-I000069
In another embodiment of the present invention, a composition for an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport layer.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between said first and second electrodes. Said organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition used for the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, said organic layer may form an organic electroluminescent device emitting 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 organic electroluminescent compound according to the present invention.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Further, the hole transport compound is oxidized to a cation, and thus it 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 according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, 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.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-52
Figure PCTKR2013011237-appb-I000070
Preparation of compound 1-1
After dissolving 1H-indole (20 g, 0.170 mol), 4-bromo-4'-iodo-1,1'-biphenyl (61 g, 0.187 mol), iodocopper (CuI) (6.5 g, 0.034 mol), ethylenediamine (EDA) (23 mL, 0.341 mol), and potassium phosphate (K3PO4) (72.5 g, 0.341 mol) in toluene 0.9 L, the mixture was stirred at 120°C for 3 hours, and then cooled to room temperature. The mixture was then extracted with ethylacetate, and the obtained organic layer was washed with distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered, and dried. The obtained product was then separated with column chromatography to obtain compound 1-1 (39 g, 66%).
Preparation of compound C-52
After dissolving compound 1-1 (10 g, 28 mmol), di([1,1'-biphenyl]-4-yl)amine (10.2 g, 32 mmol), tris-(dibenzylideneacetone)-dipalladium (Pd2(dba)3) (0.5 g, 0.57 mmol), tris(ortho-toluyl)phosphine (P(o-Tol)3) (0.7 g, 2.28 mmol), and sodiumbutoxide (NaOt-Bu) (4.1 g, 43.08 mmol) in toluene 150 mL, the mixture was stirred at 120°C for 3 hours, and then cooled to room temperature. The mixture was then extracted with ethylacetate, and the obtained organic layer was washed with distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered, and dried. The obtained product was then separated with column chromatography to obtain compound C-52 (2.7 g, 16%).
Data of physical properties: melting point 195°C, UV 386 nm (in toluene),
PL 405 nm (in toluene), molecular weight 588.74
Example 2: Preparation of compound C-101
Figure PCTKR2013011237-appb-I000071
Preparation of compound 2-1
Compound 2-1 (31 g, 66%) was obtained by the same synthetic method for preparing compound 1-1 in Example 1, except using 2,3,4,9-tetrahydrocarbazole (20 g, 170 mmol) instead of 1H-indole.
Preparation of compound C-101
After dissolving compound 2-1 (10 g, 25 mmol), di([1,1'-biphenyl]-4-yl)amine (8 g, 25 mmol), palladiumacetate (Pd(OAc)2) (0.11 g, 0.5 mmol), P(t-Bu)3 (0.4 mL, 1 mmol), and NaOt-Bu (3.6 g, 38 mmol) in o-xylene 150 mL, the mixture was stirred at 120°C for 3 hours, and then cooled to room temperature. The mixture was then extracted with ethylacetate, and the obtained organic layer was washed with distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered, and dried. The obtained product was then separated with column chromatography to obtain compound C-101 (6.5 g, 44%).
Data of physical properties: melting point 304°C, UV 346 nm (in toluene),
PL 396 nm (in toluene), molecular weight 642.83
Example 3: Preparation of compound C-92
Figure PCTKR2013011237-appb-I000072
Preparation of compound 3-1
After mixing tetrahydrofuran (THF) (700 mL), and 4-bromo-N,N-diphenylaniline (30 g, 0.093 mmol) in a flask, and stirring the mixture under nitrogen atmosphere, n-BuLi (55 mL, 2.25 M) was slowly added to the mixture at -78°C. The mixture was then stirred at -78°C for 1 hour, and trismethoxyborane (B(OMe)3) (21 mL, 0.19 mol) was slowly added to the mixture at -78°C. The mixture was then heated to room temperature, and reacted for 12 hours. After the reaction, the mixture was extracted with ethylacetate, and the obtained organic layer was dried with anhydrous magnesium sulfate (MgSO4), and filtered. The solvent was removed under reduced pressure, and the remaining substance was recrystallized to obtain a white solid compound 3-1 (17 g, 62%).
Preparation of compound C-92
After mixing compound 1-1 (7 g, 0.02 mol), compound 3-1 (7 g, 0.02 mol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.7 g, 0.6 mol), sodium carbonate (5.3 g, 0.05 mol), toluene 100 mL, ethanol 25 mL, and distilled water 25 mL, the mixture was stirred at 120°C for 12 hours. After the reaction, the mixture was extracted with ethylacetate, and the obtained organic layer was dried with anhydrous MgSO4, and filtered. The solvent was removed under reduced pressure, and the remaining substance was separated with column chromatography to obtain a white solid compound C-92 (4.6 g, 45%).
Data of physical properties: melting point 205°C, UV 390 nm (in toluene),
PL 411 nm (in toluene), molecular weight 512.64
Example 4: Preparation of compound C-86
Figure PCTKR2013011237-appb-I000073
Preparation of compound 4-1
After mixing 4-aminobiphenyl (19 g, 112 mmol), 2-(4-bromophenyl)naphthalene (26 g, 94 mmol), Pd(OAc)2 (0.5 g, 1.9 mmol), P(t-Bu)3 (5 mL, 9.4 mmol), cesium carbonate (Cs2CO3) (60 g, 190 mmol), and toluene 500 mL in a flask, the mixture was reacted under reflux for 18 hours. Purified water was then slowly added to the mixture to complete the reaction, and the reaction mixture was extracted with distilled water and ethylacetate. The organic layer was dried with anhydrous MgSO4, and the solvent was removed. The remaining substance was then separated with column chromatography to obtain compound 4-1 (18 g, 52%).
Preparation of compound C-86
After mixing compound 4-1 (9 g, 24 mmol), compound 1-1 (8.4 g, 24 mmol), Pd(OAc)2 (0.16 g, 0.72 mmol), P(t-Bu)3 (1 mL, 2.4 mmol), NaOt-Bu (3.5 g, 36 mmol), and o-xylene 50 mL in a flask, the mixture was reacted under reflux for 1 hour. Purified water was then slowly added to the mixture to complete the reaction, and the reaction mixture was extracted with distilled water and ethylacetate. The organic layer was dried with anhydrous MgSO4, and the solvent was removed. The remaining substance was then separated with column chromatography to obtain compound C-86 (9.1 g, 59%).
Data of physical properties: melting point 235°C, UV 346 nm (in toluene),
PL 404 nm (in toluene), molecular weight 638.80
Example 5: Preparation of compound C-23
Figure PCTKR2013011237-appb-I000074
Preparation of compound 5-1
After mixing phenylhydrazine (60 g, 415 mmol), 2-methylcyclohexanone (47 g, 415 mmol), and acetic acid (AcOH) 270 mL in a flask, the mixture was stirred at 120°C for 5 hours. After completing stirring, the mixture was slowly basified with cooled 1 M aqueous sodium hydroxide solution. The reaction mixture was then extracted with methylenechloride (MC), and the obtained organic layer was concentrated. The product was then separated with column chromatography to obtain compound 5-1 (64 g, 84%).
Preparation of compound 5-2
After mixing compound 5-1 (43 g, 230 mmol) and toluene 130 mL in a flask under nitrogen atmosphere, the mixture was cooled down to -20°C. 3 M methyllithium (Me-Li) 100 mL was then slowly added dropwise to the mixture, and the mixture was stirred at the same temperature for 3 hours. After the reaction, toluene 150 mL and distilled water 150 mL were added slowly to the mixture, and the organic layer was concentrated. The product was then separated with column chromatography to obtain compound 5-2 (36 g, 62%).
Preparation of compound 5-3
After dissolving compound 5-2 (36 g, 138 mmol), 4-bromo-4'-iodobiphenyl (74 g, 207 mmol), Pd(OAc)2 (1.2 g, 5.54 mmol), 2,2'-bisdiphenylphosphino-1,1'-binaphthalene (BINAP) (3.45 g, 5.54 mmol), and NaOt-Bu (53 g, 554 mmol) in xylene 700 mL, the mixture was reacted under reflux for 1 hour. After the reaction, the mixture was filtered, and the filtrate was concentrated. The concentrated mixture was then separated with column chromatography to obtain compound 5-3 (28 g, 50%).
Figure PCTKR2013011237-appb-I000075
Preparation of compound C-23
Compound C-23 (5.4 g, 37%) was obtained by the same synthetic method for preparing compound C-101 in Example 2, except using compound 5-3 (10 g, 23.1 mmol) instead of compound 2-1.
Data of physical properties: melting point 232°C, UV 356 nm (in toluene),
PL 404 nm (in toluene), molecular weight 672.90
Device Example 1: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced using the light emitting material according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, compound C-23 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-7,9'-diphenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, compound E-1 as below was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
Figure PCTKR2013011237-appb-I000076
The produced OLED device showed a green emission having a luminance of 3660 cd/m2 and a current density of 7.7 mA/cm2.
Device Example 2: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for forming a hole transport layer having a thickness of 20 nm by using compound C-52, introducing 9-phenyl-3-(4-(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)phenyl)-9H-carbazole into one cell of the vacuum vapor depositing apparatus, introducing compound D-78 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 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.
The produced OLED device showed a red emission having a luminance of 1500 cd/m2 and a current density of 10.8 mA/cm2.
Device Example 3: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound C-92 for a hole transport layer.
The produced OLED device showed a green emission having a luminance of 2800 cd/m2 and a current density of 5.8 mA/cm2.
Device Example 4: Production of an OLED device using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 2, except for using compound C-86 for a hole transport layer.
The produced OLED device showed a red emission having a luminance of 2600 cd/m2 and a current density of 19.7 mA/cm2.
Comparative Example 1: Luminous characteristic of an OLED device
using conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as below in a thickness of 20 nm for the hole transport layer.
The produced OLED device showed a green emission having a luminance of 8730 cd/m2 and a current density of 21.4 mA/cm2.
Comparative Example 2: Luminous characteristic of an OLED device
using conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound R-2 as below in a thickness of 20 nm for the hole transport layer.
The produced OLED device showed a red emission having a luminance of 4800 cd/m2 and a current density of 59.3 mA/cm2.
Figure PCTKR2013011237-appb-I000077
Figure PCTKR2013011237-appb-I000078
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device which has excellent current efficiency and luminous efficiency.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013011237-appb-I000079
    wherein
    L1 represents a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
    L2 and L3 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30- membered) heteroarylene;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl;
    R1 to R5 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30- membered) heteroaryl, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic, substituted or unsubstituted (3- to 30- membered) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    R2 and R3 may be bonded to each other to form a double bond; provided that R5 is not -NR11R12;
    R11 to R20 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7- membered) heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    a represents an integer of 1 to 4; where a is an integer of 2 or more, each of R5 may be the same or different;
    the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P; and
    the heterocycloalkyl group contains at least one hetero atom selected from O, S and N.
  2. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 2.
    Figure PCTKR2013011237-appb-I000080
    wherein L1 to L3, Ar1, Ar2, R1, R4, R5, and a are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7- membered) heterocycloalkyl, the substituted (C6-C30)aryl(ene), and the substituted (3- to 30- membered) heteroaryl(ene) groups in L1 to L3, Ar1, Ar2, R1 to R5, and R11 to R20 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7- membered) heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30- membered) heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- 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.
  4. The organic electroluminescent compound according to claim 1, wherein L1 represents a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene;
    L2 and L3 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5- to 20- membered) heteroarylene;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; and
    R1 to R5 each independently represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a monocyclic, substituted or unsubstituted (5- to 20- membered) alicyclic ring; and R2 and R3 may be bonded to each other to form a double bond.
  5. The organic electroluminescent compound according to claim 1, wherein L1 represents a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene;
    L2 and L3 each independently represent a single bond, a (C6-C18)arylene unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 7- membered) heteroarylene;
    Ar1 and Ar2 each independently represent a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (C6-C18)aryl, a (5- to 15- membered) heteroaryl or a di(C6-C10)arylamino; or a (5- to 7- membered) heteroaryl unsubstituted or substituted with a (C6-C10)aryl or a (5- to 7- membered) heteroaryl; and
    R1 to R5 each independently represent hydrogen, an unsubstituted (C1-C6)alkyl, a (C6-C18)aryl unsubstituted or substituted with a (C1-C6)alkyl, or an unsubstituted (5- to 15- membered) heteroaryl; or are linked to an adjacent substituent(s) to form a cyclopentyl or cyclohexyl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; and R2 and R3 may be bonded to each other to form a double bond.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013011237-appb-I000081
    Figure PCTKR2013011237-appb-I000082
    Figure PCTKR2013011237-appb-I000083
    Figure PCTKR2013011237-appb-I000084
    Figure PCTKR2013011237-appb-I000085
    Figure PCTKR2013011237-appb-I000086
    Figure PCTKR2013011237-appb-I000087
    Figure PCTKR2013011237-appb-I000088
    Figure PCTKR2013011237-appb-I000089
    Figure PCTKR2013011237-appb-I000090
    Figure PCTKR2013011237-appb-I000091
    Figure PCTKR2013011237-appb-I000092
    Figure PCTKR2013011237-appb-I000093
    Figure PCTKR2013011237-appb-I000094
    Figure PCTKR2013011237-appb-I000095
    Figure PCTKR2013011237-appb-I000096
    Figure PCTKR2013011237-appb-I000097
    Figure PCTKR2013011237-appb-I000098
    Figure PCTKR2013011237-appb-I000099
    Figure PCTKR2013011237-appb-I000100
    Figure PCTKR2013011237-appb-I000101
    Figure PCTKR2013011237-appb-I000102
    Figure PCTKR2013011237-appb-I000103
    Figure PCTKR2013011237-appb-I000104
    Figure PCTKR2013011237-appb-I000105
    Figure PCTKR2013011237-appb-I000106
    Figure PCTKR2013011237-appb-I000107
    Figure PCTKR2013011237-appb-I000108
    Figure PCTKR2013011237-appb-I000109
    Figure PCTKR2013011237-appb-I000110
    Figure PCTKR2013011237-appb-I000111
    Figure PCTKR2013011237-appb-I000112
    Figure PCTKR2013011237-appb-I000113
    Figure PCTKR2013011237-appb-I000114
  7. An organic electroluminescent device comprising the electroluminescent compound according to claim 1.
PCT/KR2013/011237 2012-12-06 2013-12-05 Organic electroluminescent compounds and organic electroluminescent device comprising the same WO2014088352A1 (en)

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WO2016060463A2 (en) * 2014-10-14 2016-04-21 주식회사 동진쎄미켐 Novel compound and organic light-emitting element comprising same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148660A1 (en) * 2006-06-22 2007-12-27 Idemitsu Kosan Co., Ltd. Organic electroluminescent device employing heterocycle-containing arylamine derivative
US20100033088A1 (en) * 2008-08-07 2010-02-11 Samsung Mobile Display Co., Ltd. Heterocyclic compound and organic electroluminescent device comprising the same
WO2013109027A1 (en) * 2012-01-18 2013-07-25 덕산하이메탈(주) Compound, organic electronic element using same and electronic device thereof
WO2013180456A1 (en) * 2012-05-30 2013-12-05 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148660A1 (en) * 2006-06-22 2007-12-27 Idemitsu Kosan Co., Ltd. Organic electroluminescent device employing heterocycle-containing arylamine derivative
US20100033088A1 (en) * 2008-08-07 2010-02-11 Samsung Mobile Display Co., Ltd. Heterocyclic compound and organic electroluminescent device comprising the same
WO2013109027A1 (en) * 2012-01-18 2013-07-25 덕산하이메탈(주) Compound, organic electronic element using same and electronic device thereof
WO2013180456A1 (en) * 2012-05-30 2013-12-05 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same

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