WO2014042420A1 - A novel organic electroluminescence compound and an organic electroluminescence device containing the same - Google Patents

A novel organic electroluminescence compound and an organic electroluminescence device containing the same Download PDF

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WO2014042420A1
WO2014042420A1 PCT/KR2013/008206 KR2013008206W WO2014042420A1 WO 2014042420 A1 WO2014042420 A1 WO 2014042420A1 KR 2013008206 W KR2013008206 W KR 2013008206W WO 2014042420 A1 WO2014042420 A1 WO 2014042420A1
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group
substituted
unsubstituted
aryl
independently represent
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Hee-Choon Ahn
Doo-Hyeon Moon
Seung-Ae Kim
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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Definitions

  • the present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device containing the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages over other types of display devices 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 light-emitting materials theoretically enhance the luminous efficiency by four (4) times compared to fluorescent light-emitting 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,C-3’)iridium(acetylacetonate) [(acac)Ir(btp) 2 ], tris(2-phenylpyridine)iridium [Ir(ppy) 3 ] and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium [Firpic] as red, green and blue materials, respectively.
  • a host material mixed with a light-emitting material can be used as a light-emitting material.
  • choosing the host material is important, since the host material has a large influence in efficiency and performance of a light-emitting device.
  • 4,4’-N,N’-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent light-emitting host material.
  • phosphorescent host materials have some advantages in view of light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, they may be degraded during a high-temperature deposition process in a vacuum. (2) The power efficiency of an organic EL device is given by [( ⁇ /voltage) ⁇ current efficiency], and power efficiency is inversely proportional to voltage. An organic EL device comprising phosphorescent host materials provides a higher current efficiency (cd/A) than one comprising fluorescent materials. However, it has a higher driving voltage, and thus, there is no substantial merit in terms of power efficiency (lm/W). (3) Further, when the phosphorescent host materials are used in an OLED device, the operating lifespan of the device is unsatisfactory, and luminous efficiency still needs improvement.
  • Korean Patent Appln. Laying-Open No. 2009-0035729 A discloses amine compounds containing carbazole for an organic electroluminescence device. Further, Korean Patent Appln. Laying-Open No. 2011-0129766 A discloses amine compounds containing fused carbazole for an organic electroluminescence device.
  • the organic EL devices comprising the compounds disclosed in the reference are still unsatisfactory in view of power efficiency, luminous efficiency, quantum efficiency, and lifespan, etc.
  • the objective of the present invention is to provide an organic electroluminescent compound having high luminous efficiency and superior lifespan over conventional materials, and to provide an organic electroluminescent device having high efficiency and long lifespan.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
  • X represents oxygen atom, sulfur atom, or -CR 5 R 6 -;
  • R 1 to R 6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a (C6-C30)aryl group fused with
  • R 11 to R 20 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-
  • a represents an integer of 1 to 4; where a is an integer of 2 or more, each of R 1 is the same or different;
  • b to d each independently represent an integer of 1 to 3; where b, c or d is an integer of 2 or more, each of R 2 , each of R 3 , and each of R 4 is the same or different;
  • the heterocycloalkyl group contains at least one hetero atom selected from O, S and N.
  • the organic electroluminescent compound according to the present invention has high luminous efficiency and superior lifespan characteristics of material, and thus can provide an organic electroluminescent device, which is excellent in operational lifespan of the device. Further, the organic electroluminescent compound according to the present invention can reduce driving voltage and improve power efficiency of an organic electroluminescent device at the same time.
  • the present invention relates to an organic electroluminescent compound represented by formula 1, above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; preferably a single bond, a substituted or unsubstituted (C6-C20)arylene group, or a substituted or unsubstituted 5- to 15-membered heteroarylene group; more preferably a single bond; a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, a (C1-C15)aryl group or a di(C6-C15)arylamino group; or an unsubstituted 5- to 10-membered heteroarylene group.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; preferably a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; more preferably a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, or a (C6-C15)aryl(5- to 10-membered) heteroarylamino group; or a 5- to 10-membered heteroaryl group unsubstituted or substituted with a (C6-C15)aryl group or a di(C6-C15)arylamino group.
  • X represents oxygen atom, sulfur atom, or -CR 5 R 6 -;
  • R 1 to R 6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a (C6-C30)aryl
  • R 11 to R 12 each independently represent preferably a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; more preferably an unsubstituted (C6-C15)aryl group; and R 13 to R 15 each independently represent preferably a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C15)aryl group.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene group, or a substituted or unsubstituted 5- to 15-membered heteroarylene group;
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group;
  • R 1 to R 6 each independently represent hydrogen, a halogen, a substituted or unsubstituted (C1-C15)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, a (C6-C15)aryl group fused with a (C3-C20)cycloalkyl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group, -NR 11 R 12 or -SiR 13
  • L 1 and L 2 each independently represent a single bond; a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, or a di(C6-C15)arylamino group; or an unsubstituted 5- to 10-membered heteroarylene group;
  • Ar 1 and Ar 2 each independently represent a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, or a (C6-C15)aryl (5- to 10-memebered) heteroarylamino group; or a 5- to 10-membered heteroaryl group unsubstituted or substituted with a (C6-C15)aryl group or a di(C6-C15)
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 15; more preferably 1 to 6; and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, etc.;
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20; more preferably 2 to 10; and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and 2-methylbut-2-enyl, etc.
  • “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • the representative organic electroluminescent compounds of the present invention include the following compounds:
  • organic electroluminescent compounds of the present invention can be prepared according to reactions well-known in the art, for example, the following reaction schemes:
  • X, L 1 , L 2 , Ar 1 , Ar 2 , R 1 to R 4 , a, b, c and d are as defined in formula 1 above, and Hal represents a halogen atom.
  • the reaction of Reaction Scheme 1 is performed under aromatic hydrocarbons or ordinary polar organic solvents (for example, benzene, toluene, xylene, tetrahydrofuran, dioxane, or mixture thereof), preferably toluene. Additionally, the reaction is performed under alkali metal hydroxides or carbonate (for example, NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , etc.), preferably aqueous K 2 CO 3 solution.
  • aromatic hydrocarbons or ordinary polar organic solvents for example, benzene, toluene, xylene, tetrahydrofuran, dioxane, or mixture thereof
  • alkali metal hydroxides or carbonate for example, NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , etc.
  • reaction temperature is selected in the range of 40 to 180°C under reflux
  • reaction time is selected in the range of 1 to 80 hours, preferably 2 to 24 hours.
  • Pt based catalysts especially (Ph 3 P) 4 Pd or derivates thereof, is used in the reaction as an ordinary catalyst for coupling reaction or polycondensation reaction.
  • the catalyst is added in the form of solution or suspension.
  • the obtained compound according to the present invention in the reaction can be separated through a method well-known in the art.
  • the reaction mixture is extracted with ethyl acetate(EA)/ H 2 O, and dried with MgSO 4 .
  • the resulting product is then distilled under reduced pressure and separated through column chromatography to obtain the compound according to the present invention.
  • 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 contained 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 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.
  • the organic electroluminescent compound of formula 1 according to the present invention can be comprised of in at least one of the light-emitting layer and the hole transport layer.
  • the compound of formula 1 according to the present invention can be comprised as a hole transport material.
  • the compound of formula 1 according to the present invention can be comprised as a host material; preferably, the light-emitting layer can further comprise at least one dopant; and, if needed, another compound as a second host material in addition to the organic electroluminescent compound of formula 1 according to the present invention.
  • the second host material can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulas 2 to 4 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 group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or R 25 R 26 R 27 Si-;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroary
  • preferable examples of the second host material are as follows:
  • the dopant used in the manufacture of the organic electroluminescent device is preferably one or more phosphorescent dopants.
  • the phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but preferably may be selected from complex compounds of iridium(Ir), osmium(Os), copper(Cu) and platinum(Pt); more preferably ortho-metallated complex compounds of iridium(Ir), osmium(Os), copper(Cu) and platinum(Pt); and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant comprised in the organic electroluminescent device may be selected from compounds represented by the following formulas 5 to 7.
  • L is selected from the following structures:
  • R 100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl group
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a cyano group, a substituted or unsubstituted (C1-C30)alkoxy group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or R 120 to R 123 are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring(e.g.
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; where R 124 to R 127 are aryl groups, adjacent substituents may be linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring(e.g.
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s);
  • f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R 100 is the same or different; and n is an integer of 1 to 3.
  • the phosphorescent dopant may be selected from compounds represented by the following compounds:
  • the present invention further provides a material for an organic electroluminescent device.
  • the material comprises a first host material and a second host material, wherein the compound according to the present invention can be comprised as a first host material, wherein the ratio of the first host material to the second host material can be in the range of 1:99 to 99:1.
  • the organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, wherein the light-emitting layer comprises the material for the organic electroluminescent device according to the present invention and a phosphorescent dopant material, and the material for the organic electroluminescent device according to the present invention is used as a host material.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the compounds 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 the metal.
  • the organic layer may comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound, besides the compound according to the present invention. Additionally, if needed, it further comprises a yellow or orange light-emitting layer.
  • a surface layer of the organic electroluminescent device preferably selected from a chalcogenide layer, a metal halide layer and a metal oxide layer; may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • Such a surface layer provides operation stability for the organic electroluminescent device.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to 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 which will form each layer, into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent which the materials can dissolve or diffuse, unless the solvent has problems in film formation properties.
  • An OLED device using the organic electroluminescent compound according to the present invention was produced as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • ITO indium tin oxide
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(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-99 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.
  • a light-emitting layer was deposited on said layers as follows.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus.
  • 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 8020 cd/m 2 and a current density of 19.2 mA/cm 2 .
  • An OLED device was produced in the same manner as that of Device Example 1, except that compound C-80 was deposited as the hole transport layer having a thickness of 20 nm; and 9-(4-([1,1':3',1"-terphenyl]-4-yl)pyrimidine-2-yl)-3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole was introduced into one cell of the vacuum vapor depositing apparatus; compound D-25 was introduced into another cell as a dopant material; and the two materials were evaporated at different rates, and 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.
  • the produced OLED device showed a green emission having a luminance of 2630 cd/m 2 and a current density of 6.4 mA/cm 2 .
  • Comparative Example 1 Production of an OLED device using conventional
  • An OLED device was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was deposited as a hole transport layer having a thickness of 20 nm; 4,4'-N,N'-dicarbazole-biphenyl was used as a host material, and compound D-15 was used as a dopant material; a light-emiiting layer having a thickness of 30 nm was deposited on the hole transport layer; and a hole blocking layer having a thickness of 10 nm was deposited by using aluminium(III) bis(2-methyl-8-quinolinato)4-phenylphenolate.
  • the produced OLED device showed a green emission having a luminance of 3350 cd/m 2 and a current density of 9.7 mA/cm 2 .
  • the organic electroluminescent compounds according to the present invention have high luminous efficiency, compared with conventional materials. Further, the organic electroluminescent device using the organic electroluminescent compounds according to the present invention has superior luminous efficiency and power efficiency.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has superior luminous efficiency, and can provide an organic electroluminescent device having improved power efficiency by reducing the driving voltage of the device.

Description

A NOVEL ORGANIC ELECTROLUMINESCENCE COMPOUND AND AN ORGANIC ELECTROLUMINESCENCE DEVICE CONTAINING THE SAME
The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device containing the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages over other types of display devices 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 light-emitting materials theoretically enhance the luminous efficiency by four (4) times compared to fluorescent light-emitting materials, development of phosphorescent light-emitting materials are widely being researched. In this regard, iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)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.
In order to improve color purity, luminous efficiency, and stability, a host material mixed with a light-emitting material (dopant) can be used as a light-emitting material. When using such a light-emitting material (dopant)/a host material system, choosing the host material is important, since the host material has a large influence in efficiency and performance of a light-emitting device. Generally, 4,4’-N,N’-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent light-emitting host material. Lately, Pioneer (Japan) et al., developed a high performance organic EL device employing a Bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinato)(4-phenylphenolate) (BAlq), etc., as a host material, which were used as a hole blocking material.
Although these phosphorescent host materials have some advantages in view of light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, they may be degraded 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 power efficiency is inversely proportional to voltage. An organic EL device comprising phosphorescent host materials provides a higher current efficiency (cd/A) than one comprising fluorescent materials. However, it has a higher driving voltage, and thus, there is no substantial merit in terms of power efficiency (lm/W). (3) Further, when the phosphorescent host materials are used in an OLED device, the operating lifespan of the device is unsatisfactory, and luminous efficiency still needs improvement.
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 in an organic EL device. However, such materials have problems with decreasing quantum efficiency and the lifespan of an organic EL device, because when the organic EL device is operated at high current, thermal stress occurs between an anode and a hole injection layer, which reduces the lifespan of the device. Further, since organic materials used in a hole injection layer have high motility of holes, hole-electron charge balance is lost and quantum efficiency (cd/A) is reduced.
Korean Patent Appln. Laying-Open No. 2009-0035729 A discloses amine compounds containing carbazole for an organic electroluminescence device. Further, Korean Patent Appln. Laying-Open No. 2011-0129766 A discloses amine compounds containing fused carbazole for an organic electroluminescence device. However, the organic EL devices comprising the compounds disclosed in the reference are still unsatisfactory in view of power efficiency, luminous efficiency, quantum efficiency, and lifespan, etc.
The objective of the present invention is to provide an organic electroluminescent compound having high luminous efficiency and superior lifespan over conventional materials, and to provide an organic electroluminescent device having high efficiency and long lifespan.
The present inventors found that the objective above is achievable by a compound represented by the following formula 1:
Figure PCTKR2013008206-appb-I000001
wherein
L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
X represents oxygen atom, sulfur atom, or -CR5R6-;
R1 to R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a (C6-C30)aryl group fused with a (C3-C30)cycloalkyl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring whose carbon atom(s) may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
R11 to R20 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring whose carbon atom(s) may be replaced by at least one heteroatom 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 R1 is the same or different;
b to d each independently represent an integer of 1 to 3; where b, c or d is an integer of 2 or more, each of R2, each of R3, and each of R4 is the same or different;
the heteraryl(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.
The organic electroluminescent compound according to the present invention has high luminous efficiency and superior lifespan characteristics of material, and thus can provide an organic electroluminescent device, which is excellent in operational lifespan of the device. Further, the organic electroluminescent compound according to the present invention can reduce driving voltage and improve power efficiency of an organic electroluminescent device at the same time.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound represented by formula 1, above, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
Hereinafter, the organic electroluminescent compound represented by the above formula 1 will be described in detail.
In formula 1, above, L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; preferably a single bond, a substituted or unsubstituted (C6-C20)arylene group, or a substituted or unsubstituted 5- to 15-membered heteroarylene group; more preferably a single bond; a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, a (C1-C15)aryl group or a di(C6-C15)arylamino group; or an unsubstituted 5- to 10-membered heteroarylene group.
In formula 1, above, Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; preferably a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; more preferably a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, or a (C6-C15)aryl(5- to 10-membered) heteroarylamino group; or a 5- to 10-membered heteroaryl group unsubstituted or substituted with a (C6-C15)aryl group or a di(C6-C15)arylamino group.
In formula 1, above, X represents oxygen atom, sulfur atom, or -CR5R6-;
In formula 1, above, R1 to R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a (C6-C30)aryl group fused with a (C3-C30)cycloalkyl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring whose carbon atom(s) may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; preferably hydrogen, a halogen, a substituted or unsubstituted (C1-C15)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, a (C6-C15)aryl group fused with a (C3-C20)cycloalkyl group, a substituted or unsubstituted 5- to 15-membered heteroaryl group, -NR11R12, or -SiR13R14R15; more preferably hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group or a (C6-C15)aryl group; a (C6-C15)aryl group fused with a (C3-C7)cycloalkyl group; an unsubstituted 5- to 15-membered heteroaryl group; or -NR11R12;
R11 to R12 each independently represent preferably a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; more preferably an unsubstituted (C6-C15)aryl group; and R13 to R15 each independently represent preferably a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C15)aryl group.
According to an embodiment of the present invention in formula 1, above, L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene group, or a substituted or unsubstituted 5- to 15-membered heteroarylene group; Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; R1 to R6 each independently represent hydrogen, a halogen, a substituted or unsubstituted (C1-C15)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, a (C6-C15)aryl group fused with a (C3-C20)cycloalkyl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group, -NR11R12 or -SiR13R14R15; wherein R11 and R12 each independently represent a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; and R13 to R15 each independently represent a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C15)aryl group.
According to another embodiment of the present invention in formula 1, above, L1 and L2 each independently represent a single bond; a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, or a di(C6-C15)arylamino group; or an unsubstituted 5- to 10-membered heteroarylene group; Ar1 and Ar2 each independently represent a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, or a (C6-C15)aryl (5- to 10-memebered) heteroarylamino group; or a 5- to 10-membered heteroaryl group unsubstituted or substituted with a (C6-C15)aryl group or a di(C6-C15)arylamino group; R1 to R6 each independently represent hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group or a (C6-C15)aryl group; a (C6-C15)aryl group fused with a (C3-C7)cycloalkyl group; an unsubstituted 5- to 15-membered heteroaryl group; or -NR11R12; wherein R11 and R12 each independently represent an unsubstituted (C6-C15)aryl group.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 15; more preferably 1 to 6; and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, etc.; “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20; more preferably 2 to 10; and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and 2-methylbut-2-enyl, etc.; “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20; more preferably 2 to 10; and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20; more preferably 3 to 7; and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P; preferably O, S and N, and 3 to 7 ring backbone atoms; and includes tetrahydrofurane, pyrrolidine, thiolan, tetrahydropyran, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20; more preferably 6 to 15; and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “5- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 5 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 5 to 15; more preferably 5 to 10 ring backbone atoms; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “halogen” includes F, Cl, Br and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. In formula 1, above, substituents of the substituted (C1-C30)alkyl group, the substituted (C2-C30)alkenyl group, the substituted (C2-C30)alkynyl group, the substituted (C1-C30)alkoxy group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30)aryl(ene) group, or the substituted 5- to 30-membered heteroaryl(ene) group each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a (C1-C30)alkyl group, a halo(C1-C30)alkyl group, a (C2-C30)alkenyl group, a (C2-C30)alkynyl group, a (C1-C30)alkoxy group, a (C1-C30)alkylthio group, a (C3-C30)cycloalkyl group, a (C3-C30)cycloalkenyl group, a 3- to 7-membered heterocycloalkyl group, a (C6-C30)aryloxy group, a (C6-C30)arylthio group, a 5- to 30-membered heteroaryl group unsubstituted or substituted with a (C6-C30)aryl group, a (C6-C30)aryl group unsubstituted or substituted with a 5- to 30-membered heteroaryl group, a tri(C1-C30)alkylsilyl group, a tri(C6-C30)arylsilyl group, a di(C1-C30)alkyl(C6-C30)arylsilyl group, a (C1-C30)alkyldi(C6-C30)arylsilyl group, an amino group, a mono- or di-(C1-C30)alkylamino group, a mono- or di-(C6-C30)arylamino group, a (C1-C30)alkyl(C6-C30)arylamino group, a (C1-C30)alkylcarbonyl group, (C1-C30)alkoxycarbonyl group, (C6-C30)arylcarbonyl group, a di(C6-C30)arylboronyl group, a di(C1-C30)alkylboronyl group, a (C1-C30)alkyl(C6-C30)arylboronyl group, a (C6-C30)aryl(C1-C30)alkyl group, and a (C1-C30)alkyl(C6-C30)aryl group; preferably each independently are at least one selected from the group consisting of a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, and a (C6-C15)aryl(5- to 10-membered)heteroarylamino group.
The representative organic electroluminescent compounds of the present invention include the following compounds:
Figure PCTKR2013008206-appb-I000002
Figure PCTKR2013008206-appb-I000003
Figure PCTKR2013008206-appb-I000004
Figure PCTKR2013008206-appb-I000005
Figure PCTKR2013008206-appb-I000006
Figure PCTKR2013008206-appb-I000007
Figure PCTKR2013008206-appb-I000008
Figure PCTKR2013008206-appb-I000009
Figure PCTKR2013008206-appb-I000010
Figure PCTKR2013008206-appb-I000011
Figure PCTKR2013008206-appb-I000012
Figure PCTKR2013008206-appb-I000013
Figure PCTKR2013008206-appb-I000014
Figure PCTKR2013008206-appb-I000015
Figure PCTKR2013008206-appb-I000016
Figure PCTKR2013008206-appb-I000017
Figure PCTKR2013008206-appb-I000018
Figure PCTKR2013008206-appb-I000019
Figure PCTKR2013008206-appb-I000020
Figure PCTKR2013008206-appb-I000021
Figure PCTKR2013008206-appb-I000022
Figure PCTKR2013008206-appb-I000023
Figure PCTKR2013008206-appb-I000024
Figure PCTKR2013008206-appb-I000025
Figure PCTKR2013008206-appb-I000027
Figure PCTKR2013008206-appb-I000028
Figure PCTKR2013008206-appb-I000029
Figure PCTKR2013008206-appb-I000030
Figure PCTKR2013008206-appb-I000031
The organic electroluminescent compounds of the present invention can be prepared according to reactions well-known in the art, for example, the following reaction schemes:
[Reaction Scheme 1]
Figure PCTKR2013008206-appb-I000032
Wherein, in Reaction Scheme 1, X, L1, L2, Ar1, Ar2, R1 to R4, a, b, c and d are as defined in formula 1 above, and Hal represents a halogen atom.
The reaction of Reaction Scheme 1 is performed under aromatic hydrocarbons or ordinary polar organic solvents (for example, benzene, toluene, xylene, tetrahydrofuran, dioxane, or mixture thereof), preferably toluene. Additionally, the reaction is performed under alkali metal hydroxides or carbonate (for example, NaOH, KOH, Na2CO3, K2CO3, Cs2CO3, etc.), preferably aqueous K2CO3 solution.
Generally, the reaction temperature is selected in the range of 40 to 180°C under reflux, and the reaction time is selected in the range of 1 to 80 hours, preferably 2 to 24 hours.
According to prefer embodiment of the present invention, Pt based catalysts, especially (Ph3P)4Pd or derivates thereof, is used in the reaction as an ordinary catalyst for coupling reaction or polycondensation reaction. The catalyst is added in the form of solution or suspension.
Further, the obtained compound according to the present invention in the reaction can be separated through a method well-known in the art. For example, the reaction mixture is extracted with ethyl acetate(EA)/ H2O, and dried with MgSO4. The resulting product is then distilled under reduced pressure and separated through column chromatography to obtain the compound according to the present invention.
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 contained 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 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.
The organic electroluminescent compound of formula 1 according to the present invention can be comprised of in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the compound of formula 1 according to the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the compound of formula 1 according to the present invention can be comprised as a host material; preferably, the light-emitting layer can further comprise at least one dopant; and, if needed, another compound as a second host material in addition to the organic electroluminescent compound of formula 1 according to the present invention.
The second host material can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulas 2 to 4 below is preferable in view of luminous efficiency.
Figure PCTKR2013008206-appb-I000033
Figure PCTKR2013008206-appb-I000034
Figure PCTKR2013008206-appb-I000035
wherein
Cz represents the following structure;
Figure PCTKR2013008206-appb-I000036
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or R25R26R27Si-; R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; 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 group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, and R32 and R33 are 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 is the same or different.
Specifically, preferable examples of the second host material are as follows:
Figure PCTKR2013008206-appb-I000037
Figure PCTKR2013008206-appb-I000038
Figure PCTKR2013008206-appb-I000039
Figure PCTKR2013008206-appb-I000040
Figure PCTKR2013008206-appb-I000041
Figure PCTKR2013008206-appb-I000042
Figure PCTKR2013008206-appb-I000043
Figure PCTKR2013008206-appb-I000044
Figure PCTKR2013008206-appb-I000045
Figure PCTKR2013008206-appb-I000046
Figure PCTKR2013008206-appb-I000047
Figure PCTKR2013008206-appb-I000048
Figure PCTKR2013008206-appb-I000049
According to the present invention, the dopant used in the manufacture of the organic electroluminescent device is preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the electroluminescent device according to the present invention is not limited, but preferably may be selected from complex compounds of iridium(Ir), osmium(Os), copper(Cu) and platinum(Pt); more preferably ortho-metallated complex compounds of iridium(Ir), osmium(Os), copper(Cu) and platinum(Pt); and even more preferably ortho-metallated iridium complex compounds.
According to the present invention, the phosphorescent dopant comprised in the organic electroluminescent device may be selected from compounds represented by the following formulas 5 to 7.
Figure PCTKR2013008206-appb-I000050
Figure PCTKR2013008206-appb-I000051
Figure PCTKR2013008206-appb-I000052
wherein L is selected from the following structures:
Figure PCTKR2013008206-appb-I000053
R100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl group; R101 to R109, and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a cyano group, a substituted or unsubstituted (C1-C30)alkoxy group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or R120 to R123 are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring(e.g. quinoline); R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; where R124 to R127 are aryl groups, adjacent substituents may be linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring(e.g. fluorene); R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s); f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R100 is the same or different; and n is an integer of 1 to 3.
Specifically, the phosphorescent dopant may be selected from compounds represented by the following compounds:
Figure PCTKR2013008206-appb-I000054
Figure PCTKR2013008206-appb-I000055
Figure PCTKR2013008206-appb-I000056
Figure PCTKR2013008206-appb-I000057
Figure PCTKR2013008206-appb-I000058
Figure PCTKR2013008206-appb-I000059
Figure PCTKR2013008206-appb-I000060
Figure PCTKR2013008206-appb-I000061
Figure PCTKR2013008206-appb-I000062
Figure PCTKR2013008206-appb-I000063
Figure PCTKR2013008206-appb-I000064
Figure PCTKR2013008206-appb-I000065
The present invention further provides a material for an organic electroluminescent device. The material comprises a first host material and a second host material, wherein the compound according to the present invention can be comprised as a first host material, wherein the ratio of the first host material to the second host material can be in the range of 1:99 to 99:1.
Further, the organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, wherein the light-emitting layer comprises the material for the organic electroluminescent device according to the present invention and a phosphorescent dopant material, and the material for the organic electroluminescent device according to the present invention is used as a host material.
The organic electroluminescent device according to the present invention may further comprise, in addition to the compounds 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 the metal. The organic layer may comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound, besides the compound according to the present invention. Additionally, if needed, it further comprises a yellow or orange light-emitting layer.
According to the present invention, at least one layer (hereinafter, "a surface layer”) of the organic electroluminescent device preferably selected from a chalcogenide layer, a metal halide layer and a metal oxide layer; may be placed on an inner surface(s) of one or both electrode(s). Specifically, 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 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.
Preferably, in the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to 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 applying a wet film-forming method, a thin film can be formed by dissolving or diffusing materials which will form each layer, into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent which the materials can dissolve or diffuse, unless the solvent has problems in film formation properties.
Hereinafter, the representative organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device comprising the compound of the present invention will be explained in detail with reference to the following examples, but not limited thereto:
Example 1: Preparation of compound C-80
Preparation of compound 1-3
Figure PCTKR2013008206-appb-I000066
After dissolving compound 1-1, 63g (0.177mol), compound 1-2, 30g (0.177mol), sodium tert-butoxide (NaOt-Bu) 26g (0.266mol) and tri(o-tolyl)phosphine(P(o-Tol)3) 4.3g (0.014mol) in toluene 1.7L, tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) 3.2g (0.004mol) was added. The mixture was stirred for 3 hours at 120°C. The reactant was cooled to room temperature, and extracted with ethyl acetate 1L. The obtained organic layer was washed with distilled water 400mL. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol and dried after filtration. The resulting product was separated through silica gel column chromatography and recrystallization to obtain compound 1-3, 41g (58%).
Preparation of compound 1-4
Figure PCTKR2013008206-appb-I000067
After dissolving compound 1-3, 10g(25mmol) in tetrahydrofuran(THF) 150mL, n-BuLi (2.5M, in hexane) 15mL(37.50mol) was added at -78°C. The mixture was stirred for 1 hour at -78°C, and trimethoxyborane(B(OMe)3) compound 4.2mL(37.50mol) was added. The total reactant was stirred for 2 hours, and the reaction was terminated with NH4Cl 100mL. After extracting with ethyl acetate 200mL, the obtained organic layer was washed with distilled water 100mL. The organic layer was dried with MgSO4 and the organic solvent was removed under reduced pressure. The obtained solid was separated through recrystallization to obtain compound 1-4, 5.4g(59%).
Preparation of compound 1-7
Figure PCTKR2013008206-appb-I000068
After dissolving compound 1-5, 6.7g(19.60mmol), compound 1-6, 4.1g(17.82mmol) and Na2CO3 4.7g(44.55mol) in mixed solution of toluene 90mL, ethanol 20mL and distilled water 20mL, tetrakistriphenylphosphine palladium 0.6g(0.53mmol) was added. The mixture was stirred under reflux for 5 hours at 120°C. The reactant was cooled to room temperature and extracted with ethyl acetate 200mL. The obtained organic layer was washed with distilled water 100mL. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol and dried after filtration. The resulting product was separated through silica gel column chromatography and recrystallization to obtain compound 1-7, 3.7g (47%).
Preparation of compound C-80
Figure PCTKR2013008206-appb-I000069
After dissolving compound 1-7, 3.7g(8.30mmol), compound 1-4, 3.3g(9.10mmol) and Na2CO3 2.2g(20.80mmol) in a mixed solution of toluene 44mL, ethanol 11mL and distilled water 11mL, tetrakistriphenylphosphine palladium 0.5g(0.4mmol) was added. The mixture was stirred under reflux for 5 hours at 120°C. The reactant was cooled to room temperature, and extracted with ethyl acetate 200mL. The obtained organic layer was washed with distilled water 100mL. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol and dried after filtration. The resulting product was separated through silica gel column chromatography and recrystallization to obtain compound C-80, 1.8g(32%).
MS/EIMS: found 685.90; calculated 685.19, melting point(Mp): 211°C
Example 2: Preparation of compound C-99
Figure PCTKR2013008206-appb-I000070
Preparation of compound 2-9
After introducing 4-(diphenylamino)phenylboronic acid 15g(52mmol), 2,8-dibromobenzo[b,d]thiophene 103.8g(103.8mmol), tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] 3g(2.6mmol) and Na2CO3 14g(130mol) into a round flask, toluene 250mL, EtOH 50mL and H2O 50mL were added. The reaction mixture was stirred for 2 hours at 100°C. The reactant was extracted with ethyl acetate(EA)/H2O, dried with MgSO4, and distilled under reduced pressure. The resulting product was separated through column chromatography to obtain compound 2-9, 13g(58%).
Preparation of compound C-99
After introducing compound 2-9, 6g(13.9mmol), 9,9-dimethyl-9H-fluoren-2-ylboronic acid 4g(16.7mmol), Pd(PPh3)4 0.8g(0.7mmol) and K2CO3 4.8g(35mmol) into a round flask, toluene 45mL, EtOH 15mL and H2O 15mL were added. The reaction mixture was stirred for 2 hours at 120°C. The reactant was extracted with EA/H2O, dried with MgSO4, and distilled under reduced pressure. The resulting product was separated through column chromatography to obtain compound C-99, 3.9g(45%).
MS/EIMS: found 619.8; calculated 619.23, melting point(Mp): 198°C
Device Example 1: Production of an OLED device using the compound according to the present invention
An OLED device using the organic electroluminescent compound according to the present invention was produced as follows.
First, 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) 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-99 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. After the hole injection layer and the hole transport layer were formed as above, a light-emitting layer was deposited on said layers as follows.
5-(4-([1,1':4',1"-terphenyl]-3-yl)pyrimidine-2-yl)-5H-benzo[4,5]thieno[3,2-c]carbazole 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 material, and the two materials were evaporated at different rates, and 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, in order to form an electron transport layer on the formed light-emitting layer, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into a cell, and lithium quinolate was introduced into another cell, and the two materials were evaporated at the same rate to deposit in a doping amount of 50 wt%, respectively. Thus, an electron transport layer having a thickness of 30 nm was formed on the light-emitting layer. Then, in order to form an electron injection layer, after depositing lithium quinolate in a thickness of 2 nm, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus. 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.
As a result, the produced OLED device showed a green emission having a luminance of 8020 cd/m2 and a current density of 19.2 mA/cm2.
Device Example 2: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as that of Device Example 1, except that compound C-80 was deposited as the hole transport layer having a thickness of 20 nm; and 9-(4-([1,1':3',1"-terphenyl]-4-yl)pyrimidine-2-yl)-3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole was introduced into one cell of the vacuum vapor depositing apparatus; compound D-25 was introduced into another cell as a dopant material; and the two materials were evaporated at different rates, and 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.
As a result, the produced OLED device showed a green emission having a luminance of 2630 cd/m2 and a current density of 6.4 mA/cm2.
Comparative Example 1: Production of an OLED device using conventional
electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was deposited as a hole transport layer having a thickness of 20 nm; 4,4'-N,N'-dicarbazole-biphenyl was used as a host material, and compound D-15 was used as a dopant material; a light-emiiting layer having a thickness of 30 nm was deposited on the hole transport layer; and a hole blocking layer having a thickness of 10 nm was deposited by using aluminium(III) bis(2-methyl-8-quinolinato)4-phenylphenolate.
As a result, the produced OLED device showed a green emission having a luminance of 3350 cd/m2 and a current density of 9.7 mA/cm2.
It is confirmed that the organic electroluminescent compounds according to the present invention have high luminous efficiency, compared with conventional materials. Further, the organic electroluminescent device using the organic electroluminescent compounds according to the present invention has superior luminous efficiency and power efficiency.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013008206-appb-I000071
    wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;
    X represents oxygen atom, sulfur atom, or -CR5R6-;
    R1 to R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, a (C6-C30)aryl group fused with a (C3-C30)cycloalkyl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 or -B(OR19)(OR20); or are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring whose carbon atom(s) may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
    R11 to R20 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C2-C30)alkynyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic 3- to 30-memebered alicyclic or aromatic ring whose carbon atom(s) may be replaced by at least one heteroatom 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 R1 is the same or different;
    b to d each independently represent an integer of 1 to 3; where b, c or d is an integer of 2 or more, each of R2, each of R3, and each of R4 is the same or different;
    the heteraryl(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 substituents of the substituted (C1-C30)alkyl group, the substituted (C2-C30)alkenyl group, the substituted (C2-C30)alkynyl group, the substituted (C1-C30)alkoxy group, the substituted (C3-C30)cycloalkyl group, the substituted (C3-C30)cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted aryl(ene) group, and the substituted 5- to 30-membered heteroaryl(ene) group in L1, L2, Ar1, Ar2, R1 to R6, and R11 to R20 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a (C1-C30)alkyl group, a halo(C1-C30)alkyl group, a (C2-C30)alkenyl group, a (C2-C30)alkynyl group, a (C1-C30)alkoxy group, a (C1-C30)alkylthio group, a (C3-C30)cycloalkyl group, a (C3-C30)cycloalkenyl group, a 3- to 7-membered heterocycloalkyl group, a (C6-C30)aryloxy group, a (C6-C30)arylthio group, a 5- to 30-membered heteroaryl group unsubstituted or substituted with a (C6-C30)aryl group, a (C6-C30)aryl group unsubstituted or substituted with a 5- to 30-membered heteroaryl group, a tri(C1-C30)alkylsilyl group, a tri(C6-C30)arylsilyl group, a di(C1-C30)alkyl(C6-C30)arylsilyl group, a (C1-C30)alkyldi(C6-C30)arylsilyl group, an amino group, a mono- or di-(C1-C30)alkylamino group, a mono- or di-(C6-C30)arylamino group, a (C1-C30)alkyl(C6-C30)arylamino group, a (C1-C30)alkylcarbonyl group, (C1-C30)alkoxycarbonyl group, (C6-C30)arylcarbonyl group, a di(C6-C30)arylboronyl group, a di(C1-C30)alkylboronyl group, a (C1-C30)alkyl(C6-C30)arylboronyl group, a (C6-C30)aryl(C1-C30)alkyl group, and a (C1-C30)alkyl(C6-C30)aryl group.
  3. The organic electroluminescent compound according to claim 1, wherein L1 and L2 each independently represent a single bond, a substituted or unsubstituted (C6-C20)arylene group, or a substituted or unsubstituted 5- to 15-membered heteroarylene group;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group;
    R1 to R6 each independently represent hydrogen, a halogen, a substituted or unsubstituted (C1-C15)alkyl group, a substituted or unsubstituted (C6-C15)aryl group, a (C6-C15)aryl group fused with a (C3-C20)cycloalkyl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group, -NR11R12 or -SiR13R14R15; wherein R11 and R12 each independently represent a substituted or unsubstituted (C6-C15)aryl group, or a substituted or unsubstituted 5- to 15-membered heteroaryl group; and R13 to R15 each independently represent a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C15)aryl group.
  4. The organic electroluminescent compound according to claim 1, wherein L1 and L2 each independently represent a single bond; a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, or a di(C6-C15)arylamino group; or an unsubstituted 5- to 10-membered heteroarylene group;
    Ar1 and Ar2 each independently represent a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group, a (C6-C15)aryl group, a di(C6-C15)arylamino group, or a (C6-C15)aryl(5- to 10-memebered) heteroarylamino group; or a 5- to 10-membered heteroaryl group unsubstituted or substituted with a (C6-C15)aryl group or a di(C6-C15)arylamino group;
    R1 to R6 each independently represent hydrogen; a halogen; an unsubstituted (C1-C6)alkyl group; a (C6-C15)aryl group unsubstituted or substituted with a (C1-C6)alkyl group or a (C6-C15)aryl group; a (C6-C15)aryl group fused with a (C3-C7)cycloalkyl group; an unsubstituted 5- to 15-membered heteroaryl group; or -NR11R12; wherein R11 and R12 each independently represent an unsubstituted (C6-C15)aryl group.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013008206-appb-I000072
    Figure PCTKR2013008206-appb-I000073
    Figure PCTKR2013008206-appb-I000074
    Figure PCTKR2013008206-appb-I000075
    Figure PCTKR2013008206-appb-I000076
    Figure PCTKR2013008206-appb-I000077
    Figure PCTKR2013008206-appb-I000078
    Figure PCTKR2013008206-appb-I000079
    Figure PCTKR2013008206-appb-I000080
    Figure PCTKR2013008206-appb-I000081
    Figure PCTKR2013008206-appb-I000082
    Figure PCTKR2013008206-appb-I000083
    Figure PCTKR2013008206-appb-I000084
    Figure PCTKR2013008206-appb-I000085
    Figure PCTKR2013008206-appb-I000086
    Figure PCTKR2013008206-appb-I000087
    Figure PCTKR2013008206-appb-I000088
    Figure PCTKR2013008206-appb-I000089
    Figure PCTKR2013008206-appb-I000090
    Figure PCTKR2013008206-appb-I000091
    Figure PCTKR2013008206-appb-I000092
    Figure PCTKR2013008206-appb-I000093
    Figure PCTKR2013008206-appb-I000094
    Figure PCTKR2013008206-appb-I000095
    Figure PCTKR2013008206-appb-I000096
    Figure PCTKR2013008206-appb-I000097
    Figure PCTKR2013008206-appb-I000098
    Figure PCTKR2013008206-appb-I000099
    Figure PCTKR2013008206-appb-I000100
    Figure PCTKR2013008206-appb-I000101
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2013/008206 2012-09-14 2013-09-11 A novel organic electroluminescence compound and an organic electroluminescence device containing the same WO2014042420A1 (en)

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