WO2014098518A1 - Novel organic electroluminescent compounds and an organic electroluminescent device comprising the same - Google Patents

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

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WO2014098518A1
WO2014098518A1 PCT/KR2013/011949 KR2013011949W WO2014098518A1 WO 2014098518 A1 WO2014098518 A1 WO 2014098518A1 KR 2013011949 W KR2013011949 W KR 2013011949W WO 2014098518 A1 WO2014098518 A1 WO 2014098518A1
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unsubstituted
substituted
group
membered
aryl
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Hee-Choon Ahn
Soo-Jin Yang
Doo-Hyeon Moon
Ji-Song JUN
Tae-Jin Lee
Kyung-Joo Lee
Hyuck-Joo Kwon
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2014098518A1 publication Critical patent/WO2014098518A1/en

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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Definitions

  • the present invention relates to novel 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 light-emitting 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.
  • a luminescent material can be used in combination with a host material as a light-emitting material to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as a light emitting material, their selection is important.
  • 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 Appln. Laying-Open No. 2011-0129766 A discloses a compound in which an arylamine group or an aryl group substituted with an arylamine group is bonded to a carbon atom of a carbazole of a backbone in which the carbazole is fused with a five-membered heterocyclic ring and a benzene ring, as an organic dye for an organic EL device.
  • Korean Patent Appln. Laying-Open No. 2010-0131271 A discloses a compound in which an arylamine group, an aryloxy group, or an aryl group substituted with an arylamine group or an aryloxy group is bonded to a carbon atom of a carbazole of an indenocarbazole, as a compound for an organic EL device.
  • Korean Patent Appln. Laying-Open No. 2011-0049665 A discloses a compound in which an aryl group substituted with two diarylamino groups is bonded to a carbon atom of a carbazole of a backbone which consist of a carbazole, a dibenzocarbazole, or a carbazole fused with an acridine, as a compound for an organic EL device.
  • Korean Patent Appln. Laying-Open No. 2011-0061792 A discloses a compound in which an aryl group substituted with one or two diarylamino groups is bonded to a nitrogen atom of a dibenzocarbazole backbone, as a compound for an organic EL device.
  • the objective of the present invention is to provide an organic electroluminescent compound which is comprised in at least one of a light-emitting layer and a hole transport layer, and has higher current efficiency and luminous efficiency than conventional materials, and an organic EL device comprising the compound.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
  • Ar 1 to Ar 4 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;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that only one of Y 1 and Y 2 exists;
  • R 31 to R 33 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; or R 32 and R 33 may be linked to each other 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;
  • R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano group, 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamin
  • a and b each independently represent an integer of 1 to 4; where a or b is 2 or more, each of R 1 and R 2 may be the same or different.
  • 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 luminous characteristics due to 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 organic electroluminescent compound represented by the above formula 1 will be described in detail.
  • L 1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group, preferably represents an unsubstituted (C6-C30)arylene group, and more preferably represents an unsubstituted (C6-C20)arylene group.
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group, preferably represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or an unsubstituted (5- to 30- membered)heteroarylene group, and more preferably represents a single bond, a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group; or an unsubstituted (5- to 20- membered)heteroarylene group.
  • Ar 1 to Ar 4 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, preferably each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted (5- to 30- membered)heteroaryl group, and more preferably each independently represent a (C6-C20)aryl group unsubstituted or substituted with deuterium, a cyano, a (C1-C6)alkyl group, or a (C6-C20)arylamino group; or a (5- to 20- membered)heteroaryl group unsubstituted or substituted with a (C6-C20)aryl group.
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that only one of Y 1 and Y 2 exists
  • R 31 to R 33 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, or R 32 and R 33 may be linked to each other 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.
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that only one of Y 1 and Y 2 exists, and R 31 to R 33 each independently represent an unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl, or R 32 and R 33 may be linked to each other to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring.
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that only one of Y 1 and Y 2 exists
  • R 31 to R 33 each independently represent an unsubstituted (C1-C6)alkyl, or a (C6-C20)aryl unsubstituted or substituted with deuterium, or R 32 and R 33 may be linked to each other to form a mono- or polycyclic, (3- to 20- membered) alicyclic or aromatic ring.
  • R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano group, 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamin
  • a and b each independently represent an integer of 1 to 4, preferably each independently represent an integer of 1 to 2, where a or b is 2 or more, each of R 1 and R 2 may be the same or different.
  • L 1 represents an unsubstituted (C6-C30)arylene group
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or an unsubstituted (5- to 30- membered)heteroarylene group
  • Ar 1 to Ar 4 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted (5- to 30- membered)heteroaryl group
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33 )-, provided that only one of Y 1 and Y 2 exists
  • R 31 to R 33 each independently represent an unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl, or R
  • L 1 represents an unsubstituted (C6-C20)arylene group
  • L 2 represents a single bond, a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, or an unsubstituted (5- to 20- membered)heteroarylene group
  • Ar 1 to Ar 4 each independently represent a (C6-C20)aryl group unsubstituted or substituted with deuterium, a cyano, a (C1-C6)alkyl group, or a (C6-C20)arylamino group; or a (5- to 20- membered)heteroaryl group unsubstituted or substituted with a (C6-C20)aryl group
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )-, or -C(R 32 )(R 33
  • 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.
  • (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 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.;
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is meant to be a linear or branched alkyl having 2 to 30 carbon atoms, in which the number of carbon atoms
  • 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 scheme 1.
  • L 1 , L 2 , Ar 1 to Ar 4 , R 1 , R 2 , Y 1 , Y 2 , a and b 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 compound of formula 1.
  • 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.
  • 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.
  • the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material.
  • the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
  • the light-emitting layer 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 may be in the range of 1:99 to 99:1.
  • 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 formulae 2 to 6 below is preferable in view of luminous efficiency.
  • X represents -O- or -S-;
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- 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;
  • Y 3 and Y 4 each independently represent -O-, -S-, -N(R 41 )- or -C(R 42 )(R 43 )-, provided that Y 3 and Y 4 do not simultaneously exist;
  • R 41 to R 43 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 R 42 and R 43 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, l and m each independently represent an integer of 0 to 4.
  • each of (Cz-L 4 ), each of (Cz), each of R 21 , each of R 22 , each of R 23 or each of R 24 may be the same or different.
  • preferable examples of the second host material are as follows:
  • the dopant applied to the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant.
  • These phosphorescent dopant materials are 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 7 to 9.
  • 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;
  • 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 may be the same or different; and
  • n an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • a material for an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • 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 material 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 at least one more light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • 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, 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 2-2 (6.5 g, 44%) was obtained by the same synthetic method for preparing compound 1-2 in Example 1, except for using compound 2-1 (8 g, 0.029 mol), 1,3,5-tribromobenzene (27.7 g, 0.087 mol), CuI (552 mg, 0.0029 mol), 1,10-phenanthroline (528 mg, 0.0029 mol), K 2 CO 3 (4.4 g, 0.03 mol), and dimethylformamide (DMF) 200 mL.
  • compound 2-1 8 g, 0.029 mol
  • 1,3,5-tribromobenzene 27.7 g, 0.087 mol
  • CuI 552 mg, 0.0029 mol
  • 1,10-phenanthroline 528 mg, 0.0029 mol
  • K 2 CO 3 4.4 g, 0.03 mol
  • DMF dimethylformamide
  • Compound C-7 (5.5 g, 78%) was obtained by the same synthetic method for preparing compound C-1 in Example 1, except using compound 1-2 (4.2 g, 8.55 mmol), N-phenylbiphenyl-4-amine (4.8 g, 19.6 mmol), Pd 2 (dba) 3 (0.31 g, 0.34 mmol), P(o-Tol) 3 (0.41 g, 1.36 mmol), NaOt-Bu (2.4 g, 25.6 mmol), and toluene 50 mL.
  • Compound 5-2 (4.1 g, 31%) was obtained by the same synthetic method for preparing compound 1-2 in Example 1, except using compound 5-1 (7.3 g, 25.76 mmol), 1,3,5-tribromobenzene (24.3 g, 77.28 mmol), CuI (0.5 g, 2.58 mmol), 1,10-phenanthroline (0.5 g, 2.58 mmol), K 2 CO 3 (3.9 g, 28.34 mmol), and DMF 130 mL.
  • Compound C-46 (3 g, 55%) was obtained by the same synthetic method for preparing compound C-1 in Example 1, except using compound 5-2 (4.1 g, 7.93 mmol), diphenylamine (3.2 g, 19.02 mmol), Pd 2 (dba) 3 (0.3 g, 0.32 mmol), P(o-Tol) 3 (0.4 g, 1.27 mmol), NaOt-Bu (2.3 g, 23.79 mmol), and toluene 80 mL.
  • 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-46 according to the present invention 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-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-biscarbazole 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, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole 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 1850 cd/m 2 and a current density of 3.5 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-2 ; 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 as a host, introducing compound D-87 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 2840 cd/m 2 and a current density of 21.8 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-7 in a thickness of 20 nm for a hole transport layer.
  • the produced OLED device showed a green emission having a luminance of 2880 cd/m 2 and a current density of 5.9 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound C-1 in a thickness of 20 nm for a hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 3500 cd/m 2 and a current density of 28.7 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 10 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 7850 cd/m 2 and a current density of 19.9 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 11 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 1480 cd/m 2 and a current density of 14.5 mA/cm 2 .
  • 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, it is possible to produce an organic electroluminescent device having excellent current efficiency and luminous efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND AN ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent 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 light-emitting 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.
A luminescent material (dopant) can be used in combination with a host material as a light-emitting material to improve color purity, luminous efficiency, and stability. Since host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as a light emitting material, their selection is important.
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 phosphorescent host 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 Appln. Laying-Open No. 2011-0129766 A discloses a compound in which an arylamine group or an aryl group substituted with an arylamine group is bonded to a carbon atom of a carbazole of a backbone in which the carbazole is fused with a five-membered heterocyclic ring and a benzene ring, as an organic dye for an organic EL device.
Korean Patent Appln. Laying-Open No. 2010-0131271 A discloses a compound in which an arylamine group, an aryloxy group, or an aryl group substituted with an arylamine group or an aryloxy group is bonded to a carbon atom of a carbazole of an indenocarbazole, as a compound for an organic EL device.
Korean Patent Appln. Laying-Open No. 2011-0049665 A discloses a compound in which an aryl group substituted with two diarylamino groups is bonded to a carbon atom of a carbazole of a backbone which consist of a carbazole, a dibenzocarbazole, or a carbazole fused with an acridine, as a compound for an organic EL device.
Korean Patent Appln. Laying-Open No. 2011-0061792 A discloses a compound in which an aryl group substituted with one or two diarylamino groups is bonded to a nitrogen atom of a dibenzocarbazole backbone, as a compound for an organic EL device.
However, the above references do not disclose a compound in which an aryl group substituted with two diarylamine groups is bonded to a nitrogen atom of a carbazole of a backbone in which the carbazole is fused with a benzene ring and a five-membered ring, nor an organic EL device using the compound for a hole transport layer.
The objective of the present invention is to provide an organic electroluminescent compound which is comprised in at least one of a light-emitting layer and a hole transport layer, and has higher current efficiency and luminous efficiency than conventional materials, and an organic EL device comprising the compound.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2013011949-appb-I000001
wherein
L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
Ar1 to Ar4 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;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists;
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; or R32 and R33 may be linked to each other 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;
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or may be 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;
the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P; and
a and b each independently represent an integer of 1 to 4; where a or b is 2 or more, each of R1 and R2 may be the same or different.
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device which has excellent luminous characteristics due to 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 organic electroluminescent compound represented by the above formula 1 will be described in detail.
In formula 1 above, L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group, preferably represents an unsubstituted (C6-C30)arylene group, and more preferably represents an unsubstituted (C6-C20)arylene group.
L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group, preferably represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or an unsubstituted (5- to 30- membered)heteroarylene group, and more preferably represents a single bond, a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group; or an unsubstituted (5- to 20- membered)heteroarylene group.
Ar1 to Ar4 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, preferably each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted (5- to 30- membered)heteroaryl group, and more preferably each independently represent a (C6-C20)aryl group unsubstituted or substituted with deuterium, a cyano, a (C1-C6)alkyl group, or a (C6-C20)arylamino group; or a (5- to 20- membered)heteroaryl group unsubstituted or substituted with a (C6-C20)aryl group.
Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists, and 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, or R32 and R33 may be linked to each other 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. Preferably, Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists, and R31 to R33 each independently represent an unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl, or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring. More preferably, Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists, and R31 to R33 each independently represent an unsubstituted (C1-C6)alkyl, or a (C6-C20)aryl unsubstituted or substituted with deuterium, or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 20- membered) alicyclic or aromatic ring.
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or may be 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, preferably each independently represent hydrogen, deuterium, an unsubstituted (C6-C30)aryl group, an unsubstituted (5- to 30- membered)heteroaryl group, or an unsubstituted (C6-C30)arylamino group, and more preferably each independently represent hydrogen, an unsubstituted (C6-C20)aryl group, an unsubstituted (5- to 20- membered)heteroaryl group, or an unsubstituted (C6-C20)arylamino group.
a and b each independently represent an integer of 1 to 4, preferably each independently represent an integer of 1 to 2, where a or b is 2 or more, each of R1 and R2 may be the same or different.
According to one embodiment of the present invention, in formula 1 above, L1 represents an unsubstituted (C6-C30)arylene group; L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or an unsubstituted (5- to 30- membered)heteroarylene group; Ar1 to Ar4 each independently represent 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 only one of Y1 and Y2 exists, R31 to R33 each independently represent an unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl, or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring; R1 and R2 each independently represent hydrogen, deuterium, an unsubstituted (C6-C30)aryl group, an unsubstituted (5- to 30- membered)heteroaryl group, or an unsubstituted (C6-C30)arylamino group; and a and b each independently represent an integer of 1 to 2, where a or b is 2, each of R1 and R2 may be the same or different.
According to another embodiment of the present invention, in formula 1 above, L1 represents an unsubstituted (C6-C20)arylene group; L2 represents a single bond, a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, or an unsubstituted (5- to 20- membered)heteroarylene group; Ar1 to Ar4 each independently represent a (C6-C20)aryl group unsubstituted or substituted with deuterium, a cyano, a (C1-C6)alkyl group, or a (C6-C20)arylamino group; or a (5- to 20- membered)heteroaryl group unsubstituted or substituted with a (C6-C20)aryl group; Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists, R31 to R33 each independently represent an unsubstituted (C1-C6)alkyl, or a (C6-C20)aryl unsubstituted or substituted with deuterium, or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 20- membered) alicyclic or aromatic ring; R1 and R2 each independently represent hydrogen, an unsubstituted (C6-C20)aryl group, an unsubstituted (5- to 20- membered)heteroaryl group, or an unsubstituted (C6-C20)arylamino group; and a and b each independently represent an integer of 1 to 2, where a or b is 2, each of R1 and R2 may be the same or different.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkoxy, the substituted cycloalkyl, the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted alkylamino, the substituted arylamino, or the substituted alkylarylamino in L1, L2, Ar1 to Ar4, R31 to R33, R1, and R2 in formula 1, and R21 to R27, L4, M, and R41 to R43 in formulae 2 to 6 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 (5- to 30- membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (5- to 30- membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di-(C1-C30)alkylamino, a mono- or di-(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C6-C30)aryl(5- to 30- membered)heteroarylamino, 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 deuterium, a (C1-C6)alkyl, a (C6-C12)aryl, a di(C6-C12)arylamino, and a cyano.
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 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “(C2-C30)alkynyl” is meant to be a linear or branched alkyl 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 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.; “(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, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “5- to 30-membered heteroaryl(ene)” is an aryl 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; 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.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2013011949-appb-I000002
Figure PCTKR2013011949-appb-I000003
Figure PCTKR2013011949-appb-I000004
Figure PCTKR2013011949-appb-I000005
Figure PCTKR2013011949-appb-I000006
Figure PCTKR2013011949-appb-I000007
Figure PCTKR2013011949-appb-I000008
Figure PCTKR2013011949-appb-I000009
Figure PCTKR2013011949-appb-I000010
Figure PCTKR2013011949-appb-I000011
Figure PCTKR2013011949-appb-I000012
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 scheme 1.
[Reaction Scheme 1]
Figure PCTKR2013011949-appb-I000013
wherein L1, L2, Ar1 to Ar4, R1, R2, Y1, Y2, a and b 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 compound of formula 1.
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.
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. Preferably, the light-emitting layer 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 may be in the range of 1:99 to 99:1.
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 formulae 2 to 6 below is preferable in view of luminous efficiency.
Figure PCTKR2013011949-appb-I000014
Figure PCTKR2013011949-appb-I000015
Figure PCTKR2013011949-appb-I000016
Figure PCTKR2013011949-appb-I000017
Figure PCTKR2013011949-appb-I000018
wherein Cz represents the following structure;
Figure PCTKR2013011949-appb-I000019
X represents -O- or -S-;
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- 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;
Y3 and Y4 each independently represent -O-, -S-, -N(R41)- or -C(R42)(R43)-, provided that Y3 and Y4 do not simultaneously exist;
R41 to R43 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 R42 and R43 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 the second host material are as follows:
Figure PCTKR2013011949-appb-I000020
Figure PCTKR2013011949-appb-I000021
Figure PCTKR2013011949-appb-I000022
Figure PCTKR2013011949-appb-I000023
Figure PCTKR2013011949-appb-I000024
Figure PCTKR2013011949-appb-I000025
Figure PCTKR2013011949-appb-I000026
Figure PCTKR2013011949-appb-I000027
Figure PCTKR2013011949-appb-I000028
Figure PCTKR2013011949-appb-I000029
Figure PCTKR2013011949-appb-I000030
Figure PCTKR2013011949-appb-I000031
Figure PCTKR2013011949-appb-I000032
Figure PCTKR2013011949-appb-I000033
Figure PCTKR2013011949-appb-I000034
Figure PCTKR2013011949-appb-I000035
The dopant applied to the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant. These phosphorescent dopant materials are 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 7 to 9.
Figure PCTKR2013011949-appb-I000036
Figure PCTKR2013011949-appb-I000037
Figure PCTKR2013011949-appb-I000038
wherein L is selected from the following structures:
Figure PCTKR2013011949-appb-I000039
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;
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 may be the same or different; and
n represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2013011949-appb-I000040
Figure PCTKR2013011949-appb-I000041
Figure PCTKR2013011949-appb-I000042
Figure PCTKR2013011949-appb-I000043
Figure PCTKR2013011949-appb-I000044
Figure PCTKR2013011949-appb-I000045
Figure PCTKR2013011949-appb-I000046
Figure PCTKR2013011949-appb-I000047
Figure PCTKR2013011949-appb-I000048
Figure PCTKR2013011949-appb-I000049
Figure PCTKR2013011949-appb-I000050
Figure PCTKR2013011949-appb-I000051
Figure PCTKR2013011949-appb-I000052
Figure PCTKR2013011949-appb-I000053
Figure PCTKR2013011949-appb-I000054
Figure PCTKR2013011949-appb-I000055
Figure PCTKR2013011949-appb-I000056
In another embodiment of the present invention, a material for an organic electroluminescent device is provided. The material comprises the compound according to the present invention as a host material or a hole transport material.
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 material 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 at least one more light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
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, 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-1
Figure PCTKR2013011949-appb-I000057
Preparation of compound 1-2
After dissolving compound 1-1 (13.7 g, 53.3 mmol), 1,3,5-tribromobenzene (42.0 g, 133.4 mmol), CuI (1.0 g, 5.33 mmol), 1,10-phenanthroline (0.9 g, 5.33 mmol), and K2CO3 (8.0 g, 58.7 mmol) in dimethylformamide (DMF) 270 mL, the mixture was stirred at 190°C for 7 hours. After the reaction, H2O was slowly added to the mixture to complete the reaction, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and subjected to silica gel column chromatography to separate compound 1-2 (12.0 g, 47%).
Preparation of compound C-1
After dissolving compound 1-2 (8.0 g, 16.0 mmol), diphenylamine (6.5 g, 38.6 mmol), Pd2(dba)3 (0.58 g, 0.643 mmol), P(o-Tol)3 (0.78 g, 2.57 mmol), and NaOt-Bu (4.6 g, 48.2 mmol) in toluene 100 mL, the mixture was stirred at 120°C for 2 hours. After the reaction, H2O was slowly added to the mixture to complete the reaction, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and subjected to silica gel column chromatography to separate compound C-1 (8.3 g, 77%).
Data of physical properties: melting point 285°C, UV 366 nm (in toluene),
PL 480 nm (in toluene), MS/EIMS found 667.53
Example 2: Preparation of compound C-2
Figure PCTKR2013011949-appb-I000058
Preparation of compound 2-2
Compound 2-2 (6.5 g, 44%) was obtained by the same synthetic method for preparing compound 1-2 in Example 1, except for using compound 2-1 (8 g, 0.029 mol), 1,3,5-tribromobenzene (27.7 g, 0.087 mol), CuI (552 mg, 0.0029 mol), 1,10-phenanthroline (528 mg, 0.0029 mol), K2CO3 (4.4 g, 0.03 mol), and dimethylformamide (DMF) 200 mL.
Preparation of compound C-2
After mixing compound 2-2 (6 g, 0.0118 mol) and diphenylamine (6 g, 0.0354 mol) in a flask, Pd(OAc)2 (80 mg, 0.35 mmol), P(t-Bu)3 (0.5 mL, 0.0011 mol), NaOt-Bu (3.4 g, 0.0354 mol), and toluene 120 mL were added to the mixture and dissolved therein. The mixture was then stirred at 120°C for 10 hours. After the reaction, H2O was slowly added to the mixture to complete the reaction, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and subjected to silica gel column chromatography to separate compound C-2 (3.5 g, 43%).
Data of physical properties: melting point 240°C, UV 307 nm (in toluene),
PL 380 nm (in toluene), MS/EIMS found 683.7
Example 3: Preparation of compound C-3
Figure PCTKR2013011949-appb-I000059
Preparation of compound 3-2
After mixing compound 1-1 (30 g, 0.12 mol), 1-bromo-4-iodobenzene (73 g, 0.26 mol), CuI (11 g, 0.05 mol), potassium phosphate (74 g, 0.35 mol), and toluene 600 mL in a flask, the mixture was then stirred at 120°C for 3 hours. After completing the reaction, the mixture was filtered, washed with methanol, and subjected to column chromatography. The solvent was then removed under reduced pressure, and the remaining substance was recrystallized to obtain compound 3-2 (39 g, 82%).
Preparation of compound 3-3
After mixing compound 3-2 (25 g, 0.06 mol) and tetrahydrofuran 300 mL in a flask, n-butyl lithium (36 mL, 2.25 M) was slowly added to the mixture at -78°C while stirring the mixture under nitrogen atmosphere. The mixture was then stirred at -78°C for 1 hour, and trisisopropylborane (28 mL, 0.12 mol) was slowly added to the mixture at -78°C. The mixture was then heated to room temperature and reacted for 12 hours. After completing the reaction, the mixture was extracted with ethylacetate, and the obtained organic layer was dried with anhydrous magnesium sulfate and filtered. The solvent was then removed under reduced pressure, and the remaining substance was recrystallized to obtain compound 3-3 (20 g, 89%).
Preparation of compound 3-4
After mixing compound 3-3 (10 g, 0.02 mol), 1-bromo-3,5-dichlorobenzene (7.2 g, 0.03 mol), tetrakis(triphenylphosphine)palladium(O) (0.92 mg, 0.79 mmol), sodium carbonate (5.6 g, 0.05 mol), toluene 130 mL, ethanol 33 mL, and distilled water 33 mL in a flask, the mixture was stirred at 120°C for 12 hours. After completing the reaction, the mixture was extracted with ethylacetate, and the obtained organic layer was dried with anhydrous magnesium sulfate and filtered. The solvent was then removed under reduced pressure, and the remaining substance was subjected to column chromatography to separate compound 3-4 (4.4 g, 35%).
Preparation of compound C-3
After mixing compound 3-4 (4.4 g, 0.009 mol), diphenylamine (3.4 g, 0.02 mol), Pd(OAc)2 (0.4 g, 0.02 mol), s-phos (1.5 g, 3.7 mol), and xylene 100 mL, the mixture was stirred at 120°C for 3 hours. After completing the reaction, the mixture was filtered, washed with methanol, and subjected to column chromatography. The solvent was then removed under reduced pressure, and the remaining substance was recrystallized to obtain compound C-3 (2 g, 30%).
Data of physical properties: melting point 222°C, UV 376 nm (in toluene),
PL 413 nm (in toluene), MS/EIMS found 743.89
Example 4: Preparation of compound C-7
Figure PCTKR2013011949-appb-I000060
Compound C-7 (5.5 g, 78%) was obtained by the same synthetic method for preparing compound C-1 in Example 1, except using compound 1-2 (4.2 g, 8.55 mmol), N-phenylbiphenyl-4-amine (4.8 g, 19.6 mmol), Pd2(dba)3 (0.31 g, 0.34 mmol), P(o-Tol)3 (0.41 g, 1.36 mmol), NaOt-Bu (2.4 g, 25.6 mmol), and toluene 50 mL.
Data of physical properties: melting point 289°C, UV 368 nm (in toluene),
PL 382 nm (in toluene), MS/EIMS found 820.01
Example 5: Preparation of compound C-46
Figure PCTKR2013011949-appb-I000061
Preparation of compound 5-2
Compound 5-2 (4.1 g, 31%) was obtained by the same synthetic method for preparing compound 1-2 in Example 1, except using compound 5-1 (7.3 g, 25.76 mmol), 1,3,5-tribromobenzene (24.3 g, 77.28 mmol), CuI (0.5 g, 2.58 mmol), 1,10-phenanthroline (0.5 g, 2.58 mmol), K2CO3 (3.9 g, 28.34 mmol), and DMF 130 mL.
Preparation of compound C-46
Compound C-46 (3 g, 55%) was obtained by the same synthetic method for preparing compound C-1 in Example 1, except using compound 5-2 (4.1 g, 7.93 mmol), diphenylamine (3.2 g, 19.02 mmol), Pd2(dba)3 (0.3 g, 0.32 mmol), P(o-Tol)3 (0.4 g, 1.27 mmol), NaOt-Bu (2.3 g, 23.79 mmol), and toluene 80 mL.
Data of physical properties: melting point 247°C, UV 370 nm (in toluene),
PL 389 nm (in toluene), MS/EIMS found 693.5
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-46 according to the present invention 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-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-biscarbazole 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, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole 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.
The produced OLED device showed a green emission having a luminance of 1850 cd/m2 and a current density of 3.5 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-2; 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 as a host, introducing compound D-87 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 2840 cd/m2 and a current density of 21.8 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 evaporating compound C-7 in a thickness of 20 nm for a hole transport layer.
The produced OLED device showed a green emission having a luminance of 2880 cd/m2 and a current density of 5.9 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 evaporating compound C-1 in a thickness of 20 nm for a hole transport layer.
The produced OLED device showed a red emission having a luminance of 3500 cd/m2 and a current density of 28.7 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 10 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 7850 cd/m2 and a current density of 19.9 mA/cm2.
Figure PCTKR2013011949-appb-I000062
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 11 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 1480 cd/m2 and a current density of 14.5 mA/cm2.
Figure PCTKR2013011949-appb-I000063
Comparing Device Examples 1 and 3 with Comparative Example 1, and Device Examples 2 and 4 with Comparative Example 2, Device Examples 1 to 4 using the organic electroluminescent compound according to the present invention showed higher current efficiency. That is, the organic electroluminescent compound according to the present invention and the organic electroluminescent device comprising said compound have superior luminous characteristics than the conventional compounds and devices.
Therefore, 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 (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013011949-appb-I000064
    wherein
    L1 represents a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
    L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (5- to 30- membered)heteroarylene group;
    Ar1 to Ar4 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;
    Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists;
    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; or R32 and R33 may be linked to each other 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;
    R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or may be 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;
    the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P; and
    a and b each independently represent an integer of 1 to 4; where a or b is 2 or more, each of R1 and R2 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkoxy, the substituted cycloalkyl, the substituted alkylsilyl, the substituted arylsilyl, the substituted arylalkylsilyl, the substituted alkylamino, the substituted arylamino, or the substituted alkylarylamino in L1, L2, Ar1 to Ar4, R31 to R33, R1, and R2 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 (5- to 30- membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (5- to 30- membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono or di(C1-C30)alkylamino, a mono or di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C6-C30)aryl(5- to 30- membered)heteroarylamino, 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.
  3. The organic electroluminescent compound according to claim 1, wherein L1 represents an unsubstituted (C6-C30)arylene group;
    L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or an unsubstituted (5- to 30- membered)heteroarylene group;
    Ar1 to Ar4 each independently represent 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 only one of Y1 and Y2 exists;
    R31 to R33 each independently represent an unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 30- membered) alicyclic or aromatic ring;
    R1 and R2 each independently represent hydrogen, deuterium, an unsubstituted (C6-C30)aryl group, an unsubstituted (5- to 30- membered)heteroaryl group, or an unsubstituted (C6-C30)arylamino group; and
    a and b each independently represent an integer of 1 to 2.
  4. The organic electroluminescent compound according to claim 1, wherein L1 represents an unsubstituted (C6-C20)arylene group;
    L2 represents a single bond, a (C6-C20)arylene group unsubstituted or substituted with a (C1-C6)alkyl group, or an unsubstituted (5- to 20- membered)heteroarylene group;
    Ar1 to Ar4 each independently represent a (C6-C20)aryl group unsubstituted or substituted with deuterium, a cyano, a (C1-C6)alkyl group, or a (C6-C20)arylamino group; or a (5- to 20- membered)heteroaryl group unsubstituted or substituted with a (C6-C20)aryl group;
    Y1 and Y2 each independently represent -O-, -S-, -N(R31)-, or -C(R32)(R33)-, provided that only one of Y1 and Y2 exists;
    R31 to R33 each independently represent an unsubstituted (C1-C6)alkyl, or a (C6-C20)aryl unsubstituted or substituted with deuterium; or R32 and R33 may be linked to each other to form a mono- or polycyclic, (3- to 20- membered) alicyclic or aromatic ring;
    R1 and R2 each independently represent hydrogen, an unsubstituted (C6-C20)aryl group, an unsubstituted (5- to 20- membered)heteroaryl group, or an unsubstituted (C6-C20)arylamino group; and
    a and b each independently represent an integer of 1 to 2.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013011949-appb-I000065
    Figure PCTKR2013011949-appb-I000066
    Figure PCTKR2013011949-appb-I000067
    Figure PCTKR2013011949-appb-I000068
    Figure PCTKR2013011949-appb-I000069
    Figure PCTKR2013011949-appb-I000070
    Figure PCTKR2013011949-appb-I000071
    Figure PCTKR2013011949-appb-I000072
    Figure PCTKR2013011949-appb-I000073
    Figure PCTKR2013011949-appb-I000074
    Figure PCTKR2013011949-appb-I000075
  6. An organic electroluminescent device comprising the electroluminescent compound according to claim 1.
PCT/KR2013/011949 2012-12-21 2013-12-20 Novel organic electroluminescent compounds and an organic electroluminescent device comprising the same WO2014098518A1 (en)

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CN109928911A (en) * 2019-04-09 2019-06-25 江苏三月光电科技有限公司 A kind of organic compound containing triaryl amine and carbazole and its application
CN111440175A (en) * 2019-10-31 2020-07-24 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
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KR102579611B1 (en) * 2016-07-22 2023-09-20 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof

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WO2011132865A1 (en) * 2010-04-20 2011-10-27 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011136755A1 (en) * 2010-04-28 2011-11-03 Universal Display Corporation Depositing premixed materials

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WO2011132865A1 (en) * 2010-04-20 2011-10-27 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011136755A1 (en) * 2010-04-28 2011-11-03 Universal Display Corporation Depositing premixed materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014196805A1 (en) * 2013-06-03 2014-12-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
CN109928911A (en) * 2019-04-09 2019-06-25 江苏三月光电科技有限公司 A kind of organic compound containing triaryl amine and carbazole and its application
CN111440175A (en) * 2019-10-31 2020-07-24 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
CN111440175B (en) * 2019-10-31 2021-07-20 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
WO2023214651A1 (en) * 2022-05-02 2023-11-09 엘티소재주식회사 Heterocyclic compound and organic light-emitting element comprising same

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