KR102599292B1 - Hetero-cyclic compound and organic light emitting device using the same - Google Patents
Hetero-cyclic compound and organic light emitting device using the same Download PDFInfo
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- KR102599292B1 KR102599292B1 KR1020160162350A KR20160162350A KR102599292B1 KR 102599292 B1 KR102599292 B1 KR 102599292B1 KR 1020160162350 A KR1020160162350 A KR 1020160162350A KR 20160162350 A KR20160162350 A KR 20160162350A KR 102599292 B1 KR102599292 B1 KR 102599292B1
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- emitting device
- organic light
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims description 97
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000001072 heteroaryl group Chemical group 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
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- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 11
- 229910052805 deuterium Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
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- 125000000592 heterocycloalkyl group Chemical group 0.000 description 10
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
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- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
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- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 3
- COVQNTLWCVVPBW-UHFFFAOYSA-N CC(C)(C)C(=O)ON=C(C)C1=CC=C(Br)C=C1 Chemical compound CC(C)(C)C(=O)ON=C(C)C1=CC=C(Br)C=C1 COVQNTLWCVVPBW-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 125000005842 heteroatom Chemical group 0.000 description 3
- YGBMCLDVRUGXOV-UHFFFAOYSA-N n-[6-[6-chloro-5-[(4-fluorophenyl)sulfonylamino]pyridin-3-yl]-1,3-benzothiazol-2-yl]acetamide Chemical compound C1=C2SC(NC(=O)C)=NC2=CC=C1C(C=1)=CN=C(Cl)C=1NS(=O)(=O)C1=CC=C(F)C=C1 YGBMCLDVRUGXOV-UHFFFAOYSA-N 0.000 description 3
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- HDLLABDKPIMJMF-UHFFFAOYSA-N (1-phenylethylideneamino) 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)ON=C(C)C1=CC=CC=C1 HDLLABDKPIMJMF-UHFFFAOYSA-N 0.000 description 2
- MMJLKBCDTFTSCT-UHFFFAOYSA-N 2-(6-diphenylphosphorylnaphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(OB(OC1(C)C)C1=CC2=CC=C(C=C2C=C1)P(C1=CC=CC=C1)(C1=CC=CC=C1)=O)C MMJLKBCDTFTSCT-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 238000000434 field desorption mass spectrometry Methods 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- OZQLWSABIFMTOM-UHFFFAOYSA-N n-phenyldibenzofuran-4-amine Chemical compound C=1C=CC(C2=CC=CC=C2O2)=C2C=1NC1=CC=CC=C1 OZQLWSABIFMTOM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- FXEKHCWUVFWWBL-UHFFFAOYSA-N (3-chlorophenyl)-naphthalen-2-ylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=C3C=CC=CC3=CC=2)=C1 FXEKHCWUVFWWBL-UHFFFAOYSA-N 0.000 description 1
- RPYONPWJLGOFGD-UHFFFAOYSA-N (4-bromophenyl)-naphthalen-2-ylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=C(C=CC=C2)C2=C1 RPYONPWJLGOFGD-UHFFFAOYSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
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- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SPDPTFAJSFKAMT-UHFFFAOYSA-N 1-n-[4-[4-(n-[4-(3-methyl-n-(3-methylphenyl)anilino)phenyl]anilino)phenyl]phenyl]-4-n,4-n-bis(3-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 SPDPTFAJSFKAMT-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
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- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical class C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
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- ZSMRRZONCYIFNB-UHFFFAOYSA-N 6,11-dihydro-5h-benzo[b][1]benzazepine Chemical group C1CC2=CC=CC=C2NC2=CC=CC=C12 ZSMRRZONCYIFNB-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
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- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
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Abstract
본 출원은 유기 발광 소자의 수명, 효율, 전기 화학적 안정성 및 열적 안정성을 크게 향상시킬 수 있는 헤테로고리 화합물, 및 상기 헤테로고리 화합물이 유기 화합물층에 함유되어 있는 유기 발광 소자를 제공한다.The present application provides a heterocyclic compound that can significantly improve the lifespan, efficiency, electrochemical stability, and thermal stability of an organic light-emitting device, and an organic light-emitting device in which the heterocyclic compound is contained in an organic compound layer.
Description
본 출원은 헤테로고리 화합물 및 이를 이용한 유기 발광 소자에 관한 것이다.This application relates to heterocyclic compounds and organic light-emitting devices using the same.
전계 발광 소자는 자체 발광형 표시 소자의 일종으로서, 시야각이 넓고, 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다.Electroluminescent devices are a type of self-luminous display devices and have the advantages of a wide viewing angle, excellent contrast, and fast response speed.
유기 발광 소자는 2개의 전극 사이에 유기 박막을 배치시킨 구조를 가지고 있다. 이와 같은 구조의 유기 발광 소자에 전압이 인가되면, 2개의 전극으로부터 주입된 전자와 정공이 유기 박막에서 결합하여 쌍을 이룬 후 소멸하면서 빛을 발하게 된다. 상기 유기 박막은 필요에 따라 단층 또는 다층으로 구성될 수 있다.Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then disappear, emitting light. The organic thin film may be composed of a single layer or multiple layers, depending on need.
유기 박막의 재료는 필요에 따라 발광 기능을 가질 수 있다. 예컨대, 유기 박막 재료로는 그 자체가 단독으로 발광층을 구성할 수 있는 화합물이 사용될 수도 있고, 또는 호스트-도펀트계 발광층의 호스트 또는 도펀트 역할을 할 수 있는 화합물이 사용될 수도 있다. 그 외에도, 유기 박막의 재료로서, 정공 주입, 정공 수송, 전자 차단, 정공 차단, 전자 수송, 전자 주입 등의 역할을 수행할 수 있는 화합물이 사용될 수도 있다.The material of the organic thin film may have a light-emitting function as needed. For example, as an organic thin film material, a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used. In addition, as a material for the organic thin film, compounds that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.
유기 발광 소자의 성능, 수명 또는 효율을 향상시키기 위하여, 유기 박막의 재료의 개발이 지속적으로 요구되고 있다.In order to improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of organic thin film materials is continuously required.
유기 발광 소자에서 사용 가능한 물질에 요구되는 조건, 예컨대 적절한 에너지 준위, 전기 화학적 안정성 및 열적 안정성 등을 만족시킬 수 있으며, 치환기에 따라 유기 발광 소자에서 요구되는 다양한 역할을 할 수 있는 화학 구조를 갖는 화합물을 포함하는 유기 발광 소자에 대한 연구가 필요하다.A compound that can satisfy the conditions required for materials usable in organic light-emitting devices, such as appropriate energy level, electrochemical stability, and thermal stability, and has a chemical structure that can play various roles required in organic light-emitting devices depending on the substituent. Research on organic light-emitting devices containing is needed.
본 출원의 일 실시상태는, 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다:An exemplary embodiment of the present application provides a heterocyclic compound represented by the following formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 내지 R10 중 적어도 하나는 -(L1)m-(Z1)n으로 표시되고, 나머지는 수소; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 C2 내지 C60의 헤테로아릴기이며,At least one of R1 to R10 is represented by -(L1)m-(Z1)n, and the remainder are hydrogen; Substituted or unsubstituted C 6 to C 60 aryl group; Or a C 2 to C 60 heteroaryl group,
L1은 직접결합; 치환 또는 비치환된 C6 내지 C60의 아릴렌기; 또는 C2 내지 C60의 헤테로아릴렌기이고,L1 is direct bonding; Substituted or unsubstituted C 6 to C 60 arylene group; Or a C 2 to C 60 heteroarylene group,
Z1은 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -SiRR'R"; -P(=O)RR'; 및 C1 내지 C20의 알킬기, 치환 또는 비치환된 C6 내지 C60의 아릴기, 또는 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 아민기로 이루어진 군으로부터 선택되며,Z1 is a substituted or unsubstituted C 1 to C 60 alkyl group; Substituted or unsubstituted C 2 to C 60 alkenyl group; Substituted or unsubstituted C 2 to C 60 alkynyl group; Substituted or unsubstituted C 1 to C 60 alkoxy group; Substituted or unsubstituted C 3 to C 60 cycloalkyl group; Substituted or unsubstituted C 2 to C 60 heterocycloalkyl group; Substituted or unsubstituted C 6 to C 60 aryl group; Substituted or unsubstituted C 2 to C 60 heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 60 aryl group, or a C 2 to C 60 heteroaryl group, or is selected from the group consisting of unsubstituted amine groups,
m 및 n은 각각 독립적으로 1 내지 4의 정수이고,m and n are each independently integers from 1 to 4,
R11 내지 R17은 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; -CN; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -SiRR'R"; -P(=O)RR'; 및 C1 내지 C20의 알킬기, 치환 또는 비치환된 C6 내지 C60의 아릴기, 또는 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 아민기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기는 서로 결합하여 치환 또는 비치환된 지방족 또는 방향족 탄화수소 고리를 형성하며,R11 to R17 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C 1 to C 60 alkyl group; Substituted or unsubstituted C 2 to C 60 alkenyl group; Substituted or unsubstituted C 2 to C 60 alkynyl group; Substituted or unsubstituted C 1 to C 60 alkoxy group; Substituted or unsubstituted C 3 to C 60 cycloalkyl group; Substituted or unsubstituted C 2 to C 60 heterocycloalkyl group; Substituted or unsubstituted C 6 to C 60 aryl group; Substituted or unsubstituted C 2 to C 60 heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 60 aryl group, or a C 2 to C 60 heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R, R' 및 R"는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; -CN; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이다.R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C 1 to C 60 alkyl group; substituted or unsubstituted C 3 to C 60 cycloalkyl group ; A substituted or unsubstituted C 6 to C 60 aryl group; or a substituted or unsubstituted C 2 to C 60 heteroaryl group.
또한, 본 출원의 다른 실시상태는, 양극, 음극 및 상기 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상이 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, another embodiment of the present application is an organic light-emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, wherein at least one layer of the organic material layer is a heterocyclic compound represented by the formula (1) It provides an organic light emitting device comprising a.
본 출원의 일 실시상태에 따른 헤테로고리 화합물은 유기 발광 소자의 유기물층 재료로서 사용할 수 있다. 상기 헤테로고리 화합물은 유기 발광 소자에서 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층, 전하 생성층 등의 재료로서 사용될 수 있다. 특히, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자의 전자 수송층 또는 전하 생성층의 재료로서 사용될 수 있다. 또한, 상기 화학식 1로 표시되는 헤테로고리 화합물 유기 발광 소자에 사용하는 경우 소자의 구동전압을 낮추고, 광효율을 향상시키며, 화합물의 열적 안정성에 의하여 소자의 수명 특성을 향상시킬 수 있다.The heterocyclic compound according to an exemplary embodiment of the present application can be used as an organic layer material of an organic light-emitting device. The heterocyclic compound can be used as a material such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a charge generation layer in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 can be used as a material for the electron transport layer or charge generation layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Formula 1 is used in an organic light-emitting device, the driving voltage of the device can be lowered, luminous efficiency can be improved, and the lifespan characteristics of the device can be improved due to the thermal stability of the compound.
도 1 내지 도 4는 각각 본 출원의 일 실시상태에 따른 유기 발광 소자의 적층구조를 개략적으로 나타낸 도이다.1 to 4 are diagrams schematically showing the stacked structure of an organic light-emitting device according to an exemplary embodiment of the present application.
이하 본 출원에 대해서 자세히 설명한다.The present application will be described in detail below.
본 출원의 일 실시상태에 따른 헤테로고리 화합물은 상기 화학식 1로 표시되는 것을 특징으로 한다. 보다 구체적으로, 상기 화학식 1로 표시되는 헤테로고리 화합물은 상기와 같은 코어 구조 및 치환기의 구조적 특징에 의하여 유기 발광 소자의 유기물층 재료로 사용될 수 있다.The heterocyclic compound according to an exemplary embodiment of the present application is characterized by being represented by the above formula (1). More specifically, the heterocyclic compound represented by Formula 1 can be used as an organic layer material of an organic light-emitting device due to the structural characteristics of the core structure and substituents as described above.
본 출원의 일 실시상태에서, 상기 화학식 1의 m이 2 이상인 경우에는 2 이상의 L1은 서로 동일하거나 상이할 수 있다. 또한, 상기 화학식 1의 n이 2 이상인 경우에는 2 이상의 Z1은 서로 동일하거나 상이할 수 있다.In an exemplary embodiment of the present application, when m in Formula 1 is 2 or more, 2 or more L1 may be the same or different from each other. Additionally, when n in Formula 1 is 2 or more, 2 or more Z1 may be the same or different from each other.
본 출원의 일 실시상태에서, 상기 화학식 1의 R1 내지 R10 중 적어도 하나는 -(L1)m-(Z1)n으로 표시되고, 나머지는 수소일 수 있다.In an exemplary embodiment of the present application, at least one of R1 to R10 in Formula 1 may be represented by -(L1)m-(Z1)n, and the remainder may be hydrogen.
본 출원의 일 실시상태에서, 상기 화학식 1의 Z1은 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -P(=O)RR'; 및 C1 내지 C20의 알킬기, 치환 또는 비치환된 C6 내지 C60의 아릴기, 또는 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 아민기로 이루어진 군으로부터 선택될 수 있다.In an exemplary embodiment of the present application, Z1 of Formula 1 is a substituted or unsubstituted aryl group of C 6 to C 60 ; Substituted or unsubstituted C 2 to C 60 heteroaryl group; -P(=O)RR'; and a C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 60 aryl group, or a C 2 to C 60 heteroaryl group substituted or unsubstituted amine group.
본 출원의 일 실시상태에서, 상기 화학식 1의 R3, R4, R8 또는 R9는 -(L1)m-(Z1)n으로 표시될 수 있다.In an exemplary embodiment of the present application, R3, R4, R8, or R9 of Formula 1 may be expressed as -(L1)m-(Z1)n.
본 출원의 일 실시상태에서, 상기 화학식 1의 R3 및 R4 중 어느 하나와 R8 및 R9 중 어느 하나는 각각 독립적으로 -(L1)m-(Z1)n으로 표시될 수 있다.In an exemplary embodiment of the present application, any one of R3 and R4 and any one of R8 and R9 in Formula 1 may each independently be represented as -(L1)m-(Z1)n.
본 출원의 일 실시상태에서, 상기 화학식 1의 R11 내지 R17은 각각 독립적으로 수소 또는 중수소일 수 있다.In an exemplary embodiment of the present application, R11 to R17 in Formula 1 may each independently be hydrogen or deuterium.
본 출원의 일 실시상태에 있어서, 상기 화학식 1의 R, R' 및 R"는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 알킬기; 또는 치환 또는 비치환된 C6 내지 C60의 아릴기일 수 있다.In an exemplary embodiment of the present application, R, R' and R" in Formula 1 are the same or different from each other, and are each independently hydrogen; a substituted or unsubstituted C 1 to C 60 alkyl group; or a substituted or unsubstituted It may be an aryl group of C 6 to C 60 .
본 출원에 있어서, 상기 화학식 1의 치환기들을 보다 구체적으로 설명하면 하기와 같다.In the present application, the substituents of Formula 1 are described in more detail as follows.
본 명세서에 있어서, "치환 또는 비치환"이란 중수소; 할로겐기; -CN; C1 내지 C60의 알킬기; C2 내지 C60의 알케닐기; C2 내지 C60의 알키닐기; C3 내지 C60의 시클로알킬기; C2 내지 C60의 헤테로시클로알킬기; C6 내지 C60의 아릴기; C2 내지 C60의 헤테로아릴기; -SiRR'R"; -P(=O)RR'; C1 내지 C20의 알킬아민기; C6 내지 C60의 아릴아민기; 및 C2 내지 C60의 헤테로아릴아민기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환되거나, 상기 치환기 중 2 이상이 결합된 치환기로 치환 또는 비치환되거나, 상기 치환기 중에서 선택된 2 이상의 치환기가 연결된 치환기로 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다. 상기 추가의 치환기들은 추가로 더 치환될 수도 있다. 상기 R, R' 및 R"는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; -CN; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이다.In this specification, “substituted or unsubstituted” means deuterium; halogen group; -CN; C 1 to C 60 alkyl group; C 2 to C 60 alkenyl group; C 2 to C 60 alkynyl group; C 3 to C 60 cycloalkyl group; C 2 to C 60 heterocycloalkyl group; C 6 to C 60 aryl group; C 2 to C 60 heteroaryl group; -SiRR'R"; -P(=O)RR'; C 1 to C 20 alkylamine group; C 6 to C 60 arylamine group; and substituted or unsubstituted with one or more substituents selected from the group consisting of C 2 to C 60 heteroarylamine groups, or substituted or unsubstituted with substituents in which two or more of the substituents are combined, or where two or more substituents selected from the above substituents are connected. It means substituted or unsubstituted with a substituent. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected. The additional substituents may be further substituted. R, R' and R" are the same or different from each other, and each independently represents hydrogen; deuterium; -CN; substituted or unsubstituted C 1 to C 60 alkyl group; substituted or unsubstituted C 3 to C 60 cyclo An alkyl group; a substituted or unsubstituted C 6 to C 60 aryl group; or a substituted or unsubstituted C 2 to C 60 heteroaryl group.
본 출원의 일 실시상태에 따르면, 상기 "치환 또는 비치환"이란 중수소, 할로겐기, -CN, SiRR'R", P(=O)RR', C1 내지 C20의 직쇄 또는 분지쇄의 알킬기, C6 내지 C60의 아릴기, 및 C2 내지 C60의 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 것이며,According to an exemplary embodiment of the present application, the "substituted or unsubstituted" refers to deuterium, halogen group, -CN, SiRR'R", P(=O)RR', C 1 to C 20 straight or branched alkyl group. , C 6 to C 60 aryl group, and C 2 to C 60 heteroaryl group, which is substituted or unsubstituted with one or more substituents selected from the group consisting of,
상기 R, R' 및 R"는 서로 동일하거나 상이하며, 각각 독립적으로 수소; 중수소; -CN; 중수소, 할로겐기, -CN, C1 내지 C20의 알킬기, C6 내지 C60의 아릴기, 및 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 C1 내지 C60의 알킬기; 중수소, 할로겐, -CN, C1 내지 C20의 알킬기, C6 내지 C60의 아릴기, 및 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 중수소, 할로겐, -CN, C1 내지 C20의 알킬기, C6 내지 C60의 아릴기, 및 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 중수소, 할로겐, -CN, C1 내지 C20의 알킬기, C6 내지 C60의 아릴기, 및 C2 내지 C60의 헤테로아릴기로 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이다.R, R' and R" are the same or different from each other, and each independently represents hydrogen; deuterium; -CN; deuterium, halogen group, -CN, C 1 to C 20 alkyl group, C 6 to C 60 aryl group, and a C 1 to C 60 alkyl group substituted or unsubstituted with a C 2 to C 60 heteroaryl group; deuterium, halogen, -CN, C 1 to C 20 alkyl group, C 6 to C 60 aryl group, and C 2 C 3 to C 60 cycloalkyl group substituted or unsubstituted with C 60 heteroaryl group; deuterium, halogen, -CN, C 1 to C 20 alkyl group, C 6 to C 60 aryl group, and C 2 to C C 6 to C 60 aryl group substituted or unsubstituted with 60 heteroaryl group; or deuterium, halogen, -CN, C 1 to C 20 alkyl group, C 6 to C 60 aryl group, and C 2 to C 60 It is a C 2 to C 60 heteroaryl group that is substituted or unsubstituted with a heteroaryl group.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent. The position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and if two or more substituents are substituted. , two or more substituents may be the same or different from each other.
본 명세서에 있어서, 상기 할로겐은 불소, 염소, 브롬 또는 요오드일 수 있다.In the present specification, the halogen may be fluorine, chlorine, bromine, or iodine.
본 명세서에 있어서, 상기 알킬기는 탄소수 1 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알킬기의 탄소수는 1 내지 60, 구체적으로 1 내지 40, 더욱 구체적으로, 1 내지 20일 수 있다. 구체적인 예로는 메틸기, 에틸기, 프로필기, n-프로필기, 이소프로필기, 부틸기, n-부틸기, 이소부틸기, tert-부틸기, sec-부틸기, 1-메틸-부틸기, 1-에틸-부틸기, 펜틸기, n-펜틸기, 이소펜틸기, 네오펜틸기, tert-펜틸기, 헥실기, n-헥실기, 1-메틸펜틸기, 2-메틸펜틸기, 4-메틸-2-펜틸기, 3,3-디메틸부틸기, 2-에틸부틸기, 헵틸기, n-헵틸기, 1-메틸헥실기, 시클로펜틸메틸기, 시클로헥실메틸기, 옥틸기, n-옥틸기, tert-옥틸기, 1-메틸헵틸기, 2-에틸헥실기, 2-프로필펜틸기, n-노닐기, 2,2-디메틸헵틸기, 1-에틸-프로필기, 1,1-디메틸-프로필기, 이소헥실기, 2-메틸펜틸기, 4-메틸헥실기, 5-메틸헥실기 등이 있으나, 이에만 한정되는 것은 아니다.In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알케닐기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다. 구체적인 예로는 비닐기, 1-프로페닐기, 이소프로페닐기, 1-부테닐기, 2-부테닐기, 3-부테닐기, 1-펜테닐기, 2-펜테닐기, 3-펜테닐기, 3-메틸-1-부테닐기, 1,3-부타디에닐기, 알릴기, 1-페닐비닐-1-일기, 2-페닐비닐-1-일기, 2,2-디페닐비닐-1-일기, 2-페닐-2-(나프틸-1-일)비닐-1-일기, 2,2-비스(디페닐-1-일)비닐-1-일기, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited to these.
본 명세서에 있어서, 상기 알키닐기는 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알키닐기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다.In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.
본 명세서에 있어서, 상기 시클로알킬기는 탄소수 3 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 시클로알킬기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 시클로알킬기일 수도 있으나, 다른 종류의 고리기, 예컨대 헤테로시클로알킬기, 아릴기, 헤테로아릴기 등일 수도 있다. 상기 시클로알킬기의 탄소수는 3 내지 60, 구체적으로 3 내지 40, 더욱 구체적으로 5 내지 20일 수 있다. 구체적으로, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 3-메틸시클로펜틸기, 2,3-디메틸시클로펜틸기, 시클로헥실기, 3-메틸시클로헥실기, 4-메틸시클로헥실기, 2,3-디메틸시클로헥실기, 3,4,5-트리메틸시클로헥실기, 4-tert-부틸시클로헥실기, 시클로헵틸기, 시클로옥틸기 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is not limited thereto.
본 명세서에 있어서, 상기 헤테로시클로알킬기는 헤테로 원자로서 O, S, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 헤테로시클로알킬기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로시클로알킬기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 아릴기, 헤테로아릴기 등일 수도 있다. 상기 헤테로시클로알킬기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 20일 수 있다.In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.
본 명세서에 있어서, 상기 아릴기는 탄소수 6 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 아릴기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 아릴기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 헤테로시클로알킬기, 헤테로아릴기 등일 수도 있다. 상기 아릴기는 스피로기를 포함한다. 상기 아릴기의 탄소수는 6 내지 60, 구체적으로 6 내지 40, 더욱 구체적으로 6 내지 25일 수 있다. 상기 아릴기의 구체적인 예로는 페닐기, 비페닐기, 트리페닐기, 나프틸기, 안트릴기, 크라이세닐기, 페난트레닐기, 페릴레닐기, 플루오란테닐기, 트리페닐레닐기, 페날레닐기, 파이레닐기, 테트라세닐기, 펜타세닐기, 플루오레닐기, 인데닐기, 아세나프틸레닐기, 벤조플루오레닐기, 스피로비플루오레닐기, 2,3-디히드로-1H-인데닐기, 이들의 축합고리기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, heteroaryl group, etc. The aryl group includes a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, and pyrethyl group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed rings thereof These may include, but are not limited to this.
본 명세서에 있어서, 상기 스피로기는 스피로 구조를 포함하는 기로서, 탄소수 15 내지 60일 수 있다. 예컨대, 상기 스피로기는 플루오레닐기에 2,3-디히드로-1H-인덴기 또는 시클로헥산기가 스피로 결합된 구조를 포함할 수 있다. 구체적으로, 하기 스피로기는 하기 구조식의 기 중 어느 하나를 포함할 수 있다.In the present specification, the spiro group is a group containing a spiro structure and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the spiro group below may include any one of the groups of the structural formula below.
본 명세서에 있어서, 상기 헤테로아릴기는 헤테로 원자로서 S, O, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60인 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 상기 다환이란 헤테로아릴기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로아릴기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 헤테로시클로알킬기, 아릴기 등일 수도 있다. 상기 헤테로아릴기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 25일 수 있다. 상기 헤테로아릴기의 구체적인 예로는 피리딜기, 피롤릴기, 피리미딜기, 피리다지닐기, 푸라닐기, 티오펜기, 이미다졸릴기, 피라졸릴기, 옥사졸릴기, 이속사졸릴기, 티아졸릴기, 이소티아졸릴기, 트리아졸릴기, 푸라자닐기, 옥사디아졸릴기, 티아디아졸릴기, 디티아졸릴기, 테트라졸릴기, 파이라닐기, 티오파이라닐기, 디아지닐기, 옥사지닐기, 티아지닐기, 디옥시닐기, 트리아지닐기, 테트라지닐기, 퀴놀릴기, 이소퀴놀릴기, 퀴나졸리닐기, 이소퀴나졸리닐기, 퀴노졸리릴기, 나프티리딜기, 아크리디닐기, 페난트리디닐기, 이미다조피리디닐기, 디아자나프탈레닐기, 트리아자인덴기, 인돌릴기, 인돌리지닐기, 벤조티아졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티오펜기, 벤조푸란기, 디벤조티오펜기, 디벤조푸란기, 카바졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 페나지닐기, 디벤조실롤기, 스피로비(디벤조실롤), 디히드로페나지닐기, 페녹사지닐기, 페난트리딜기, 이미다조피리디닐기, 티에닐기, 인돌로[2,3-a]카바졸릴기, 인돌로[2,3-b]카바졸릴기, 인돌리닐기, 10,11-디히드로-디벤조[b,f]아제핀기, 9,10-디히드로아크리디닐기, 페난트라지닐기, 페노티아티아지닐기, 프탈라지닐기, 나프틸리디닐기, 페난트롤리닐기, 벤조[c][1,2,5]티아디아졸릴기, 5,10-디히드로디벤조[b,e][1,4]아자실리닐, 피라졸로[1,5-c]퀴나졸리닐기, 피리도[1,2-b]인다졸릴기, 피리도[1,2-a]이미다조[1,2-e]인돌리닐기, 5,11-디히드로인데노[1,2-b]카바졸릴기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.In the present specification, the heteroaryl group includes S, O, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, or aryl group. The carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, and thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyryl group, naphthyridyl group, acridinyl group, phenanthridide Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azacylinyl, pyrazolo[1,5-c]quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] Carbazolyl group, etc. may be mentioned, but it is not limited thereto.
본 명세서에 있어서, 상기 아민기는 모노알킬아민기; 모노아릴아민기; 모노헤테로아릴아민기; -NH2; 디알킬아민기; 디아릴아민기; 디헤테로아릴아민기; 알킬아릴아민기; 알킬헤테로아릴아민기; 및 아릴헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 상기 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 비페닐아민기, 디비페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, 페닐나프틸아민기, 디톨릴아민기, 페닐톨릴아민기, 트리페닐아민기, 비페닐나프틸아민기, 페닐비페닐아민기, 비페닐플루오레닐아민기, 페닐트리페닐레닐아민기, 비페닐트리페닐레닐아민기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH 2 ; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluorescein Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited to these.
본 명세서에 있어서, 아릴렌기는 아릴기에 결합 위치가 두 개 있는 것, 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다. 또한, 헤테로아릴렌기는 헤테로아릴기에 결합 위치가 두 개 있는 것, 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 헤테로아릴기의 설명이 적용될 수 있다.In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group. In addition, a heteroarylene group means that a heteroaryl group has two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.
본 출원에 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물 중 어느 하나로 표시될 수 있으나, 이에만 한정되는 것은 아니다.According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.
또한, 상기 화학식 1의 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기 발광 소자 제조시 사용되는 정공 주입층 물질, 정공 수송용 물질, 발광층 물질 및 전자 수송층 물질에 주로 사용되는 치환기를 상기 코어 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 합성할 수 있다.Additionally, by introducing various substituents into the structure of Formula 1, a compound having the unique properties of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, and electron transport layer materials used in the manufacture of organic light-emitting devices into the core structure, a material that satisfies the conditions required for each organic material layer can be synthesized. You can.
또한, 상기 화학식 1의 구조에 다양한 치환기를 도입함으로써 에너지 밴드갭을 미세하게 조절이 가능하게 하며, 한편으로 유기물 사이에서의 계면에서의 특성을 향상되게 하며 물질의 용도를 다양하게 할 수 있다.In addition, by introducing various substituents into the structure of Formula 1, the energy band gap can be finely adjusted, while the properties at the interface between organic materials can be improved and the uses of the material can be diversified.
한편, 상기 헤테로고리 화합물은 유리 전이 온도(Tg)가 높아 열적 안정성이 우수하다. 이러한 열적 안정성의 증가는 소자에 구동 안정성을 제공하는 중요한 요인이 된다.Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg) and has excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.
본 출원의 일 실시상태에 따른 헤테로고리 화합물은 다단계 화학반응으로 제조할 수 있다. 일부 중간체 화합물이 먼저 제조되고, 그 중간체 화합물들로부터 화학식 1의 화합물이 제조될 수 있다. 보다 구체적으로, 본 출원의 일 실시상태에 따른 헤테로고리 화합물은 후술하는 제조예를 기초로 제조될 수 있다.Heterocyclic compounds according to an exemplary embodiment of the present application can be produced through a multi-step chemical reaction. Some intermediate compounds are first prepared, and the compound of Formula 1 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application can be prepared based on the production example described later.
본 출원의 다른 실시상태는, 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 유기 발광 소자를 제공한다.Another embodiment of the present application provides an organic light-emitting device containing the heterocyclic compound represented by Formula 1 above.
본 출원의 일 실시상태에 따른 유기 발광 소자는 전술한 헤테로고리 화합물을 이용하여 한 층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기 발광 소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic light-emitting device according to an exemplary embodiment of the present application can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the heterocyclic compound described above.
상기 헤테로고리 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The heterocyclic compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
구체적으로, 본 출원의 일 실시상태에 따른 유기 발광 소자는, 양극, 음극 및 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함한다.Specifically, the organic light-emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 above. Contains compounds.
도 1 내지 3에 본 출원의 일 실시상태에 따른 유기 발광 소자의 전극과 유기물층의 적층 순서를 예시하였다. 그러나, 이들 도면에 의하여 본 출원의 범위가 한정될 것을 의도한 것은 아니며, 당 기술분야에 알려져 있는 유기 발광 소자의 구조가 본 출원에도 적용될 수 있다.1 to 3 illustrate the stacking order of electrodes and organic material layers of an organic light-emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light-emitting devices known in the art may also be applied to the present application.
도 1에 따르면, 기판(100) 상에 양극(200), 유기물층(300) 및 음극(400)이 순차적으로 적층된 유기 발광 소자가 도시된다. 그러나, 이와 같은 구조에만 한정되는 것은 아니고, 도 2와 같이, 기판 상에 음극, 유기물층 및 양극이 순차적으로 적층된 유기 발광 소자가 구현될 수도 있다.According to Figure 1, an organic light emitting device is shown in which an
도 3은 유기물층이 다층인 경우를 예시한 것이다. 도 3에 따른 유기 발광 소자는 정공 주입층(301), 정공 수송층(302), 발광층(303), 정공 저지층(304), 전자 수송층(305) 및 전자 주입층(306)을 포함한다. 그러나, 이와 같은 적층 구조에 의하여 본 출원의 범위가 한정되는 것은 아니며, 필요에 따라 발광층을 제외한 나머지 층은 생략될 수도 있고, 필요한 다른 기능층이 더 추가될 수 있다.Figure 3 illustrates the case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a
또한, 본 출원의 일 실시상태에 따른 유기 발광 소자는, 양극, 음극 및 양극과 음극 사이에 구비된 2 이상의 스택을 포함하고, 상기 2 이상의 스택은 각각 독립적으로 발광층을 포함하며, 상기 2 이상의 스택 간의 사이에는 전하 생성층을 포함하고, 상기 전하 생성층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함한다.In addition, the organic light emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and two or more stacks provided between the anode and the cathode, the two or more stacks each independently including a light emitting layer, and the two or more stacks It includes a charge generation layer between the livers, and the charge generation layer includes a heterocyclic compound represented by Formula 1 above.
또한, 본 출원의 일 실시상태에 따른 유기 발광 소자는, 양극, 상기 양극 상에 구비되고 제1 발광층을 포함하는 제1 스택, 상기 제1 스택 상에 구비되는 전하 생성층, 상기 전하 생성층 상에 구비되고 제2 발광층을 포함하는 제2 스택, 및 상기 제2 스택 상에 구비되는 음극을 포함한다. 이 때, 상기 전하 생성층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함할 수 있다. 또한, 상기 제1 스택 및 제2 스택은 각각 독립적으로 전술한 정공 주입층, 정공 수송층, 정공 저지층, 전자 수송층, 전자 주입층 등을 1종 이상 추가로 포함할 수 있다.In addition, an organic light emitting device according to an exemplary embodiment of the present application includes an anode, a first stack provided on the anode and including a first light emitting layer, a charge generation layer provided on the first stack, and a top layer on the charge generation layer. It includes a second stack provided on and including a second light emitting layer, and a cathode provided on the second stack. At this time, the charge generation layer may include a heterocyclic compound represented by Formula 1 above. In addition, the first stack and the second stack may each independently additionally include one or more of the above-described hole injection layer, hole transport layer, hole blocking layer, electron transport layer, and electron injection layer.
상기 전하 생성층은 N-타입 전하 생성층일 수 있고, 상기 전하 생성층은 화학식 1로 표시되는 헤테로고리 화합물 이외에 당 기술분야에 알려진 도펀트를 추가로 포함할 수 있다.The charge generation layer may be an N-type charge generation layer, and the charge generation layer may further include a dopant known in the art in addition to the heterocyclic compound represented by Formula 1.
본 출원의 일 실시상태에 따른 유기 발광 소자로서, 2-스텍 텐덤 구조의 유기 발광 소자를 하기 도 4에 개략적으로 나타내었다.As an organic light emitting device according to an exemplary embodiment of the present application, an organic light emitting device with a 2-stack tandem structure is schematically shown in FIG. 4 below.
이 때, 상기 도 4에 기재된 제 1 전자저지층, 제 1 정공저지층 및 제 2 정공저지층 등은 경우에 따라 생략될 수 있다.At this time, the first electron blocking layer, first hole blocking layer, and second hole blocking layer shown in FIG. 4 may be omitted depending on the case.
본 명세서에 따른 유기 발광 소자는 유기물층 중 1층 이상에 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic light-emitting device according to the present specification can be manufactured using materials and methods known in the art, except that at least one organic material layer contains a heterocyclic compound represented by Formula 1 above.
상기 화학식 1로 표시되는 헤테로고리 화합물은 단독으로 유기 발광 소자의 유기물층 중 1층 이상을 구성할 수 있다. 그러나, 필요에 따라 다른 물질과 혼합하여 유기물층을 구성할 수도 있다.The heterocyclic compound represented by Formula 1 may independently constitute one or more layers among the organic material layers of the organic light-emitting device. However, if necessary, it can be mixed with other materials to form an organic layer.
상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자에서 전하 생성층의 재료로서 사용될 수 있다.The heterocyclic compound represented by Formula 1 can be used as a material for a charge generation layer in an organic light-emitting device.
상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자에서 전자 수송층, 정공 저지층, 발광층의 재료 등으로 사용될 수 있다. 한 예로서, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자의 전자 수송층, 정공 수송층 또는 발광층의 재료로서 사용될 수 있다.The heterocyclic compound represented by Formula 1 can be used as a material for an electron transport layer, hole blocking layer, and light emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material for the electron transport layer, hole transport layer, or light emitting layer of an organic light-emitting device.
또한, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자에서 발광층의 재료로서 사용될 수 있다. 한 예로서, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자에서 발광층의 인광 호스트의 재료로서 사용될 수 있다.In addition, the heterocyclic compound represented by Formula 1 can be used as a material for the light-emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 can be used as a phosphorescent host material of the light-emitting layer in an organic light-emitting device.
본 출원의 일 실시상태에 따른 유기 발광 소자에 있어서, 상기 화학식 1의 헤테로고리 화합물 이외의 재료를 하기에 예시하지만, 이들은 예시를 위한 것일 뿐 본 출원의 범위를 한정하기 위한 것은 아니며, 당 기술분야에 공지된 재료들로 대체될 수 있다.In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application, and are not intended to limit the scope of the present application. It can be replaced with known materials.
양극 재료로는 비교적 일함수가 큰 재료들을 이용할 수 있으며, 투명 전도성 산화물, 금속 또는 전도성 고분자 등을 사용할 수 있다. 상기 양극 재료의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO : Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.As the anode material, materials with a relatively large work function can be used, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combination of metal and oxide such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline are included, but are not limited to these.
음극 재료로는 비교적 일함수가 낮은 재료들을 이용할 수 있으며, 금속, 금속 산화물 또는 전도성 고분자 등을 사용할 수 있다. 상기 음극 재료의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.As the cathode material, materials with a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO 2 /Al.
정공 주입 재료로는 공지된 정공 주입 재료를 이용할 수도 있는데, 예를 들면, 미국 특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 문헌 [Advanced Material, 6, p.677 (1994)]에 기재되어 있는 스타버스트형 아민 유도체류, 예컨대 트리스(4-카바조일-9-일페닐)아민(TCTA), 4,4',4"-트리[페닐(m-톨릴)아미노]트리페닐아민(m-MTDATA), 1,3,5-트리스[4-(3-메틸페닐페닐아미노)페닐]벤젠(m-MTDAPB), 용해성이 있는 전도성 고분자인 폴리아닐린/도데실벤젠술폰산(Polyaniline/Dodecylbenzenesulfonic acid) 또는 폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)(Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), 폴리아닐린/캠퍼술폰산(Polyaniline/Camphor sulfonic acid) 또는 폴리아닐린/폴리(4-스티렌술포네이트)(Polyaniline/Poly(4-styrene-sulfonate))등을 사용할 수 있다.As the hole injection material, known hole injection materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). Starburst type amine derivatives such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), Polyaniline/Camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.
정공 수송 재료로는 피라졸린 유도체, 아릴아민계 유도체, 스틸벤 유도체, 트리페닐디아민 유도체 등이 사용될 수 있으며, 저분자 또는 고분자 재료가 사용될 수도 있다.As hole transport materials, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular or high molecular materials may also be used.
전자 수송 재료로는 옥사디아졸 유도체, 안트라퀴노디메탄 및 이의 유도체, 벤조퀴논 및 이의 유도체, 나프토퀴논 및 이의 유도체, 안트라퀴논 및 이의 유도체, 테트라시아노안트라퀴노디메탄 및 이의 유도체, 플루오레논 유도체, 디페닐디시아노에틸렌 및 이의 유도체, 디페노퀴논 유도체, 8-히드록시퀴놀린 및 이의 유도체의 금속 착체 등이 사용될 수 있으며, 저분자 물질 뿐만 아니라 고분자 물질이 사용될 수도 있다.Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and not only low molecular substances but also high molecular substances may be used.
전자 주입 재료로는 예를 들어, LiF가 당업계 대표적으로 사용되나, 본 출원이 이에 한정되는 것은 아니다.For example, LiF is typically used as an electron injection material in the industry, but the present application is not limited thereto.
발광 재료로는 적색, 녹색 또는 청색 발광재료가 사용될 수 있으며, 필요한 경우, 2 이상의 발광 재료를 혼합하여 사용할 수 있다. 이 때, 2 이상의 발광 재료를 개별적인 공급원으로 증착하여 사용하거나, 예비혼합하여 하나의 공급원으로 증착하여 사용할 수 있다. 또한, 발광 재료로서 형광 재료를 사용할 수도 있으나, 인광 재료로서 사용할 수도 있다. 발광 재료로는 단독으로서 양극과 음극으로부터 각각 주입된 정공과 전자를 결합하여 발광시키는 재료가 사용될 수도 있으나, 호스트 재료와 도펀트 재료가 함께 발광에 관여하는 재료들이 사용될 수도 있다.Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed. At this time, two or more light emitting materials can be deposited and used from individual sources, or they can be premixed and deposited from a single source. Additionally, a fluorescent material can be used as a light-emitting material, but it can also be used as a phosphorescent material. As a light-emitting material, a material that emits light by combining holes and electrons injected from an anode and a cathode, respectively, may be used, but materials that participate in light emission together with a host material and a dopant material may also be used.
발광 재료의 호스트를 혼합하여 사용하는 경우에는, 동일 계열의 호스트를 혼합하여 사용할 수도 있고, 다른 계열의 호스트를 혼합하여 사용할 수도 있다. 예를 들어, n 타입 호스트 재료 또는 P 타입 호스트 재료 중 어느 두 종류 이상의 재료를 선택하여 발광층의 호스트 재료로 사용할 수 있다.When using a mixture of hosts of a light emitting material, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, any two or more types of materials, such as an n-type host material or a P-type host material, can be selected and used as a host material for the light-emitting layer.
본 출원의 일 실시상태에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to an exemplary embodiment of the present application may be a front emitting type, a rear emitting type, or a double-sided emitting type depending on the material used.
본 출원의 일 실시상태에 따른 헤테로고리 화합물은 유기 태양 전지, 유기 감광체, 유기 트랜지스터 등을 비롯한 유기 전자 소자에서도 유기 발광 소자에 적용되는 것과 유사한 원리로 작용할 수 있다.The heterocyclic compound according to an exemplary embodiment of the present application may function in organic electronic devices, including organic solar cells, organic photoreceptors, organic transistors, etc., on a principle similar to that applied to organic light-emitting devices.
이하에서, 실시예를 통하여 본 명세서를 더욱 상세하게 설명하지만, 이들은 본 출원을 예시하기 위한 것일 뿐, 본 출원 범위를 한정하기 위한 것은 아니다.Below, the present specification is described in more detail through examples, but these are only for illustrating the present application and are not intended to limit the scope of the present application.
<< 실시예Example >>
<< 제조예Manufacturing example 1> 화합물 1의 제조 1> Preparation of Compound 1
1) 화합물 1-1의 제조1) Preparation of compound 1-1
naphthalen-2-yl(phenyl)methanone(60g, 258.31mmol, 1eq), hydroxylamine hydrochloride(44.9g, 645.78mmol, 2.5eq), KOAc(63.4g, 645.78mmol, 2.5eq)에 methanol(600ml)를 넣고 60℃에서 40분간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(600ml)에 녹인 후 triethylamine(78.4g, 774.9mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(62.3g, 516.6mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 30분간 교반하였다.Add methanol (600ml) to naphthalen-2-yl(phenyl)methanone (60g, 258.31mmol, 1eq), hydroxylamine hydrochloride (44.9g, 645.78mmol, 2.5eq), and KOAc (63.4g, 645.78mmol, 2.5eq). It was stirred at ℃ for 40 minutes. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (600ml), and triethylamine (78.4g, 774.9mmol, 3eq) was added at 0°C. Pivaloyl chloride (62.3g, 516.6mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 30 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다.After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10 EA:Hex=1:8), 화합물 1-1 71.9g을 84%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10 EA:Hex=1:8), 71.9g of compound 1-1 was obtained with a yield of 84%.
2) 화합물 1-2의 제조2) Preparation of Compound 1-2
화합물 1-1 (70g, 211.22mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime(62.98g, 211.22mmol, 1eq), diacetoxypalladium(4.7g, 21.1mmol, 0.1eq)를 toluene(700ml)에 넣고 150℃에서 24시간 교반하였다.Compound 1-1 (70g, 211.22mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime (62.98g, 211.22mmol, 1eq), diacetoxypalladium (4.7g, 21.1mmol, 0.1eq) was added to toluene (700ml) and stirred at 150°C for 24 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다.After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10), 화합물 1-2 56g을 65%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10), 56g of compound 1-2 was obtained with a yield of 65%.
3) 화합물 1-3의 제조3) Preparation of Compound 1-3
화합물 1-2 (56g, 137.3mmol, 1eq), Bis(pinacolato)diboron(52.3g, 206.0mmol, 1.5eq)을 1,4-dioxane(280ml)에 녹인 후 (N2 condition) PdCl2(dppf)(5.03g, 6.87mmol, 0.05eq)과 KOAc(40.42g, 411.9mmol, 3eq)을 넣고 100℃에서 6h 교반하였다.Compound 1-2 (56g, 137.3mmol, 1eq) and Bis(pinacolato)diboron (52.3g, 206.0mmol, 1.5eq) were dissolved in 1,4-dioxane (280ml) (N 2 condition) and then dissolved in PdCl 2 (dppf). (5.03g, 6.87mmol, 0.05eq) and KOAc (40.42g, 411.9mmol, 3eq) were added and stirred at 100°C for 6h.
MC와 물로 추출한 후 유기층을 무수 Na2SO4로 건조 후 실리카겔 필터하였다.After extraction with MC and water, the organic layer was dried over anhydrous Na 2 SO 4 and filtered with silica gel.
MC/MeOH로 precipitation 하였다. 침전을 여과하여 화합물 1-3 56.5g을 90%의 수율로 얻었다.Precipitation was performed with MC/MeOH. The precipitate was filtered to obtain 56.5 g of compound 1-3 with a yield of 90%.
4) 화합물 1의 제조4) Preparation of Compound 1
화합물 1-3 (10g, 21.86mmol, 1eq)과 2-bromo-1,10-phenanthroline(5.66g, 21.86mmol, 1eq)을 Tol 100ml와 EtOH 20ml, H2O 20ml에 녹인 후 (N2 condition) Pd(PPh3)4(1.26g, 1.09mmol, 0.05eq)과 K2CO3(6.04g, 43.72mmol, 2eq)을 넣고 15h 환류 교반하였다.Compound 1-3 (10g, 21.86mmol, 1eq) and 2-bromo-1,10-phenanthroline (5.66g, 21.86mmol, 1eq) were dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H 2 O (N 2 condition). Pd(PPh 3 ) 4 (1.26g, 1.09mmol, 0.05eq) and K 2 CO 3 (6.04g, 43.72mmol, 2eq) were added and stirred under reflux for 15h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 MC/MeOH precipitation 하였다.After silica gel filter (Silisca-gel filter), MC/MeOH precipitation was performed.
soxhlet하여 화합물 1 7.8g을 70%의 수율로 얻었다.By soxhlet, 7.8 g of Compound 1 was obtained with a yield of 70%.
상기 제조예 1에서 2-bromo-1,10-phenanthroline 대신 하기 표 1의 중간체 A를 사용하여 동일한 방법으로 제조하여 목적화합물 A를 합성하였다.Target compound A was synthesized in the same manner as in Preparation Example 1 using Intermediate A of Table 1 instead of 2-bromo-1,10-phenanthroline.
[표 1][Table 1]
<< 제조예Manufacturing example 2> 화합물 93의 제조 2> Preparation of compound 93
1) 화합물 93-1의 제조1) Preparation of compound 93-1
naphthalen-2-yl(phenyl)methanone(60g, 258.31mmol, 1eq), hydroxylamine hydrochloride(44.9g, 645.78mmol, 2.5eq), KOAc(63.4g, 645.78mmol, 2.5eq)에 methanol(600ml)를 넣고 60℃에서 40분간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(600ml)에 녹인 후 triethylamine(78.4g, 774.9mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(62.3g, 516.6mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 30분간 교반하였다. Add methanol (600ml) to naphthalen-2-yl(phenyl)methanone (60g, 258.31mmol, 1eq), hydroxylamine hydrochloride (44.9g, 645.78mmol, 2.5eq), and KOAc (63.4g, 645.78mmol, 2.5eq). It was stirred at ℃ for 40 minutes. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (600ml), and triethylamine (78.4g, 774.9mmol, 3eq) was added at 0°C. Pivaloyl chloride (62.3g, 516.6mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 30 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10 EA:Hex=1:8), 화합물 93-1 71.9g을 84%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10 EA:Hex=1:8), 71.9g of compound 93-1 was obtained with a yield of 84%.
2) 화합물 93-2의 제조2) Preparation of compound 93-2
화합물 93-1 (70g, 211.22mmol, 1eq), 1-(3-bromophenyl)ethan-1-one O-pivaloyl oxime(62.98g, 211.22mmol, 1eq), diacetoxypalladium(4.7g, 21.1mmol, 0.1eq)를 toluene(700ml)에 넣고 150℃에서 18시간 교반하였다. Compound 93-1 (70g, 211.22mmol, 1eq), 1-(3-bromophenyl)ethan-1-one O-pivaloyl oxime (62.98g, 211.22mmol, 1eq), diacetoxypalladium (4.7g, 21.1mmol, 0.1eq) was added to toluene (700ml) and stirred at 150°C for 18 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10), 화합물 93-2 60.7g을 70%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10), 60.7 g of compound 93-2 was obtained with a yield of 70%.
3) 화합물 93-3의 제조3) Preparation of compound 93-3
화합물 93-2 (30g, 73.12mmol, 1eq), Bis(pinacolato)diboron(27.9g, 109.68mmol, 1.5eq)을 1,4-dioxane(150ml)에 녹인 후 (N2 condition) PdCl2(dppf)(2.68g, 3.66mmol, 0.05eq)과 KOAc(21.53g, 219.36mmol, 3eq)을 넣고 100℃에서 8h 교반하였다.Compound 93-2 (30g, 73.12mmol, 1eq) and Bis(pinacolato)diboron (27.9g, 109.68mmol, 1.5eq) were dissolved in 1,4-dioxane (150ml) (N 2 condition) and then dissolved in PdCl 2 (dppf). (2.68g, 3.66mmol, 0.05eq) and KOAc (21.53g, 219.36mmol, 3eq) were added and stirred at 100°C for 8h.
MC와 물로 추출한 후 유기층을 무수 Na2SO4로 건조 후 실리카겔 필터하였다.After extraction with MC and water, the organic layer was dried over anhydrous Na 2 SO 4 and filtered with silica gel.
MC/MeOH로 precipitation 하였다. 침전을 여과하여 화합물 93-3 28.8g을 86%의 수율로 얻었다.Precipitation was performed with MC/MeOH. The precipitate was filtered to obtain 28.8 g of compound 93-3 with a yield of 86%.
4) 화합물 93의 제조4) Preparation of compound 93
화합물 93-3 (10g, 21.86mmol, 1eq)과 2-bromo-1,10-phenanthroline(5.66g, 21.86mmol, 1eq)을 Tol 100ml와 EtOH 20ml, H2O 20ml에 녹인 후 (N2 condition) Pd(PPh3)4(1.26g, 1.09mmol, 0.05eq)과 K2CO3(6.04g, 43.72mmol, 2eq)을 넣고 17h 환류 교반하였다.Compound 93-3 (10g, 21.86mmol, 1eq) and 2-bromo-1,10-phenanthroline (5.66g, 21.86mmol, 1eq) were dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H 2 O (N 2 condition). Pd(PPh 3 ) 4 (1.26g, 1.09mmol, 0.05eq) and K 2 CO 3 (6.04g, 43.72mmol, 2eq) were added and stirred under reflux for 17h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 MC/MeOH precipitation 하였다.After silica gel filter (Silisca-gel filter), MC/MeOH precipitation was performed.
soxhlet하여 화합물 93 9.02g을 81%의 수율로 얻었다.By soxhlet, 9.02 g of compound 93 was obtained with a yield of 81%.
상기 제조예 2에서 2-bromo-1,10-phenanthroline 대신 하기 표 2의 중간체 B를 사용하여 동일한 방법으로 제조하여 목적화합물 B를 합성하였다.Target compound B was synthesized in the same manner as in Preparation Example 2 using Intermediate B of Table 2 instead of 2-bromo-1,10-phenanthroline.
[표 2][Table 2]
<< 제조예Manufacturing example 3> 화합물 185의 제조 3> Preparation of compound 185
1) 화합물 185-1의 제조1) Preparation of compound 185-1
(4-bromophenyl)(naphthalen-2-yl)methanone(30g, 96.41mmol, 1eq), hydroxylamine hydrochloride(16.7g, 241.03mmol, 2.5eq), KOAc(23.7g, 241.03mmol, 2.5eq)에 methanol(300ml)를 넣고 60℃에서 30분간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(400ml)에 녹인 후 triethylamine(29.3g, 289.23mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(23.3g, 192.8mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 20분간 교반하였다. (4-bromophenyl)(naphthalen-2-yl)methanone (30g, 96.41mmol, 1eq), hydroxylamine hydrochloride (16.7g, 241.03mmol, 2.5eq), KOAc (23.7g, 241.03mmol, 2.5eq) and methanol (300ml). ) was added and stirred at 60°C for 30 minutes. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (400ml) and triethylamine (29.3g, 289.23mmol, 3eq) was added at 0°C. Pivaloyl chloride (23.3g, 192.8mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 20 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10 EA:Hex=1:8), 화합물 185-1 28.9g을 73%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10 EA:Hex=1:8), 28.9g of compound 185-1 was obtained with a yield of 73%.
2) 화합물 185-2의 제조2) Preparation of compound 185-2
화합물 185-1 (20g, 48.74mmol, 1eq), 1-phenylethan-1-one O-pivaloyl oxime (10.7g, 48.74mmol, 1eq), diacetoxypalladium(1.09g, 4.87mmol, 0.1eq)를 toluene(200ml)에 넣고 150℃에서 15시간 교반하였다. Compound 185-1 (20g, 48.74mmol, 1eq), 1-phenylethan-1-one O-pivaloyl oxime (10.7g, 48.74mmol, 1eq), and diacetoxypalladium (1.09g, 4.87mmol, 0.1eq) were mixed with toluene (200ml). and stirred at 150°C for 15 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10), 화합물 185-2 13.6g을 68%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10), 13.6 g of compound 185-2 was obtained with a yield of 68%.
3) 화합물 185-3의 제조3) Preparation of compound 185-3
화합물 185-2 (13.6g, 33.14mmol, 1eq), Bis(pinacolato)diboron(12.6g, 49.71mmol, 1.5eq)을 1,4-dioxane(70ml)에 녹인 후 (N2 condition) PdCl2(dppf)(1.21g, 1.66mmol, 0.05eq)과 KOAc(9.76g, 99.42mmol, 3eq)을 넣고 100℃에서 5h 교반하였다.Compound 185-2 (13.6g, 33.14mmol, 1eq) and Bis(pinacolato)diboron (12.6g, 49.71mmol, 1.5eq) were dissolved in 1,4-dioxane (70ml) (N 2 condition) and PdCl 2 (dppf). ) (1.21g, 1.66mmol, 0.05eq) and KOAc (9.76g, 99.42mmol, 3eq) were added and stirred at 100°C for 5h.
MC와 물로 추출한 후 유기층을 무수 Na2SO4로 건조 후 실리카겔 필터하였다.After extraction with MC and water, the organic layer was dried over anhydrous Na 2 SO 4 and filtered with silica gel.
MC/MeOH로 precipitation 하였다. 침전을 여과하여 화합물 185-3 13.95g을 92%의 수율로 얻었다.Precipitation was performed with MC/MeOH. The precipitate was filtered to obtain 13.95 g of compound 185-3 with a yield of 92%.
4) 화합물 185의 제조4) Preparation of compound 185
화합물 185-3 (13.95g, 30.49mmol, 1eq)과 2-bromo-1,10-phenanthroline(7.9g, 30.49mmol, 1eq)을 Tol 150ml와 EtOH 30ml, H2O 30ml에 녹인 후 (N2 condition) Pd(PPh3)4(1.76g, 1.52mmol, 0.05eq)과 K2CO3(8.43g, 60.98mmol, 2eq)을 넣고 10h 환류 교반하였다.Compound 185-3 (13.95g, 30.49mmol, 1eq) and 2-bromo-1,10-phenanthroline (7.9g, 30.49mmol, 1eq) were dissolved in 150ml of Tol, 30ml of EtOH, and 30ml of H 2 O (N 2 condition). ) Pd(PPh 3 ) 4 (1.76g, 1.52mmol, 0.05eq) and K 2 CO 3 (8.43g, 60.98mmol, 2eq) were added and stirred under reflux for 10h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 MC/MeOH precipitation 하였다.After silica gel filter (Silisca-gel filter), MC/MeOH precipitation was performed.
soxhlet하여 화합물 185 13.98g을 90%의 수율로 얻었다.By soxhlet, 13.98 g of compound 185 was obtained with a yield of 90%.
상기 제조예 3에서 2-bromo-1,10-phenanthroline 대신 하기 표 3의 중간체 C를 사용하여 동일한 방법으로 제조하여 목적화합물 C를 합성하였다.The target compound C was synthesized in the same manner as in Preparation Example 3 using Intermediate C of Table 3 instead of 2-bromo-1,10-phenanthroline.
[표 3][Table 3]
<< 제조예Manufacturing example 4> 화합물 277의 제조 4> Preparation of Compound 277
1) 화합물 277-1의 제조1) Preparation of compound 277-1
(3-bromophenyl)(naphthalen-2-yl)methanone(30g, 96.41mmol, 1eq), hydroxylamine hydrochloride(16.7g, 241.03mmol, 2.5eq), KOAc(23.7g, 241.03mmol, 2.5eq)에 methanol(300ml)를 넣고 60℃에서 30분간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(400ml)에 녹인 후 triethylamine(29.3g, 289.23mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(23.3g, 192.8mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 20분간 교반하였다. (3-bromophenyl)(naphthalen-2-yl)methanone (30g, 96.41mmol, 1eq), hydroxylamine hydrochloride (16.7g, 241.03mmol, 2.5eq), KOAc (23.7g, 241.03mmol, 2.5eq) and methanol (300ml). ) was added and stirred at 60°C for 30 minutes. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (400ml) and triethylamine (29.3g, 289.23mmol, 3eq) was added at 0°C. Pivaloyl chloride (23.3g, 192.8mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 20 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10 EA:Hex=1:8), 화합물 277-1 26.9g을 68%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10 EA:Hex=1:8), 26.9g of compound 277-1 was obtained with a yield of 68%.
2) 화합물 277-2의 제조2) Preparation of compound 277-2
화합물 277-1 (20g, 48.74mmol, 1eq), 1-phenylethan-1-one O-pivaloyl oxime (10.7g, 48.74mmol, 1eq), diacetoxypalladium(1.09g, 4.87mmol, 0.1eq)를 toluene(200ml)에 넣고 150℃에서 8시간 교반하였다. Compound 277-1 (20g, 48.74mmol, 1eq), 1-phenylethan-1-one O-pivaloyl oxime (10.7g, 48.74mmol, 1eq), and diacetoxypalladium (1.09g, 4.87mmol, 0.1eq) were mixed with toluene (200ml). and stirred at 150°C for 8 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10), 화합물 277-2 16g을 80%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10), 16g of compound 277-2 was obtained with a yield of 80%.
3) 화합물 277-3의 제조3) Preparation of compound 277-3
화합물 277-2 (16g, 38.99mmol, 1eq), Bis(pinacolato)diboron(14.85g, 58.49mmol, 1.5eq)을 1,4-dioxane(80ml)에 녹인 후 (N2 condition) PdCl2(dppf)(1.43g, 1.95mmol, 0.05eq)과 KOAc(11.48g, 116.97mmol, 3eq)을 넣고 100에서 3h 교반하였다.Compound 277-2 (16g, 38.99mmol, 1eq) and Bis(pinacolato)diboron (14.85g, 58.49mmol, 1.5eq) were dissolved in 1,4-dioxane (80ml) (N 2 condition) and then dissolved in PdCl 2 (dppf). (1.43g, 1.95mmol, 0.05eq) and KOAc (11.48g, 116.97mmol, 3eq) were added and stirred at 100°C for 3h.
MC와 물로 추출한 후 유기층을 무수 Na2SO4로 건조 후 실리카겔 필터하였다.After extraction with MC and water, the organic layer was dried over anhydrous Na 2 SO 4 and filtered with silica gel.
MC/MeOH로 precipitation 하였다. 침전을 여과하여 화합물 277-3 16.05g을 90%의 수율로 얻었다.Precipitation was performed with MC/MeOH. The precipitate was filtered to obtain 16.05 g of compound 277-3 with a yield of 90%.
4) 화합물 277의 제조4) Preparation of compound 277
화합물 277-3 (16.05g, 35.09mmol, 1eq)과 2-bromo-1,10-phenanthroline(9.09g, 35.09mmol, 1eq)을 Tol 175ml와 EtOH 35ml, H2O 35ml에 녹인 후 (N2 condition) Pd(PPh3)4(2.02g, 1.75mmol, 0.05eq)과 K2CO3(9.7g, 70.18mmol, 2eq)을 넣고 18h 환류 교반하였다.Compound 277-3 (16.05g, 35.09mmol, 1eq) and 2-bromo-1,10-phenanthroline (9.09g, 35.09mmol, 1eq) were dissolved in 175ml of Tol, 35ml of EtOH, and 35ml of H 2 O (N 2 condition). ) Pd(PPh 3 ) 4 (2.02g, 1.75mmol, 0.05eq) and K 2 CO 3 (9.7g, 70.18mmol, 2eq) were added and stirred under reflux for 18h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 MC/MeOH precipitation 하였다.After silica gel filter (Silisca-gel filter), MC/MeOH precipitation was performed.
soxhlet하여 화합물 277 13.06g을 73%의 수율로 얻었다.By soxhlet, 13.06 g of compound 277 was obtained with a yield of 73%.
상기 제조예 4에서 2-bromo-1,10-phenanthroline 대신 하기 표 4의 중간체 D를 사용하여 동일한 방법으로 제조하여 목적화합물 D를 합성하였다.The target compound D was synthesized in the same manner as in Preparation Example 4 using Intermediate D of Table 4 instead of 2-bromo-1,10-phenanthroline.
[표 4][Table 4]
<< 제조예Manufacturing example 5> 화합물 82의 제조 5> Preparation of Compound 82
1) 화합물 82-1의 제조1) Preparation of compound 82-1
naphthalen-2-yl(phenyl)methanone(60g, 258.31mmol, 1eq), hydroxylamine hydrochloride(44.9g, 645.78mmol, 2.5eq), KOAc(63.4g, 645.78mmol, 2.5eq)에 methanol(600ml)를 넣고 60℃에서 40분간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(600ml)에 녹인 후 triethylamine(78.4g, 774.9mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(62.3g, 516.6mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 30분간 교반하였다. Add methanol (600ml) to naphthalen-2-yl(phenyl)methanone (60g, 258.31mmol, 1eq), hydroxylamine hydrochloride (44.9g, 645.78mmol, 2.5eq), and KOAc (63.4g, 645.78mmol, 2.5eq). It was stirred at ℃ for 40 minutes. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (600ml), and triethylamine (78.4g, 774.9mmol, 3eq) was added at 0°C. Pivaloyl chloride (62.3g, 516.6mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 30 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10 EA:Hex=1:8), 화합물 82-1 71.9g을 84%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10 EA:Hex=1:8), 71.9g of compound 82-1 was obtained with a yield of 84%.
2) 화합물 82-2의 제조2) Preparation of compound 82-2
화합물 82-1 (70g, 211.22mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime(62.98g, 211.22mmol, 1eq), diacetoxypalladium(4.7g, 21.1mmol, 0.1eq)를 toluene(700ml)에 넣고 150에서 24시간 교반하였다. Compound 82-1 (70g, 211.22mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime (62.98g, 211.22mmol, 1eq), diacetoxypalladium (4.7g, 21.1mmol, 0.1eq) was added to toluene (700ml) and stirred at 150°C for 24 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:10), 화합물 82-2 56g을 65%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:10), 56g of compound 82-2 was obtained with a yield of 65%.
3) 화합물 82의 제조3) Preparation of compound 82
화합물 82-2 (10g, 21.86mmol, 1eq)과 N-phenyldibenzo[b,d]furan-4-amine (5.67g, 21.86mmol, 1eq)을 Tol 100ml와 EtOH 20ml, H2O 20ml에 녹인 후 (N2 condition) Pd2(dba)3(1.00g, 1.09mmol, 0.05eq)과 P(t-Bu)3(1.02ml, 2.19mmol, 0.1eq)과 NaOt-Bu(6.3g, 65.58mmol, 3eq)을 넣고 5시간 환류 교반하였다.Compound 82-2 (10g, 21.86mmol, 1eq) and N -phenyldibenzo[b,d]furan-4-amine (5.67g, 21.86mmol, 1eq) were dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H 2 O ( N 2 condition) Pd 2 (dba) 3 (1.00g, 1.09mmol, 0.05eq) and P( t -Bu) 3 (1.02ml, 2.19mmol, 0.1eq) and NaO t -Bu (6.3g, 65.58mmol, 3eq) was added and stirred under reflux for 5 hours.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 toluene 재결정 하였다.Toluene was recrystallized after silica gel filter.
soxhlet하여 화합물 82 7.7g을 60%의 수율로 얻었다.By soxhlet, 7.7 g of compound 82 was obtained with a yield of 60%.
상기 제조예 5에서 N-phenyldibenzo[b,d]furan-4-amine 대신 하기 표 5의 중간체 E를 사용하여 동일한 방법으로 제조하여 목적화합물 E를 합성하였다.The target compound E was synthesized in the same manner as in Preparation Example 5 using Intermediate E of Table 5 instead of N -phenyldibenzo[b,d]furan-4-amine.
[표 5][Table 5]
<< 제조예Manufacturing example 6> 화합물 395의 제조 6> Preparation of compound 395
1) 화합물 395-1의 제조1) Preparation of compound 395-1
(3-chlorophenyl)(naphthalen-2-yl)methanone(30g, 112.48mmol, 1eq), hydroxylamine hydrochloride(19.5g, 281.2mmol, 2.5eq), KOAc(27.6g, 281.2mmol, 2.5eq)에 methanol(300ml)를 넣고 60℃에서 1시간 교반하였다. 실온으로 식힌 후 고체를 여과한 후 여액을 농축하였다. 농축한 용액을 MC(300ml)에 녹인 후 triethylamine(34.1g, 337.44mmol, 3eq)을 0℃에서 첨가하였다. pivaloyl chloride(27.1g, 224.96mmol, 2eq)을 0℃에서 천천히 적가한 후 실온에서 30분간 교반하였다. (3-chlorophenyl)(naphthalen-2-yl)methanone (30g, 112.48mmol, 1eq), hydroxylamine hydrochloride (19.5g, 281.2mmol, 2.5eq), KOAc (27.6g, 281.2mmol, 2.5eq) and methanol (300ml) ) was added and stirred at 60°C for 1 hour. After cooling to room temperature, the solid was filtered and the filtrate was concentrated. The concentrated solution was dissolved in MC (300ml), and triethylamine (34.1g, 337.44mmol, 3eq) was added at 0°C. Pivaloyl chloride (27.1g, 224.96mmol, 2eq) was slowly added dropwise at 0°C and stirred at room temperature for 30 minutes.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층을 탄산수소나트륨용액으로 씻어주었다. 그 후 무수 Na2CO3로 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. The organic layer was washed with sodium bicarbonate solution. Afterwards, moisture was removed with anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:8 EA:Hex=1:6), 화합물 395-1 28.8g을 70%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:8 EA:Hex=1:6), 28.8g of compound 395-1 was obtained with a yield of 70%.
2) 화합물 395-2의 제조2) Preparation of compound 395-2
화합물 395-1 (28.8g, 78.74mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime(17.3g, 78.74mmol, 1eq), diacetoxypalladium(1.77g, 7.87mmol, 0.1eq)를 toluene(300ml)에 넣고 150℃에서 24시간 교반하였다. Compound 395-1 (28.8g, 78.74mmol, 1eq), 1-(4-bromophenyl)ethan-1-one O-pivaloyl oxime (17.3g, 78.74mmol, 1eq), diacetoxypalladium (1.77g, 7.87mmol, 0.1eq) ) was added to toluene (300ml) and stirred at 150°C for 24 hours.
물을 넣어 반응을 종결시킨 후 MC와 물을 이용하여 추출하였다. 유기층에 무수 Na2CO3을 이용하여 수분을 제거하였다. After adding water to terminate the reaction, extraction was performed using MC and water. Moisture was removed from the organic layer using anhydrous Na 2 CO 3 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:7), 화합물 395-2 25.2g을 72%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:7), 25.2 g of compound 395-2 was obtained with a yield of 72%.
3) 화합물 395-3의 제조3) Preparation of compound 395-3
화합물 395-2 (25.2g, 56.69mmol, 1eq)과 diphenyl(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)phosphine oxide (25.75g, 56.69mmol, 1eq)을 Tol 250ml와 EtOH 50ml, H2O 50ml에 녹인 후 (N2 condition) Pd(PPh3)4(3.27g, 2.83mmol, 0.05eq)과 K2CO3(23.51g, 170.07mmol, 3eq)을 넣고 10h 환류 교반하였다.Compound 395-2 (25.2g, 56.69mmol, 1eq) and diphenyl(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)phosphine oxide ( After dissolving 25.75g, 56.69mmol, 1eq) in 250ml of Tol, 50ml of EtOH, and 50ml of H 2 O (N 2 condition), Pd(PPh 3 ) 4 (3.27g, 2.83mmol, 0.05eq) and K 2 CO 3 (23.51 g, 170.07mmol, 3eq) was added and stirred under reflux for 10h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔 필터(Silisca-gel filter) 후 MC/MeOH precipitation 하였다.After silica gel filter (Silisca-gel filter), MC/MeOH precipitation was performed.
soxhlet하여 화합물 395-3 35.32g을 90%의 수율로 얻었다.By soxhlet, 35.32 g of compound 395-3 was obtained with a yield of 90%.
4) 화합물 395-4의 제조4) Preparation of compound 395-4
화합물 395-3 (35.32g, 51.02mmol, 1eq), Bis(pinacolato)diboron(19.43g, 76.53mmol, 1.5eq)을 1,4-dioxane(300ml)에 녹인 후 (N2 condition) Pd(dba)2(2.93g, 5.1mmol, 0.1eq)과 PCy3(2.86g, 10.2mmol, 0.2eq)과 KOAc(15.02g, 153.06mmol, 3eq)을 넣고 100에서 15h 교반하였다.Compound 395-3 (35.32g, 51.02mmol, 1eq) and Bis(pinacolato)diboron (19.43g, 76.53mmol, 1.5eq) were dissolved in 1,4-dioxane (300ml) (N 2 condition) and Pd(dba) 2 (2.93g, 5.1mmol, 0.1eq), PCy 3 (2.86g, 10.2mmol, 0.2eq) and KOAc (15.02g, 153.06mmol, 3eq) were added and stirred at 100°C for 15h.
MC와 물로 추출한 후 유기층을 무수 Na2SO4로 건조 후 실리카겔 필터하였다.After extraction with MC and water, the organic layer was dried over anhydrous Na 2 SO 4 and filtered with silica gel.
MC/MeOH로 precipitation 하였다. 침전을 여과하여 화합물 395-4 37.59g을 94%의 수율로 얻었다.Precipitation was performed with MC/MeOH. The precipitate was filtered to obtain 37.59 g of compound 395-4 with a yield of 94%.
5) 화합물 395의 제조5) Preparation of compound 395
화합물 395-4 (37.59g, 47.96mmol, 1eq)과 2-bromo-1,10-phenanthroline(12.43g, 47.96mmol, 1eq)을 Tol 400ml와 EtOH 80ml, H2O 80ml에 녹인 후 (N2 condition) Pd(PPh3)4(2.77g, 2.4mmol, 0.05eq)과 K2CO3(19.89g, 143.88mmol, 3eq)을 넣고 3h 환류 교반하였다.Compound 395-4 (37.59g, 47.96mmol, 1eq) and 2-bromo-1,10-phenanthroline (12.43g, 47.96mmol, 1eq) were dissolved in 400ml of Tol, 80ml of EtOH, and 80ml of H 2 O (N 2 condition). ) Pd(PPh 3 ) 4 (2.77g, 2.4mmol, 0.05eq) and K 2 CO 3 (19.89g, 143.88mmol, 3eq) were added and stirred under reflux for 3h.
반응액에 MC를 넣어 녹인 후 물로 추출하고 유기층을 무수 Na2SO4로 건조하였다.MC was added and dissolved in the reaction solution, extracted with water, and the organic layer was dried over anhydrous Na 2 SO 4 .
실리카겔(Silicagel) 컬럼으로 분리하여(전개용매 EA:Hex=1:1), 화합물 395 28.87g을 72%의 수율로 얻었다.By separation using a silica gel column (developing solvent EA:Hex=1:1), 28.87 g of compound 395 was obtained with a yield of 72%.
상기 제조예 6의 3)에서 diphenyl(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)phosphine oxide 대신 하기 표 6의 중간체 F와 제조예 6의 5)에서 2-bromo-1,10-phenanthroline 대신 하기 표 6의 중간체 G를 사용하여 동일한 방법으로 제조하여 목적화합물 F를 합성하였다.In 3) of Preparation Example 6, intermediate F of Table 6 below was used instead of diphenyl(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)phosphine oxide. and 5) of Preparation Example 6, the target compound F was synthesized in the same manner using Intermediate G of Table 6 instead of 2-bromo-1,10-phenanthroline.
[표 6][Table 6]
상기 제조예들과 같은 방법으로 화합물을 제조하고, 그 합성확인결과를 표 7 및 표 8에 나타내었다. 표 7는 1H NMR(CDCl3, 200Mz)의 측정값이고, 표 8은 FD-질량분석계(FD-MS: Field desorption mass spectrometry)의 측정값이다.Compounds were prepared in the same manner as in the above preparation examples, and the synthesis confirmation results are shown in Tables 7 and 8. Table 7 shows the measured values of 1 H NMR (CDCl 3 , 200Mz), and Table 8 shows the measured values of FD-MS (Field desorption mass spectrometry).
[표 7][Table 7]
[표 8][Table 8]
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1) 유기 발광 소자의 제작1) Fabrication of organic light emitting device
1500Å의 두께로 ITO가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 아세톤, 메탄올, 이소프로필 알코올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV 세정기에서 UV를 이용하여 5분간 UVO 처리하였다. 이후 기판을 플라즈마 세정기(PT)로 이송시킨 후, 진공상태에서 ITO 일함수 및 잔막 제거를 위해 플라즈마 처리를 하여, 유기 증착용 열증착 장비로 이송하였다. 상기 ITO 투명 전극(양극)위에 단일 스택 구조로 유기물을 형성하였다. 정공 주입층으로 HAT-CN을 50Å의 두께로 증착하고, 이어 정공 수송층인 NPD에 DNTPD을 10% 이내로 도핑하여, 1500Å의 두께로 증착하여 형성하고, TCTA를 200Å의 두께로 연속하여 증착하였다. 이어서, ADN 호스트에 t-Bu-페릴린 도펀트를 포함하는 발광층을 250Å의 두께로 형성하였다. 이어서, 전자 수송층인 Alq3를 250Å의 두께로 성막하고, N-type 전하 생성층으로 하기 표 9에 기재된 화합물에 알칼리 금속인 리튬을 도핑하여 100Å의 두께로 성막하고, 음극인 Al을 약 1,000Å의 두께로 성막하여 유기 발광 소자를 제작하였다.A glass substrate coated with a thin film of ITO with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV for 5 minutes using UV light in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition. An organic material was formed in a single stack structure on the ITO transparent electrode (anode). HAT-CN was deposited to a thickness of 50 Å as a hole injection layer, and then NPD, which is a hole transport layer, was doped with DNTPD to within 10% and deposited to a thickness of 1500 Å, and TCTA was continuously deposited to a thickness of 200 Å. Subsequently, an emission layer containing t-Bu-perylene dopant was formed on the ADN host to a thickness of 250 Å. Next, Alq 3 , an electron transport layer, was formed to a thickness of 250 Å, and as an N-type charge generation layer, the compound shown in Table 9 below was doped with lithium, an alkali metal, to form a film to a thickness of 100 Å, and Al, the cathode, was formed to a thickness of about 1,000 Å. An organic light-emitting device was manufactured by forming a film to a thickness of .
2) 유기 발광 소자의 구동 전압 및 발광 효율2) Driving voltage and luminous efficiency of organic light emitting devices
상기와 같이 제조된 유기 발광 소자에 대하여 맥사이어스사의 M7000으로 전계 발광(EL) 특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명측정장비(M6000)를 통해 기준 휘도가 750 cd/m2 일 때, T95을 측정하였다. 본 발명에 따라 제조된 백색 유기 전계 발광 소자의 구동전압, 발광효율, 외부양자효율, 색좌표(CIE)를 측정한 결과는 표 9과 같았다.The electroluminescence (EL) characteristics of the organic light-emitting device manufactured as described above were measured using M7000 from McScience, and the standard luminance was measured at 750 cd/mm using the lifespan measurement equipment (M6000) manufactured by McScience based on the measurement results. When m 2 , T 95 was measured. The results of measuring the driving voltage, luminous efficiency, external quantum efficiency, and color coordinate (CIE) of the white organic electroluminescent device manufactured according to the present invention are shown in Table 9.
[표 9][Table 9]
상기 표 9의 결과로부터 알 수 있듯이, 본 발명의 청색 유기 발광 소자의 전하 생성층 재료를 이용한 유기 발광 소자는 비교예에 비해 구동 전압이 낮고, 발광효율이 개선되었다. 특히 화합물 17, 18, 20, 93, 108, 277, 291, 292는 구동, 효율, 수명 모든 면에서 현저히 우수함을 확인하였다. As can be seen from the results in Table 9, the organic light emitting device using the charge generation layer material of the blue organic light emitting device of the present invention had a lower driving voltage and improved luminous efficiency compared to the comparative example. In particular, compounds 17, 18, 20, 93, 108, 277, 291, and 292 were confirmed to be significantly superior in all aspects of operation, efficiency, and lifespan.
이러한 결과가 나온 이유는 적절한 길이와 강도 및 평단한 특성을 가진 발명된 골격과 메탈과 바인딩할 수 있는 적절한 헤테로 화합물로 구성된 N 타입 전하 생성층으로 사용된 본 발명의 화합물이 알칼리 금속 또는 알칼리 토금속을 도핑되어 N 타입 전하 생성층 내에 갭 스테이트가 형성한 것으로 추정되고, P 타입 전하 생성층으로부터 생성된 전자가 N 타입 전하 생성층 내에서 생선된 갭 스테이트를 통해 전자 수송층으로 전자주입이 용이하게 되었을 것으로 판단된다. 따라서, P 타입 전하 생성층은 N 타입 전하 생성층으로 전자 주입과 전자 전달을 잘 할 수 있게 되고, 이 때문에 유기 발광 소자의 구동 전압이 낮아졌고 효율과 수명이 개선을 것으로 판단된다. The reason for this result is that the compound of the present invention used as an N-type charge generation layer consisting of the invented skeleton with appropriate length, strength, and flat properties and an appropriate hetero compound capable of binding to the metal is capable of absorbing alkali metal or alkaline earth metal. It is presumed that a gap state was formed within the N-type charge generation layer by doping, and it is believed that electrons generated from the P-type charge generation layer were easily injected into the electron transport layer through the gap state created within the N-type charge generation layer. It is judged. Therefore, the P-type charge generation layer is able to effectively inject and transfer electrons to the N-type charge generation layer, and for this reason, the driving voltage of the organic light-emitting device is lowered and the efficiency and lifespan are expected to be improved.
또한, 본 특허의 기본 골격인 화합물 Ref 1은 비교예 1-2, 1-3과 비교해 보았을 때 구동, 효율 및 수명이 나쁜 결과를 확인하였다. 이는 본 특허의 기본골격만으로는 평가 소자구조에서 향상된 전광특성 및 수명특성을 보여 주지 않는 것을 확인하였고, 다양한 치환기와의 적절하게 조합된 화합물만이 적절한 물리화학적 특성 및 열적 특성을 보유할 수 있으며, 소자평가에서도 우수한 특성 및 결과를 보여 주었다고 판단된다. In addition, Compound Ref 1, the basic framework of this patent, was confirmed to have poor operation, efficiency, and lifespan when compared to Comparative Examples 1-2 and 1-3. This confirms that the basic framework of this patent alone does not show improved electro-optical and lifespan characteristics in the evaluated device structure, and only compounds appropriately combined with various substituents can possess appropriate physicochemical and thermal properties, and the device It is judged that the evaluation showed excellent characteristics and results.
<< 실험예Experiment example 2> 2>
1) 유기 발광 소자의 제작1) Fabrication of organic light emitting device
1500Å의 두께로 ITO가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 아세톤, 메탄올, 이소프로필 알코올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV 세정기에서 UV를 이용하여 5분간 UVO 처리하였다. 이후 기판을 플라즈마 세정기(PT)로 이송시킨 후, 진공상태에서 ITO 일함수 및 잔막 제거를 위해 플라즈마 처리를 하여, 유기 증착용 열증착 장비로 이송하였다.A glass substrate coated with a thin film of ITO with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV for 5 minutes using UV light in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition.
상기 ITO 투명 전극(양극)위에 2 스택 WOLED(White Orgainc Light Device) 구조로 유기물을 형성하였다. 제1 스택은 우선 TAPC을 300Å의 두께로 열진공 증착하여 정공 수송층을 형성하였다. 정공 수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 열 진공 증착시켰다. 발광층은 호스트인 TCz1에 청색 인광도펀트로 FIrpic를 8% 도핑하여 300Å 증착하였다. 전자 수송층은 TmPyPB을 사용하여 400Å을 형성한 후, 전하 생성층으로 하기 표 10에 기재된 화합물에 Cs2CO3를 20% 도핑하여 100Å 형성하였다.An organic material was formed in a two-stack WOLED (White Orgainc Light Device) structure on the ITO transparent electrode (anode). In the first stack, TAPC was first thermally vacuum deposited to a thickness of 300 Å to form a hole transport layer. After forming the hole transport layer, a light emitting layer was thermally vacuum deposited on it as follows. The light-emitting layer was deposited at 300 Å by doping 8% of FIrpic as a blue phosphorescent dopant on TCz1, the host. The electron transport layer was formed to have a thickness of 400 Å using TmPyPB, and then the charge generation layer was formed to have a thickness of 100 Å by doping 20% of Cs 2 CO 3 into the compound shown in Table 10 below.
제2 스택은 우선 MoO3을 50Å의 두께로 열진공 증착하여 정공 주입층을 형성하였다. 공통층인 정공 수송층을 TAPC에 MoO3를 20% 도핑하여 100Å 형성한 후, TAPC를 300Å 증착하여 형성하였다, 그 위에 발광층은 호스트인 TCz1에 녹색 인광 토펀트인 Ir(ppy)3를 8% 도핑하여 300Å 증착한 후, 전자 수송층으로 TmPyPB을 사용하여 600Å을 형성하였다. 마지막으로 전자 수송층 위에 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하여 전자 주입층을 형성한 후, 전자 주입층 위에 알루미늄(Al) 음극을 1,200Å의 두께로 증착하여 음극을 형성함으로써 유기 발광 소자를 제조하였다.In the second stack, MoO 3 was first thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. The hole transport layer, which is a common layer, was formed by doping 20% of MoO 3 on TAPC to form 100 Å, and then TAPC was deposited at 300 Å. On top of this, the light emitting layer was formed by doping 8% of Ir(ppy) 3 , a green phosphorescent topant, into TCz1, the host. After depositing 300Å, 600Å was formed using TmPyPB as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic A light emitting device was manufactured.
한편, OLED 소자 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6 ~ 10-8torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다.Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 -6 to 10 -8 torr for each material and used for OLED production.
2) 유기 발광 소자의 구동 전압 및 발광 효율2) Driving voltage and luminous efficiency of organic light emitting devices
상기와 같이 제조된 유기 발광 소자에 대하여 맥사이어스사의 M7000으로 전계 발광(EL) 특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명측정장비(M6000)를 통해 기준 휘도가 3,500 cd/m2 일 때, T95을 측정하였다. 본 발명에 따라 제조된 백색 유기 발광 소자의 구동전압, 발광효율, 외부양자효율, 색좌표(CIE)를 측정한 결과는 표 10과 같았다.The electroluminescence (EL) characteristics of the organic light-emitting device manufactured as described above were measured using the M7000 from McScience, and the standard luminance was measured at 3,500 cd/ using the lifespan measurement equipment (M6000) manufactured by McScience based on the measurement results. When m 2 , T 95 was measured. The results of measuring the driving voltage, luminous efficiency, external quantum efficiency, and color coordinate (CIE) of the white organic light-emitting device manufactured according to the present invention are shown in Table 10.
[표 10][Table 10]
상기 표 10의 결과로부터 알 수 있듯이, 본 발명의 2-스택 백색 유기 발광 소자의 전하 생성층 재료를 이용한 유기 발광 소자는 비교예에 비해 구동 전압이 낮고, 발광효율이 개선되었다. 특히, 화합물 17, 18, 20, 93, 108, 277, 291, 292는 구동, 효율, 수명 모든 면에서 현저히 우수함을 확인하였다.As can be seen from the results in Table 10, the organic light emitting device using the charge generation layer material of the 2-stack white organic light emitting device of the present invention had a lower driving voltage and improved luminous efficiency compared to the comparative example. In particular, compounds 17, 18, 20, 93, 108, 277, 291, and 292 were confirmed to be significantly superior in all aspects of operation, efficiency, and lifespan.
이러한 결과가 나온 이유는 적절한 길이와 강도 및 평단한 특성을 가진 발명된 골격과 메탈과 바인딩할 수 있는 적절한 헤테로 화합물로 구성된 N 타입 전하 생성층으로 사용된 본 발명의 화합물이 알칼리 금속 또는 알칼리 토금속을 도핑되어 N 타입 전하 생성층 내에 갭 스테이트가 형성한 것으로 추정되고, P 타입 전하 생성층으로부터 생성된 전자가 N 타입 전하 생성층 내에서 생선된 갭 스테이트를 통해 전자 수송층으로 전자 주입이 용이하게 되었을 것으로 판단된다. 따라서, P 타입 전하 생성층은 N 타입 전하 생성층으로 전자 주입과 전자 전달을 잘 할 수 있게 되고, 이 때문에 유기 발광 소자의 구동 전압이 낮아졌고 효율과 수명이 개선되었을 것으로 판단된다.The reason for this result is that the compound of the present invention used as an N-type charge generation layer consisting of the invented skeleton with appropriate length, strength, and flat properties and an appropriate hetero compound capable of binding to the metal is capable of absorbing alkali metal or alkaline earth metal. It is presumed that a gap state was formed within the N-type charge generation layer by doping, and it is believed that electrons generated from the P-type charge generation layer were easily injected into the electron transport layer through the gap state created within the N-type charge generation layer. It is judged. Therefore, it is believed that the P-type charge generation layer can facilitate electron injection and electron transfer to the N-type charge generation layer, which lowers the driving voltage of the organic light-emitting device and improves efficiency and lifespan.
추가적으로, 본 특허의 기본 골격인 화합물 Ref 1을 WOLED 소자구조에서 비교예 2-2, 2-3과 비교해 보았을 때 구동, 효율 및 수명이 나쁜 결과를 확인하였다. 이런 결과도 본 특허의 기본골격만으로는 평가 소자구조에서 향상된 전광특성 및 수명특성을 보여 주지 않았고, 다양한 치환기와의 적절하게 조합된 화합물만이 적절한 물리화학적 특성 및 열적 특성을 보유할 수 있으며, 소자평가에서도 우수한 특성 및 결과를 보여 주었다고 판단된다.Additionally, when comparing Compound Ref 1, the basic framework of this patent, with Comparative Examples 2-2 and 2-3 in the WOLED device structure, poor driving, efficiency, and lifespan were confirmed. These results also did not show improved electro-optical characteristics and lifespan characteristics in the evaluation device structure using only the basic framework of this patent, and only compounds appropriately combined with various substituents can possess appropriate physicochemical and thermal properties, and device evaluation It is judged that it showed excellent characteristics and results.
<< 실험예Experiment example 3> 3>
1) 유기 발광 소자의 제작1) Fabrication of organic light emitting device
OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 각 5분간 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다.The transparent electrode ITO thin film obtained from OLED glass (manufactured by Samsung-Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol before use.
다음으로 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민 (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA)을 넣었다.Next, the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.
이어서 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 600Å 두께의 정공 주입층을 증착하였다.Subsequently, the vacuum in the chamber was evacuated until it reached 10 -6 torr, and then a current was applied to the cell to evaporate 2-TNATA to deposit a 600Å-thick hole injection layer on the ITO substrate.
진공 증착 장비 내의 다른 셀에 하기 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 넣고, 셀에 전류를 인가하여 증발시켜 정공 주입층 위에 300Å 두께의 정공 수송층을 증착하였다.In another cell in the vacuum deposition equipment, the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added and evaporated by applying a current to the cell to deposit a 300Å thick hole transport layer on the hole injection layer.
이와 같이 정공 주입층 및 정공 수송층을 형성시킨 후, 그 위에 발광층으로서 다음과 같은 구조의 청색 발광 재료를 증착시켰다. 구체적으로, 진공 증착 장비 내의 한쪽 셀에 청색 발광 호스트 재료인 H1을 200Å 두께로 진공 증착시키고 그 위에 청색 발광 도판트 재료인 D1을 호스트 재료 대비 5% 진공 증착시켰다.After forming the hole injection layer and the hole transport layer in this way, a blue light-emitting material with the following structure was deposited thereon as a light-emitting layer. Specifically, H1, a blue light-emitting host material, was vacuum-deposited to a thickness of 200 Å in one cell of the vacuum deposition equipment, and D1, a blue light-emitting dopant material, was vacuum-deposited 5% of the host material on top of it.
이어서 전자 수송층으로서 하기 구조식 E1의 화합물을 300Å 두께로 증착하였다.Next, a compound of the following structural formula E1 was deposited to a thickness of 300 Å as an electron transport layer.
전자 주입층으로 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하였고 Al 음극을 1,000Å의 두께로 하여 OLED 소자를 제작하였다.An OLED device was manufactured by depositing lithium fluoride (LiF) to a thickness of 10 Å as an electron injection layer and using an Al cathode to a thickness of 1,000 Å.
한편, OLED 소자 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8 torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 -6 to 10 -8 torr for each material and used for OLED production.
2) 유기 발광 소자의 구동 전압 및 발광 효율2) Driving voltage and luminous efficiency of organic light emitting devices
상기와 같이 제조된 유기 발광 소자에 대하여 맥사이어스사의 M7000으로 전계 발광(EL) 특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명측정장비(M6000)를 통해 기준 휘도가 700 cd/m2 일 때, T95을 측정하였다. 본 발명에 따라 제조된 백색 유기 발광 소자의 구동전압, 발광효율, 외부양자효율, 색좌표(CIE)를 측정한 결과는 표 11과 같았다.The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using the M7000 from McScience, and the standard luminance was measured at 700 cd/mm using the lifespan measurement equipment (M6000) manufactured by McScience based on the measurement results. When m 2 , T 95 was measured. The results of measuring the driving voltage, luminous efficiency, external quantum efficiency, and color coordinate (CIE) of the white organic light-emitting device manufactured according to the present invention are shown in Table 11.
[표 11][Table 11]
상기 표 11의 결과로부터 알 수 있듯이, 본 발명의 청색 유기 발광 소자의 전자 수송층 재료를 이용한 유기 발광 소자는 비교예에 비해 구동 전압이 낮고, 발광효율 및 수명이 현저히 개선되었다. 특히 화합물 68, 81, 147, 150, 157, 168, 242, 331, 334, 352, 357은 구동, 효율, 수명 모든 면에서 우수함을 확인하였다.As can be seen from the results in Table 11, the organic light emitting device using the electron transport layer material of the blue organic light emitting device of the present invention had a lower driving voltage and significantly improved luminous efficiency and lifespan compared to the comparative example. In particular, compounds 68, 81, 147, 150, 157, 168, 242, 331, 334, 352, and 357 were confirmed to be excellent in all aspects of operation, efficiency, and lifespan.
이러한 결과의 원인은 적절한 길이와 강도 및 평단한 특성을 가진 발명된 화합물이 전자 수송층으로 사용되었을 때, 특정 조건하에 전자를 받아 여기된 상태의 화합물을 만들고 특히, 화합물의 헤테로골격 부위의 여기된 상태가 형성되면, 여기된 헤테로골격 부위가 다른 반응하기 전에 여기된 에너지가 안정한 상태로 이동될 것이며 비교적 안정해진 화합물은 화합물의 분해 혹은 파괴는 일어나지 않고 전자를 효율적으로 전달할 수 있기 때문이라고 판단된다. 참고로 여기되었을 때 안정한 상태를 가지는 것들은 아릴 혹은 아센류 화합물들 혹은 다원환 헤테로 화합물들이라고 생각한다. 따라서. 본 발명의 화합물이 향상된 전자-수송 특성 혹은 개선된 안정성을 향상시켜 구동, 효율, 수명 모든 면에서 우수함을 가져다 주었다고 판단된다.The reason for this result is that when the invented compound with appropriate length, strength, and flat properties is used as an electron transport layer, it receives electrons under specific conditions to create a compound in an excited state, and in particular, the excited state of the heteroskeleton portion of the compound. When formed, the excited energy will be transferred to a stable state before the excited heteroskeleton part undergoes another reaction, and it is believed that this is because a relatively stable compound can efficiently transfer electrons without decomposition or destruction of the compound. For reference, those that are in a stable state when excited are thought to be aryl or acene compounds or multi-membered ring hetero compounds. thus. It is believed that the compound of the present invention has improved electron-transport properties or improved stability, resulting in excellence in all aspects of operation, efficiency, and lifespan.
추가적으로, 본 특허의 기본 골격인 화합물 Ref 1을 ETL로 사용한 평가에서도 역시, 비교예 3-2, 3-3과 비교해 보았을 때 구동, 효율 및 수명이 나쁜 결과를 확인하였다. 이런 결과도 본 특허의 기본골격만으로는 평가 소자구조에서 향상된 전광특성 및 수명특성을 보여 주지 않았고, 다양한 치환기와의 적절하게 조합된 화합물만이 적절한 물리화학적 특성 및 열적 특성을 보유할 수 있으며, 소자평가에서도 우수한 특성 및 결과를 보여 주었다고 판단된다.Additionally, in the evaluation using Compound Ref 1, the basic framework of this patent, as ETL, poor driving, efficiency, and lifespan results were confirmed when compared to Comparative Examples 3-2 and 3-3. These results also did not show improved electro-optical characteristics and lifespan characteristics in the evaluation device structure using only the basic framework of this patent, and only compounds appropriately combined with various substituents can possess appropriate physicochemical and thermal properties, and device evaluation It is judged that it showed excellent characteristics and results.
100: 기판
200: 양극
300: 유기물층
301: 정공 주입층
302: 정공 수송층
303: 발광층
304: 정공 저지층
305: 전자 수송층
306: 전자 주입층
400: 음극100: substrate
200: anode
300: Organic layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode
Claims (13)
[화학식 1]
상기 화학식 1에서,
R3, R4, R8 및 R9 중 적어도 하나는 -(L1)m-(Z1)n으로 표시되고, 나머지는 수소이며,
R1, R2, R5 내지 R7 및 R10은 수소이고,
L1은 직접결합; C6 내지 C60의 아릴렌기; 또는 C2 내지 C60의 헤테로아릴렌기이고,
Z1은 C6 내지 C60의 아릴기; C2 내지 C60의 헤테로아릴기; ; ; ; ; ; ; 및 C1 내지 C60의 알킬기 또는 C6 내지 C60의 아릴기로 치환 또는 비치환된 C6 내지 C60의 아릴기로 치환 또는 비치환된 아민기로 이루어진 군으로부터 선택되며,
m 및 n은 각각 독립적으로 1 내지 4의 정수이고,
R11 내지 R17은 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 중수소이다.Heterocyclic compound represented by the following formula (1):
[Formula 1]
In Formula 1,
At least one of R3, R4, R8 and R9 is represented by -(L1)m-(Z1)n, the remainder is hydrogen,
R1, R2, R5 to R7 and R10 are hydrogen,
L1 is direct bonding; C 6 to C 60 arylene group; Or a C 2 to C 60 heteroarylene group,
Z1 is an aryl group of C 6 to C 60 ; C 2 to C 60 heteroaryl group; ; ; ; ; ; ; and an amine group substituted or unsubstituted with a C 6 to C 60 aryl group substituted or unsubstituted with a C 1 to C 60 alkyl group or a C 6 to C 60 aryl group,
m and n are each independently integers from 1 to 4,
R11 to R17 are the same as or different from each other, and are each independently hydrogen; Or deuterium.
L1, Z1, m 및 n은 화학식 1에서의 정의와 동일한 것을 특징으로 하는 헤테로고리 화합물.The method of claim 1, wherein R3, R4, R8 or R9 in Formula 1 is represented by -(L1)m-(Z1)n,
A heterocyclic compound wherein L1, Z1, m and n are the same as defined in Formula 1.
L1, Z1, m 및 n은 화학식 1에서의 정의와 동일한 것을 특징으로 하는 헤테로고리 화합물.The method of claim 1, wherein any one of R3 and R4 and any one of R8 and R9 in Formula 1 are each independently represented by -(L1)m-(Z1)n,
A heterocyclic compound wherein L1, Z1, m and n are the same as defined in Formula 1.
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