KR101794795B1 - Hole transporting material and Organic electroluminescent display device using the same - Google Patents
Hole transporting material and Organic electroluminescent display device using the same Download PDFInfo
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- KR101794795B1 KR101794795B1 KR1020100114070A KR20100114070A KR101794795B1 KR 101794795 B1 KR101794795 B1 KR 101794795B1 KR 1020100114070 A KR1020100114070 A KR 1020100114070A KR 20100114070 A KR20100114070 A KR 20100114070A KR 101794795 B1 KR101794795 B1 KR 101794795B1
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- South Korea
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- electrode
- hole transport
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- WBWYYCXVPODZJI-UHFFFAOYSA-N C[Si+](C)(C)c(cc1)ccc1-[n]1c2ccc(CCCOCCCN(c(cc3)ccc3-c(cc3)ccc3N(c3ccc(COCc4ccc(C=C)cc4)cc3)c3c(cccc4)c4ccc3)c3c(cccc4)c4ccc3)cc2c2cc(CCCOCCCN(c(cc3)ccc3-c(cc3)ccc3N(c3ccc(COCc4ccc(C=C)cc4)cc3)c3c(cccc4)c4ccc3)c3c(cccc4)c4ccc3)ccc12 Chemical compound C[Si+](C)(C)c(cc1)ccc1-[n]1c2ccc(CCCOCCCN(c(cc3)ccc3-c(cc3)ccc3N(c3ccc(COCc4ccc(C=C)cc4)cc3)c3c(cccc4)c4ccc3)c3c(cccc4)c4ccc3)cc2c2cc(CCCOCCCN(c(cc3)ccc3-c(cc3)ccc3N(c3ccc(COCc4ccc(C=C)cc4)cc3)c3c(cccc4)c4ccc3)c3c(cccc4)c4ccc3)ccc12 WBWYYCXVPODZJI-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
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Abstract
본 발명은 하기 화학식으로 표시되며, R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택되며, L은 탄소(C), 산소(O)또는 황(S)에서 선택되며, m은 0또는 1의 정수이고, n은 1~3의 정수이며, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes) 중 적어도 하나를 포함하여 가교 결합 특성을 갖는 것이 특징인 유기전계발광소자용 정공수송물질을 제공한다.
Wherein R 1, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group of C 1 to C 20, a substituted or unsubstituted C 5 to C 30 An aryl group, a polycyclic aromatic or polycyclic heterocyclic group of C3 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a C3 to C30 A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. Each of R 2, R 3, R 7 and R 8 is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group having a carbon number of C 5 to C 30, a hetero-arylene group having a carbon number of 3 to 30, A substituted or unsubstituted arylalkylene group of up to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and R5, R6, R10 , And R11 may include at least one of a vinyl group, an acryloyl group, a methacyloyl group, cyclic ethers, and siloxanes, A hole transporting material for an organic electroluminescence device, and a hole transporting material for an organic electroluminescence device.
Description
본 발명은 정공 수송 물질 및 이를 사용하는 유기전계발광소자에 관한 것이다. 보다 구체적으로, 본 발명은 경화 공정에 따라 유기 용매에 대한 용해 특성이 변경되는 정공 수송 물질 및 이를 포함하여 이루어지는 유기전계발광소자에 관한 것이다.
The present invention relates to a hole transport material and an organic electroluminescent device using the same. More specifically, the present invention relates to a hole transport material in which the dissolution characteristics with respect to an organic solvent are changed according to a curing process, and an organic electroluminescent device comprising the same.
최근 표시장치의 대형화에 따라 공간 점유가 적은 평면표시소자의 요구가 증대되고 있는데, 이러한 평면표시소자 중 하나로서 유기발광다이오드(organic light emitting diode: OLED)라고도 불리는 유기전계발광소자의 기술이 빠른 속도로 발전하고 있으며, 이미 여러 시제품들이 발표된 바 있다.In recent years, the demand for a flat display device having a small space occupancy has been increased due to the enlargement of the display device. The technology of the organic electroluminescent device, which is also called an organic light emitting diode (OLED) And several prototypes have already been announced.
유기 전계 발광 소자는 전자 주입 전극(음극)과 정공 주입 전극(양극) 사이에 형성된 발광물질층에 전하를 주입하면 전자와 정공이 쌍을 이룬 후 소멸하면서 빛을 내는 소자이다. 플라스틱 같은 휠 수 있는(flexible) 투명 기판 위에도 소자를 형성할 수 있을 뿐 아니라, 플라즈마 디스플레이 패널(Plasma Display Panel)이나 무기 전계발광(EL) 디스플레이에 비해 낮은 전압에서 (10V이하) 구동이 가능하고, 또한 전력 소모가 비교적 적으며, 색감이 뛰어나다는 장점이 있다. 또한 유기 전계 발광(EL) 소자는 녹색, 청색, 적색의 3가지 색을 나타낼 수가 있어 차세대 풍부한 색 디스플레이 소자로 많은 사람들의 많은 관심의 대상이 되고 있다. An organic electroluminescent device is a device that injects electric charge into a light emitting material layer formed between an electron injecting electrode (cathode) and a hole injecting electrode (anode) to form an electron and a hole. The device can be formed on a flexible transparent substrate such as a plastic substrate and can be driven at a lower voltage (10 V or less) than a plasma display panel or an inorganic electroluminescence (EL) It also has the advantage of low power consumption and excellent color. In addition, organic electroluminescence (EL) devices can display three colors of green, blue, and red, making them a next-generation rich color display device and attracting a lot of interest from many people.
일반적으로, 유기전계발광소자는 양극(Anode), 정공주입층 (HIL:hole injecting layer), 정공수송층 (HTL: hole transporting layer), 발광물질층 (EML: emitting material layer), 전자수송층 (ETL: electron transporting layer), 전자주입층 (EIL: electron injecting layer), 음극(cathode)의 적층 구조를 갖는다. 발광층의 경우 호스트(Host)와 도펀트(dopant)로 구성된다. 정공과 전자는 각각의 전극에서 투입되어 이동하면서 발광물질층에서 재결합하여 여기자(exciton)을 형성한다. 여기자가 들뜬 상태(Excited state)에서 바닥 상태(ground state)로 떨어지면서 빛을 방출하게 된다.In general, an organic electroluminescent device includes an anode, a hole injecting layer (HIL), a hole transporting layer (HTL), an emitting material layer (EML), an electron transporting layer (ETL) an electron transporting layer, an electron injecting layer (EIL), and a cathode. In the case of the light emitting layer, it is composed of a host and a dopant. The holes and electrons are injected from the respective electrodes and recombine in the light emitting material layer while moving, thereby forming an exciton. The exciton emits light as it falls from the excited state to the ground state.
유기전계발광소자의 대면적화가 요구되고 있는데, 이를 위해서는 용액공정에 의해 유기전계발광소자가 제조되어야 한다. 증착공정의 경우 제1유기막 위에 제2유기막이 증착될 때 하부막의 손실없이 적층이 가능하지만 용액공정은 상부막을 형성할 때 사용된 용매가 하부막을 침식시켜 하부막에 손상을 발생하게 된다.An organic electroluminescent device has to be manufactured by a solution process. In the case of the deposition process, when the second organic film is deposited on the first organic film, lamination is possible without loss of the lower film, but in the solution process, the solvent used in forming the upper film causes the lower film to be damaged by the lower film.
예를 들어, 정공수송층 상에 발광물질층을 형성하는 경우, 발광물질층의 유기 용매가 정공수송층에 손상을 발생시키게 되며, 이에 의해 유기전계발광소자의 특성 저하 및 공정 수율의 저하 문제를 발생시킨다.
For example, when the light emitting material layer is formed on the hole transporting layer, the organic solvent of the light emitting material layer may cause damage to the hole transporting layer, thereby deteriorating the properties of the organic electroluminescence device and lowering the process yield .
본 발명은 유기 용매에 대한 용해도가 뛰어나 용액공정이 가능하며 추후 공정에서의 유기 용매에 의한 손상을 방지할 수 있는 정공수송층의 물질을 제공하고자 한다.
An object of the present invention is to provide a material for a hole transporting layer which is excellent in solubility in an organic solvent and is capable of a solution process and can prevent damage by an organic solvent in a subsequent process.
위와 같은 과제의 해결을 위해, 본 발명은 하기 화학식으로 표시되며, R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택되며, L은 탄소(C), 산소(O)또는 황(S)에서 선택되며, m은 0또는 1의 정수이고, n은 1~3의 정수이며, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes) 중 적어도 하나를 포함하여 가교 결합 특성을 갖는 것이 특징인 유기전계발광소자용 정공수송물질을 제공한다.R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group of C 1 to C 20, C 5 C30 substituted or unsubstituted aryl group, C3 to C30 polycyclic aromatic or polycyclic heterocyclic group, C6 to C30 substituted or unsubstituted aralkyl group an arylalkyl group, a substituted or unsubstituted cycloalkyl group of C3 to C30, a substituted or unsubstituted alkoxy group of C1 to C20, a substituted or unsubstituted aryloxyl group of C6 to C20, R2, R3, R7 and R8 are each selected from the group consisting of C1 to C20 substituted or unsubstituted alkylene group, C5 to C30 substituted or unsubstituted arylene group, C3 to C30 A hetero-arylene group, a substituted or unsubstituted arylalkylene group of C6 to C30, a C3 to C30 L is selected from carbon (C), oxygen (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, , At least two of R5, R6, R10 and R11 are a vinyl group, an acryloyl group, a methacyloyl group, cyclic ethers, siloxanes, A hole transporting material for an organic electroluminescence device, and a hole transporting material for an organic electroluminescence device.
상기 C1~C20까지의 치환 또는 비치환된 알킬기 그룹은 메틸기, 에틸기, 프로필기, 아이스프로필기, 뷰틸기, sec-뷰틸기, tert-뷰틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 데카닐기, 옥타데카닐기, 스테아릴기, 2-페닐아이소프로필기, 트라이클로로메틸기, 트라이플루오로메틸기, 벤질기, α-페녹시벤질기, α-다이메틸벤질기, α-메틸페닐벤질기, α-다이트라이플루오로메틸벤질기, 트라이페닐메틸기, α-벤질옥시벤질기를 포함하는 것이 특징이다.The C1 to C20 substituted or unsubstituted alkyl group group is preferably a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, an? -dithifluoromethylbenzyl group, a triphenylmethyl group, and an? -benzyloxybenzyl group.
상기 C5~C30의 치환 또는 비치환된 아릴기 그룹은 페닐기, 2-메틸페닐기, 3-메틸페닐기, 4-메틸페닐기, 펜타듀트륨페닐기, 2-트리메틸실릴페닐기, 3-트리메틸실릴페닐기, 4-트리메틸실릴페닐기, 3,5-다이플루오로페닐기, 4-에틸페닐기, 바이페닐기, 4-메닐바이페닐기, 4-에틸바이페닐기, 4-사이클로헥실바이페닐기, 터페닐기, 3,5-다이클로로페닐기를 포함하는 것이 특징이다.The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A 4-ethylhexylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, a 3,5-dichlorophenyl group, . ≪ / RTI >
상기 C3~C30의 다환성 방향족 또는 이형고리 그룹은 나프틸기, 1-메틸나프틸기, 2-메틸나프틸기, 아세나프틸기, 안트라세닐기, 풀루오레닐기, 페날닐기, 페난스레닐기, 파이렌닐기를 포함하는 것이 특징이다.The C3 to C30 polycyclic aromatic or aliphatic ring group is preferably a naphthyl group, a 1-methylnaphthyl group, a 2-methylnaphthyl group, an acenaphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group, a phenanthrenyl group, .
상기 C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹은 벤질기, 1-페닐에틸기, 2-페닐에틸기, 1-페닐아이소프로필기, 2-페닐아이소프로필기, 페닐-t-뷰틸기, α-나프틸메틸기, 1-α-나프틸에틸기, 2-α-나프틸에틸기, 1-α-나프틸아이소프로필기, 2-α-나프틸아이소프로필기, β-나프틸메틸기, 1-β-나프틸에틸기, 2-β-나프틸에틸기, 1-β-나프틸아이소프로필기, 2-β-나프틸아이소프로필기, 1-피롤릴메틸기, 2-(1-피롤릴)에틸기, p-메틸벤질기, m-메틸벤질기, o-메틸벤질기, p-클로로벤질기, m-클로로벤질기, o-클로로벤질기, p-브로모벤질기, m-브로모벤질기, o-브로모벤질기, p-아이오도벤질기, m-아이오도벤질기, o-아이오도벤질기, p-하이드록시벤질기, m-하이드록시벤질기, o-하이드록시벤질기, p-아미노벤질기, m-아미노벤질기, o-아미노벤질기, p-나이트로벤질기, m-나이트로벤질기, o-나이트로벤질기, p-사이아노벤질기, m-사이아노벤질기, o-사이아노벤질기, 1-하이드록시-2-페닐아이소프로필기, 1-클로로-2-페닐아이소프로필기를 포함하는 것이 특징이다.The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, o-methylbenzyl group, A p-hydroxybenzyl group, an m-hydroxybenzyl group, an o-hydroxybenzyl group, a p-iodobenzyl group, a p-iodobenzyl group, Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitro Benzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy- And a propyl group.
상기 C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹은 사이클로프로필기, 사이클로뷰틸기, 사이클로펜틸기, 사이클로헥실기, 노보넨기, 아다만틸기를 포함하는 것이 특징이다.The C3 to C30 substituted or unsubstituted cycloalkyl group group is characterized by containing a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group and an adamantyl group.
상기 C1~C20의 치환 또는 비치환된 알콕시기 그룹은 메톡시기, 에톡시기, 프로폭시기, 아이소프로폭시기, 뷰톡시기, 아이소뷰톡시기, sec-뷰톡시기, tert-뷰톡시기, 헵틸옥시기, 헥실옥시기를 포함하는 특징이다.The substituted or unsubstituted C1-C20 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, And a hexyloxy group.
상기 C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹은 페녹시기, 톨릴옥시기, 나프틸옥시기를 포함하는 것이 특징이다.The C6 to C20 substituted or unsubstituted aryloxy group group is characterized by including a phenoxy group, a tolyloxy group, and a naphthyloxy group.
상기 R5, R6, R10, R11 중 적어도 두개는 비닐페닐기(4-vinylphenyl), 비닐벤질옥시메타페닐기(4-(4-vinylbenzyl)oxymethylphenyl) 중 적어도 어느 하나의 치환체를 포함하는 것이 특징이다.At least two of R5, R6, R10 and R11 include a substituent of at least one of a 4-vinylphenyl group and a 4- (4-vinylbenzyl) oxymethylphenyl group.
상기 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 중에서 상기 R5, R6, R10, R11 중 적어도 두개를 제외한 나머지는 메틸(methyl), 에틸(ethyl), n-프로필(n-propyl), i-프로필(i-propyl), n-부틸(n-butyl), i-부틸(i-butyl) 및 t-부틸(t-butyl) 등과 같은 C1~C6 의 알킬 그룹(alkyl)과 시아닐(cyanyl), 트리메틸실릴(trimethylsilyl), 플루오린(fluorine), 트리플루오로메틸 (trifluoromethyl), 중수소(deuterium) 중 어느 하나의 치환체를 포함하는 것이 특징이다.R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10 and R 11 are other than methyl, ethyl, n- A C1 to C6 alkyl group such as n-propyl, i-propyl, n-butyl, i-butyl and t- and a substituent of any one of alkyl, cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium.
다른 관점에서, 본 발명은 제 1 전극과; 상기 제 1 전극과 마주보는 제 2 전극과; 상기 제 1 및 제 2 전극 사이에 위치하는 발광물질층과; 상기 제 1 전극과 상기 발광물질층 사이에 위치하는 정공수송층을 포함하고, 상기 정공수송층은, 하기 화학식으로 표시되며, R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택되며, L은 탄소(C), 산소(O)또는 황(S)에서 선택되며, m은 0또는 1의 정수이고, n은 1~3의 정수이며, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes) 중 적어도 하나를 포함하여 가교 결합 특성을 갖는 정공수송물질로 이루어지는 것이 특징인 유기전계발광소자를 제공한다.In another aspect, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; A light emitting material layer disposed between the first and second electrodes; And a hole transport layer disposed between the first electrode and the light emitting material layer, wherein the hole transport layer is represented by the following formula: wherein R1, R4, R5, R6, R9, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group of C5 to C30, a polycyclic aromatic or polycyclic heterocyclic group of C3 to C30, A substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30, a substituted or unsubstituted alkoxy group of C1 to C20 ), A substituted or unsubstituted aryloxy group of C6 to C20, R2, R3, R7 and R8 each represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted C5 to C30 A substituted or unsubstituted arylene group, a C3-C30 hetero-arylene group, C6-C3 L is selected from carbon (C), oxygen (O), or sulfur (S), wherein R is selected from the group consisting of a substituted or unsubstituted arylalkylene group of up to 0 carbon atoms and a substituted or unsubstituted cycloalkylene group of C3 to C30; m is an integer of 0 or 1 and n is an integer of 1 to 3 and at least two of R5, R6, R10 and R11 are a vinyl group, an acryloyl group, methacyloyl wherein the hole transporting material comprises at least one of cyclic ethers, siloxanes, cyclic ethers, and siloxanes.
상기 R5, R6, R10, R11 중 적어도 두개는 비닐페닐기(4-vinylphenyl), 비닐벤질옥시메타페닐기(4-(4-vinylbenzyl)oxymethylphenyl) 중 적어도 어느 하나의 치환체를 포함하는 것이 특징이다.At least two of R5, R6, R10 and R11 include a substituent of at least one of a 4-vinylphenyl group and a 4- (4-vinylbenzyl) oxymethylphenyl group.
상기 정공수송층은 스핀코팅 공정, 노즐프린팅 공정, 잉크젯프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정 중 어느 하나에 의해 형성되는 것이 특징이다.The hole transport layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
상기 제 1 전극과 상기 정공수송층 사이에 위치하는 정공주입층과; 상기 발광물질층과 상기 제 2 전극 사이에 위치하는 전자수송층과; 상기 전자수송층과 상기 제 2 전극 사이에 위치하는 전자주입층을 포함하는 것이 특징이다.A hole injection layer disposed between the first electrode and the hole transport layer; An electron transport layer positioned between the light emitting material layer and the second electrode; And an electron injection layer located between the electron transport layer and the second electrode.
본 발명의 정공수송물질은 유기용매에 대한 용해도가 뛰어나기 때문에 용액 공정에 의해 정공수송층을 형성할 수 있다. 따라서 대면적 유기전계발광소자의 제조가 용이하다.Since the hole transport material of the present invention is excellent in solubility in an organic solvent, a hole transport layer can be formed by a solution process. Therefore, it is easy to manufacture a large-area organic electroluminescent device.
또한, 경화 공정에 의해 가교결합이 발생하여 유기용매에 대한 용해도를 갖지 않게 됨으로써, 추후 공정에 의한 손상을 방지할 수 있다.
In addition, cross-linking occurs due to the curing process, so that solubility in an organic solvent is not obtained, and damage due to a subsequent process can be prevented.
도 1은 본 발명의 실시예에 따른 유기전계발광소자의 개략적인 단면도이다.1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
이하, 본 발명에 따른 정공수송물질의 구조 및 그 합성예와, 이를 이용한 유기전계발광소자에 대해 설명한다.Hereinafter, the structure of the hole transport material according to the present invention and its synthesis example and the organic electroluminescent device using the same will be described.
본 발명의 실시예에 따른 정공수송물질은 카바졸(carbazole) 유도체 중심부에 가교결합(cross-linking)이 가능하고 정공수송능력이 우수한 물질이 링커(linker)에 의해 연결된 구조를 가지며, 하기 화학식1로 표시된다.The hole transport material according to an embodiment of the present invention has a structure in which a substance capable of cross-linking to a center portion of a carbazole derivative and having excellent hole transporting ability is linked by a linker, .
화학식1Formula 1
본 발명의 실시예에 따른 정공수송물질은 유기 용매에 대한 용해도가 뛰어나며, 경화공정에 의해 가교결합이 발생하여 유기 용매에 대한 저항성을 갖는 것이 특징이다. 즉, 경화 공정 후에는 유기 용매에 용해되지 않는다.The hole transporting material according to an embodiment of the present invention is excellent in solubility in an organic solvent and is characterized by having resistance to an organic solvent due to cross-linking caused by a curing process. That is, it does not dissolve in the organic solvent after the curing process.
상기 화학식1에서 R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택된다. 특히, R5, R6, R10, R11 중 적어도 두개는 가교결합 특성을 갖는 물질에서 선택되고, L은 탄소(C), 산소(O)또는 황(S)에서 선택된다. 또한, m은 0또는 1의 정수이며, n은 1~3의 정수이다.Wherein R 1, R 4, R 5, R 6, R 9, R 10 and R 11 are each independently a substituted or unsubstituted alkyl group of C 1 to C 20 or a substituted or unsubstituted aryl group of C 5 to C 30 a polycyclic aromatic group or polycyclic heterocyclic group of C3 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted C3 to C30 group, A cycloalkyl group, a substituted or unsubstituted alkoxy group of C 1 to C 20, a substituted or unsubstituted aryloxy group of C 6 to C 20, and R 2 and R 3 , R7 and R8 each represent a substituted or unsubstituted alkylene group of C1-C20, a substituted or unsubstituted arylene group of C5-C30, a hetero-arylene group of C3-C30, a substituted or unsubstituted C6- An unsubstituted arylalkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30 Is selected. In particular, at least two of R5, R6, R10 and R11 are selected from materials having cross-linking properties and L is selected from carbon (C), oxygen (O) or sulfur (S). M is an integer of 0 or 1, and n is an integer of 1 to 3.
예를 들어, C1~C20까지의 치환 또는 비치환된 알킬기 그룹은 메틸기, 에틸기, 프로필기, 아이스프로필기, 뷰틸기, sec-뷰틸기, tert-뷰틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 데카닐기, 옥타데카닐기, 스테아릴기, 2-페닐아이소프로필기, 트라이클로로메틸기, 트라이플루오로메틸기, 벤질기, α-페녹시벤질기, α-다이메틸벤질기, α-메틸페닐벤질기, α-다이트라이플루오로메틸벤질기, 트라이페닐메틸기, α-벤질옥시벤질기를 포함할 수 있다.For example, the substituted or unsubstituted alkyl group group of C1 to C20 may be a methyl group, an ethyl group, a propyl group, an icopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, An alkenyl group such as an octyl group, a decanyl group, an octadecanyl group, a stearyl group, a 2-phenylisopropyl group, a trichloromethyl group, a trifluoromethyl group, a benzyl group, Benzyl group,? -Dithifluoromethylbenzyl group, triphenylmethyl group,? -Benzyloxybenzyl group.
C5~C30의 치환 또는 비치환된 아릴기 그룹은 페닐기, 2-메틸페닐기, 3-메틸페닐기, 4-메틸페닐기, 펜타듀트륨페닐기, 2-트리메틸실릴페닐기, 3-트리메틸실릴페닐기, 4-트리메틸실릴페닐기, 3,5-다이플루오로페닐기, 4-에틸페닐기, 바이페닐기, 4-메닐바이페닐기, 4-에틸바이페닐기, 4-사이클로헥실바이페닐기, 터페닐기, 3,5-다이클로로페닐기를 포함할 수 있다.The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A biphenyl group, a 4-methylbiphenyl group, a 4-ethylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, .
C3~C30의 다환성 방향족 또는 이형고리 그룹은 나프틸기, 1-메틸나프틸기, 2-메틸나프틸기, 아세나프틸기, 안트라세닐기, 풀루오레닐기, 페날닐기, 페난스레닐기, 파이렌닐기를 포함할 수 있다.The polycyclic aromatic or aliphatic ring group of C3 to C30 includes naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, acenaphthyl, anthracenyl, can do.
C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹은 벤질기, 1-페닐에틸기, 2-페닐에틸기, 1-페닐아이소프로필기, 2-페닐아이소프로필기, 페닐-t-뷰틸기, α-나프틸메틸기, 1-α-나프틸에틸기, 2-α-나프틸에틸기, 1-α-나프틸아이소프로필기, 2-α-나프틸아이소프로필기, β-나프틸메틸기, 1-β-나프틸에틸기, 2-β-나프틸에틸기, 1-β-나프틸아이소프로필기, 2-β-나프틸아이소프로필기, 1-피롤릴메틸기, 2-(1-피롤릴)에틸기, p-메틸벤질기, m-메틸벤질기, o-메틸벤질기, p-클로로벤질기, m-클로로벤질기, o-클로로벤질기, p-브로모벤질기, m-브로모벤질기, o-브로모벤질기, p-아이오도벤질기, m-아이오도벤질기, o-아이오도벤질기, p-하이드록시벤질기, m-하이드록시벤질기, o-하이드록시벤질기, p-아미노벤질기, m-아미노벤질기, o-아미노벤질기, p-나이트로벤질기, m-나이트로벤질기, o-나이트로벤질기, p-사이아노벤질기, m-사이아노벤질기, o-사이아노벤질기, 1-하이드록시-2-페닐아이소프로필기, 1-클로로-2-페닐아이소프로필기를 포함할 수 있다.The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o- Benzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzene group, A 1-hydroxy-2-phenylisopropyl group, a 1-chloro-2-phenylisopropyl group, a 1-hydroxybenzyl group, Group.
C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹은 사이클로프로필기, 사이클로뷰틸기, 사이클로펜틸기, 사이클로헥실기, 노보넨기, 아다만틸기를 포함할 수 있다.The substituted or unsubstituted cycloalkyl group group of C3 to C30 may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group, and an adamantyl group.
C1~C20의 치환 또는 비치환된 알콕시기 그룹은 메톡시기, 에톡시기, 프로폭시기, 아이소프로폭시기, 뷰톡시기, 아이소뷰톡시기, sec-뷰톡시기, tert-뷰톡시기, 헵틸옥시기, 헥실옥시기를 포함할 수 있다.The substituted or unsubstituted alkoxy group of C1 to C20 is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert- And may include a period of silk gardens.
C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹은 페녹시기, 톨릴옥시기, 나프틸옥시기를 포함할 수 있다.The C6 to C20 substituted or unsubstituted aryloxy group group may include a phenoxy group, a tolyloxy group, and a naphthyloxy group.
또한, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes)과 같은 가교 결합 특성을 갖는 치환체를 포함한다. 예를 들어, 상기 가교 결합 특성을 갖는 치환체는 하기 화힉식2-1 및 화학식2-2로 표시되는 비닐페닐기(4-vinylphenyl), 비닐벤질옥시메타페닐기(4-(4-vinylbenzyl)oxymethylphenyl)일 수 있다.At least two of R5, R6, R10 and R11 may be a vinyl group, an acryloyl group, a methacyloyl group, a cyclic ethers, a siloxanes, Lt; RTI ID = 0.0 > crosslinked < / RTI > For example, the substituent having the above-mentioned crosslinking property may be a vinylphenyl group (4-vinylphenyl), a vinylbenzyloxymetaphenyl group (4- (4-vinylbenzyl) oxymethylphenyl) represented by the following Chemical Formula 2-1 and Chemical Formula 2-2 .
화학식2(2) -1-One
화학식2(2) -2-2
또한, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 중 가교 결합 특성을 갖는 치환체를 포함하는 것을 제외한 나머지의 치환체는 메틸(methyl), 에틸(ethyl), n-프로필(n-propyl), i-프로필(i-propyl), n-부틸(n-butyl), i-부틸(i-butyl) 및 t-부틸(t-butyl) 등과 같은 C1~C6 의 알킬 그룹(alkyl)과 시아닐(cyanyl), 트리메틸실릴(trimethylsilyl), 플루오린(fluorine), 트리플루오로메틸(trifluoromethyl), 중수소(deuterium) 중 어느 하나일 수 있다.
The substituents other than the substituents having the crosslinking property among R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 include methyl, ethyl, C 1 -C 6 alkyl such as n-propyl, i-propyl, n-butyl, i-butyl and t- May be any one of alkyl and cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium.
전술한 바와 같이 본 발명의 실시예에 따른 정공수송물질은 카바졸 유도체 중심부에 가교결합이 가능한 물질이 링커(linker)에 의해 연결된 구조를 가지며, 유기 용매에 뛰어난 용해도를 갖기 때문에 용액공정에 의해 정공수송층을 형성할 수 있다.As described above, the hole transport material according to the embodiment of the present invention has a structure in which a substance capable of crosslinking is connected to the center of the carbazole derivative by a linker and has excellent solubility in an organic solvent. Therefore, A transport layer can be formed.
또한, 경화 공정 후 가교결합 발생에 의해 유기 용매에 대한 용해도를 상실하게 되기 때문에, 추후 공정에서의 유기 용매에 손상을 받지 않게 된다.
Further, since the solubility in the organic solvent is lost by the occurrence of crosslinking after the curing process, the organic solvent in the subsequent step is not damaged.
상기 화학식1로 표시된 본 발명의 정공수송물질은 아래 화학식3에 표시된 다수의 물질 중 하나일 수 있다. 설명의 편의를 위해 각 물질 하단에 A1~A148의 기호를 부여하였다.The hole transport material of the present invention represented by Formula 1 may be one of a plurality of materials represented by Formula 3 below. For convenience of explanation, symbols A1 to A148 were assigned to the bottom of each material.
화학식3(3)
이하에서는, 본 발명에 따른 유기전계발광소자용 정공수송물질 중, 상기 화학식3에서 A-1로 표기된 정공수송물질을 예로 들어 합성예을 설명한다.Hereinafter, a hole-transporting material represented by A-1 in Formula 3 will be described as an example of the hole transporting material for an organic electroluminescence device according to the present invention.
합성예Synthetic example
1. 9-phenyl-9H-carbazole의 합성1. Synthesis of 9-phenyl-9H-carbazole
9-phenyl-9H-carbazole은 아래와 같은 반응식1에 의해 합성된다.9-phenyl-9H-carbazole is synthesized by the following reaction formula 1.
반응식1Scheme 1
구체적으로, 2구 둥근 바닥 플라스크 (two-necked round-bottomed flask)에 carbazole(25mmol), iodobenzene (30mmol), CuI (1.25mmol), trans-1,2-diaminocyclohexane (6.25mmol)과 K3PO4 (100mmol)를 1,4-dioxane(125mL)에 녹인 후, 130 ℃의 bath에서 24시간 교반시켰다. 반응 종료 후 1,4-dioxane을 제거하고 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류하고 Dichloromethane과 Methanol을 이용하여 재결정하여 여과(filter)함으로써 고체 9-phenyl-9H-carbazole 5g을 얻었다.
Specifically, carbazole (25mmol), iodobenzene (30mmol), CuI (1.25mmol), trans-1,2-diaminocyclohexane (6.25mmol) and K3PO4 (100mmol) were added to a two- necked round-bottomed flask. Was dissolved in 1,4-dioxane (125 mL), and the mixture was stirred in a bath at 130 ° C for 24 hours. After completion of the reaction, 1,4-dioxane was removed, and the mixture was extracted with dichloromethane and water, followed by distillation under reduced pressure. After the silica gel column, the solvent was distilled off under reduced pressure, and recrystallized from dichloromethane and methanol to obtain solid 9-phenyl-9H-carbazole (5 g).
2. 3,6-dibromo-9-phenyl-9H-carbazole의 합성2. Synthesis of 3,6-dibromo-9-phenyl-9H-carbazole
3,6-dibromo-9-phenyl-9H-carbazole은 아래와 같은 반응식2에 의해 합성된다.3,6-dibromo-9-phenyl-9H-carbazole is synthesized by the following Reaction Formula 2.
반응식2Scheme 2
구체적으로, 2구 둥근 바닥 플라스크에 9-phenyl-9H-carbazole (20mmol)를 Acetic Acid (125mmol)에 녹인 후, 주사기를 이용하여 bromine (45mmol)을 Acetic Acid(5ml)가 들어있는 반응용기에 투입한다. 상온에서 반응용기를 1시간 교반시킨 후 반응을 종료한다. 물과 NaOH를 이용하여 중화시킨 후, 여과하고 Ethanol로 2~3회 씻어준다. Hexane과 Dichloromathane을 이용하여 silica gel column 후 Dichloromethane과 Methanol을 이용하여 재결정하고 여과하여 고체 3,6-dibromo-9-phenyl-9H-carbazole 6g을 얻었다.
Specifically, 9-phenyl-9H-carbazole (20 mmol) was dissolved in acetic acid (125 mmol) in a two-necked round bottom flask and bromine (45 mmol) was injected into a reaction vessel containing 5 ml of acetic acid using a syringe do. After the reaction vessel is stirred at room temperature for 1 hour, the reaction is terminated. Neutralize with water and NaOH, filter and rinse with ethanol 2-3 times. Hexane and dichloromathane were used for silica gel column. After recrystallization with dichloromethane and methanol, 6 g of solid 3,6-dibromo-9-phenyl-9H-carbazole was obtained.
3. N3,N6-di(naphthalen-1-yl)-9-phenyl-9H-carbazole-3,6-diamine의 합성3. Synthesis of N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine
N3,N6-di(naphthalen-1-yl)-9-phenyl-9H-carbazole-3,6-diamine은 아래와 같은 반응식3에 의해 합성된다.N 3, N 6 -di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine is synthesized by the following reaction formula 3.
반응식3Scheme 3
구체적으로, 2구 둥근 바닥 플라스크에 3,6-dibromo-9-phenyl-9H-carbazole (10mmol), 1-naphthylamine(22mmol), Tris(dibenzylideneacetone) dipalladium(0)(0.3mmol), (±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene(0.6mmol)과 Sodium tert-butoxide(28mmol)를 Toluene(30mL)에 녹인 후, 100 ℃의 bath에서 24시간 교반시켰다. 반응 종료 후 Toluene을 제거하고 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류하여 고체 N3,N6-di(naphthalen-1-yl)-9-phenyl-9H-carbazole-3,6-diamine 5.5g을 얻었다.
Specifically, 3-dibromo-9-phenyl-9H-carbazole (10 mmol), 1-naphthylamine (22 mmol), Tris (dibenzylideneacetone) dipalladium (0) Bis (diphenylphosphino) -1,1'-binaphthalene (0.6 mmol) and sodium tert-butoxide (28 mmol) were dissolved in 30 ml of toluene and the mixture was stirred at 100 ° C for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. The silica gel column was distilled under reduced pressure to obtain 5.5 g of solid N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine.
4. (4-bromobenzyloxy)(tert-butyl)dimethylsilane의 합성4. Synthesis of (4-bromobenzyloxy) (tert-butyl) dimethylsilane
(4-bromobenzyloxy)(tert-butyl)dimethylsilane는 아래와 같은 반응식4에 의해 합성된다.(4-bromobenzyloxy) (tert-butyl) dimethylsilane is synthesized by the following reaction formula (4).
반응식4Scheme 4
구체적으로, 2구 둥근 바닥 플라스크에 4-bromobenzylalcohol (30mmol), tert-butylchlorodimethylsilane(36mmol)를 N,N-Dimethylformamide(DMF) (50ml)에 녹인 후, 0 ℃에서 주사기를 이용하여 imidazole (45mmol)을 DMF에 녹여 반응용기에 투입한다. 반응용기를 상온으로 조정하고, 24시간 교반시킨 후 반응을 종료한다. Hexane과 물을 사용하여 추출한 후 감압 증류하고 silica gel column 후 용매를 감압 증류하여 투명한 액체 (4-bromobenzyloxy)(tert-butyl)dimethylsilane 8.6g을 얻었다.
Specifically, 4-bromobenzylalcohol (30 mmol) and tert-butylchlorodimethylsilane (36 mmol) were dissolved in N, N-dimethylformamide (DMF) (50 ml), and imidazole (45 mmol) Dissolve in DMF and put into reaction vessel. The reaction vessel is adjusted to room temperature, stirred for 24 hours, and then the reaction is terminated. After extraction with hexane and water, the mixture was distilled under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure to obtain 8.6 g of 4-bromobenzyloxy (tert-butyl) dimethylsilane.
5. (N-((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(N-1-naphthyl)-amine의 합성5. Synthesis of (N - (4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl)
(N-((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(N-1-naphthyl)-amine은 아래와 같은 반응식5에 의해 합성된다.(N - (4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl) -amine is synthesized by the following reaction formula 5.
반응식5Scheme 5
구체적으로, 2구 둥근 바닥 플라스크에 (4-bromobenzyloxy)(tert-butyl)dimethylsilane (20mmol), 1-naphthylamine(22mmol), Tris(dibenzylideneacetone) dipalladium(0)(0.15mmol), (±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene(0.3mmol)과 Sodium tert-butoxide(14mmol)를 Toluene(30mL)에 녹인 후, 100 ℃의 bath에서 24시간 교반시켰다. 반응 종료 후 Toluene을 제거하고 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류하여 액체 (N-((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(N-1-naphthyl)-amine 4.7g을 얻었다.
Specifically, a 2-neck round bottom flask was charged with 4-bromobenzyloxy (tert-butyl) dimethylsilane (20 mmol), 1-naphthylamine (22 mmol), Tris (dibenzylideneacetone) dipalladium (0) 2'-Bis (diphenylphosphino) -1,1'-binaphthalene (0.3 mmol) and sodium tert-butoxide (14 mmol) were dissolved in 30 mL of toluene and stirred in a bath at 100 ° C. for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure to obtain 4.7 g of a liquid (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl) -amine.
6. 4-bromo-4'-((((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(1-naphthyl)amino)biphenyl의 합성6. Synthesis of 4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl
4-bromo-4'-((((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(1-naphthyl)amino)biphenyl은 아래와 같은 반응식6에 의해 합성된다.4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl is synthesized by the following reaction scheme 6.
반응식6Scheme 6
구체적으로, 2구 둥근 바닥 플라스크에 (N-((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(N-1-naphthyl)-amine(10mmol), 4,4'-dibromobiphenyl(11mmol), Tris(dibenzylideneacetone) dipalladium(0)(0.15mmol), tri-tert-butylphosphine(0.3mol)과 Sodium tert-butoxide(14mmol)를 Toluene(30mL)에 녹인 후, 100 ℃의 bath에서 24시간 교반시켰다. 반응 종료 후 Toluene을 제거하고 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류하여 고체 4-bromo-4'-((((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(1-naphthyl)amino)biphenyl 2.3g를 얻었다.
Specifically, a 2-necked round bottom flask was charged with (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl- (N-1-naphthyl) -amine (10 mmol), 4,4'-dibromobiphenyl dibenzylideneacetone dipalladium (0) (0.15 mmol), tri-tert-butylphosphine (0.3 mol) and sodium tert-butoxide (14 mmol) were dissolved in 30 mL of toluene and the mixture was stirred at 100 ° C. for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled under reduced pressure to obtain 2.3 g of solid 4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl.
7. 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(((4-tert-butyl)dimethylsilyloxymethyl)phenyl)))amino)phenyl)phenylcarbazole-3,6-diamine의 합성7. A process for the preparation of 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 1 -naphthyl- ) phenyl))) amino) phenyl) phenylcarbazole-3,6-diamine
9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(((4-tert-butyl)dimethylsilyloxymethyl)phenyl)))amino)phenyl)phenylcarbazole-3,6-diamine은 아래와 같은 반응식7에 의해 합성된다.9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (4- (N- 1 -naphthyl- ))) amino) phenyl) phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (7).
반응식7Scheme 7
구체적으로, 2구 둥근 바닥 플라스크에 N3,N6-di(naphthalen-1-yl)-9-phenyl-9H-carbazole-3,6-diamine(5mmol), 4-bromo-4'-((((4-tert-butyl)dimethylsilyloxymethyl)phenyl)-(1-naphthyl)amino)biphenyl(11mmol), Tris(dibenzylideneacetone) dipalladium(0)(0.15mmol), tri-tert-butylphosphine(0.3mol)과 Sodium tert-butoxide(14mmol)를 Toluene(30mL)에 녹인 후, 100 ℃의 bath에서 24시간 교반시켰다. 반응 종료 후 Toluene을 제거하고 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류한 후 Dichloromethane과 Methanol를 사용하여 재결정하고 여과하여 고체 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(((4-tert-butyl)dimethylsilyloxymethyl)phenyl)))amino)phenyl)phenylcarbazole-3,6-diamine 4.5g를 얻었다.
Specifically, in a two-neck round bottom flask, N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine (5 mmol), 4-bromo- Tris (dibenzylideneacetone) dipalladium (0) (0.15 mmol), tri-tert-butylphosphine (0.3 mol) and sodium tert-butoxide (14 mmol) were dissolved in toluene (30 mL), and the mixture was stirred in a bath at 100 ° C for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure, then recrystallized with dichloromethane and methanol and filtered to obtain solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6- N-1-naphthyl- (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine.
8. 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-hydroxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine의 합성N, N-di (4- (4- (N-1-naphthyl- (N- (4-hydroxymethyl) phenyl) amino) phenyl) phenylcarbazole-3,6-diamine
9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-hydroxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine은 아래와 같은 반응식8에 의해 합성된다.Phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 1-naphthyl- phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (8).
반응식8Scheme 8
구체적으로, 2구 둥근 바닥 플라스크에 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(((4-tert-butyl)dimethylsilyloxymethyl)phenyl)))amino)phenyl)phenylcarbazole-3,6-diamine (2mmol), tetrabutylammonium fluoride(TBAF) (4.8ml,1M solution)를 THF(20mL)에 녹인 후, 상온에서 24시간 교반시켰다. 반응 종료 후 THF를 제거하고 Hexane과 ethyl acetate를 이용하여 silica gel column 후 용매를 감압 증류하였다. Dichloromethane과 Methanol를 사용하여 재결정하고 여과하여 고체 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-hydroxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine 2.4g를 얻었다.
Specifically, a 2-neck round bottom flask was charged with 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- Tetrabutylammonium fluoride (TBAF) (4.8 ml, 1 M solution) was dissolved in THF (20 ml), and the solution was stirred at room temperature And stirred for 24 hours. After completion of the reaction, the THF was removed, and the solvent was distilled off under a silica gel column using hexane and ethyl acetate. Recrystallization using dichloromethane and methanol and filtration gave a solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 4-hydroxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine.
9. 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-(4-vinylbenzyl)oxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine의 합성N 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (4- (N- phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine
상기 화학식3에서 A-1로 표시된 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-(4-vinylbenzyl)oxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine은 아래와 같은 반응식9에 의해 합성된다.N-di (4- (4- (N-1-naphthyl- (N- (4-fluorophenyl) (4-vinylbenzyl) oxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (9).
반응식9Scheme 9
구체적으로, 2구 둥근 바닥 플라스크에 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-hydroxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine (1mmol), NaH (3mmol)를 DMF(30mL)에 녹인 후, 상온에서 1시간 교반을 시키고, 0 ℃로 온도를 낮춘 후 주사기를 이용하여 4-Vinylbenzyl chloride (3mmol)을 넣었다. 100 ℃의 bath에서 24시간 교반시킨 후 반응이 종료 되면 Dichloromethane과 물을 사용하여 추출한 후 감압 증류하였다. silica gel column 후 용매를 감압 증류하고 Dichloromethane과 Methanol를 이용하여 재결정하고 여과하여 고체 9-phenyl-N3,N6-di(naphthalen-1-yl)-N3,N6-di(4-(4-(N-1-naphthyl-(N-(4-(4-vinylbenzyl)oxymethyl)phenyl))amino)phenyl)phenylcarbazole-3,6-diamine 0.9g를 얻었다.
Specifically, a 2-necked round bottom flask was charged with 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (1 mmol) and NaH (3 mmol) were dissolved in DMF (30 mL). The mixture was stirred at room temperature for 1 hour, cooled to 0 ° C., and then injected into a syringe 4-vinylbenzyl chloride (3 mmol) was added thereto. After stirring for 24 hours at 100 ° C, the reaction mixture was extracted with dichloromethane and water and distilled under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure, recrystallized with dichloromethane and methanol and filtered to obtain solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, -1-naphthyl- (N- (4- (4-vinylbenzyl) oxymethyl) phenyl) amino) phenyl) phenylcarbazole-3,6-diamine 0.9 g.
이하, 상기한 본 발명에 따른 유기전계발광소자용 정공수송물질을 이용하여 유기전계발광소자를 제작하는 실험예1 내지 실험예3을 통해, 본 발명에 의한 정공수송물질 및 이를 이용한 유기전계발광소자의 성능을 비교 설명한다.Hereinafter, examples 1 through 3 of the organic electroluminescent device using the hole transport material for an organic electroluminescent device according to the present invention will be described. The hole transport material of the present invention and the organic electroluminescent device To compare the performance.
실험예1Experimental Example 1
기판 상에 인듐-틴-옥사이드(ITO)층의 발광 면적이 3mm X 3mm 크기가 되도록 패터닝한 후 세정하였다. 상기 기판을 Spin Coater에 장착한 후 ITO층 위에 하기 화학식4-1 및 4-2로 표시된 PEDOT:PSS를 spin-coating(500Å)한다. 150℃의 Hot plate에 10분간 건조시켜 용매를 제거한 다음, 정공수송물질 A-1을 자일렌(xylene)에 녹여 spin-coating(300Å)한다. 100℃의 Hot plate에 10분간 건조시킨 후, 200℃에서 30분간 가열하여 가교결합(cross-linking)시킨다. 하기 화학식4-3으로 표시된 호스트 AND와 하기 화학식4-4로 표시된 도펀트DPAVBi(4%)를 자일렌에 녹인 용액을 spin-coating하고 (300Å) 100℃의 Hot plate에 10분간 건조시킨 후, 진공 챔버에 장착하고 base pressure가 1X10-6torr가 되도록 한 후, Alq3(350Å), LiF(5Å), Al(500Å)의 순서로 성막하였다. The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-1 is dissolved in xylene and spin-coated (300 Å). Dried on a hot plate at 100 ° C for 10 minutes, and then cross-linked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 -6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.
9mA/cm2에서 473cd/m2(5.3V)를 나타내었으며 이때 CIE x = 0.137, y = 0.239, 1000nit에서 T(50)=762hr를 나타내었다. 여기서, T(50)은 휘도가 절반이 되는 시간이다.
Exhibited a 9mA / in cm 2 473cd / m 2 (5.3V ) The CIE x = 0.137, y = 0.239 , it exhibited a T (50) = 762hr in 1000nit. Here, T (50) is a time at which the luminance becomes half.
실험예2Experimental Example 2
기판 상에 인듐-틴-옥사이드(ITO)층의 발광 면적이 3mm X 3mm 크기가 되도록 패터닝한 후 세정하였다. 상기 기판을 Spin Coater에 장착한 후 ITO층 위에 하기 화학식4-1 및 4-2로 표시된 PEDOT:PSS를 spin-coating(500Å)한다. 150℃의 Hot plate에 10분간 건조시켜 용매를 제거한 다음, 정공수송물질 A-49을 자일렌에 녹여 spin-coating(300Å)한다. 100℃의 Hot plate에 10분간 건조시킨 후, 200℃에서 30분간 가열하여 가교결합시킨다. 하기 화학식4-3으로 표시된 호스트 AND와 하기 화학식4-4로 표시된 도펀트DPAVBi(4%)를 자일렌에 녹인 용액을 spin-coating하고 (300Å) 100℃의 Hot plate에 10분간 건조시킨 후, 진공 챔버에 장착하고 base pressure가 1X10-6torr가 되도록 한 후, Alq3(350Å), LiF(5Å), Al(500Å)의 순서로 성막하였다. The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-49 is dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 -6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.
9mA/cm2에서 443cd/m2(5.4V)를 나타내었으며 이때 CIE x = 0.145, y = 0.236, 1000nit에서 T(50)=721hr를 나타내었다.
Exhibited a 9mA / in cm 2 443cd / m 2 (5.4V ) The CIE x = 0.145, y = 0.236 , it exhibited a T (50) = 721hr in 1000nit.
실험예3Experimental Example 3
기판 상에 인듐-틴-옥사이드(ITO)층의 발광 면적이 3mm X 3mm 크기가 되도록 패터닝한 후 세정하였다. 상기 기판을 Spin Coater에 장착한 후 ITO층 위에 하기 화학식4-1 및 4-2로 표시된 PEDOT:PSS를 spin-coating(500Å)한다. 150℃의 Hot plate에 10분간 건조시켜 용매를 제거한 다음, 정공수송물질 A-61를 자일렌(xylene)에 녹여 spin-coating(300Å)한다. 100℃의 Hot plate에 10분간 건조시킨 후, 200℃에서 30분간 가열하여 가교결합시킨다. 하기 화학식4-3으로 표시된 호스트 AND와 하기 화학식4-4로 표시된 도펀트 DPAVBi(4%)를 자일렌에 녹인 용액을 spin-coating하고 (300Å) 100℃의 Hot plate에 10분간 건조시킨 후, 진공 챔버에 장착하고 base pressure가 1X10-6torr가 되도록 한 후, Alq3(350Å), LiF(5Å), Al(500Å)의 순서로 성막하였다. The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-61 is dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 -6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.
9mA/cm2에서 561cd/m2(5.1V)를 나타내었으며 이때 CIE x = 0.143, y = 0.225, 1000nit에서 T(50)=890hr를 나타내었다.
Exhibited a 9mA / in cm 2 561cd / m 2 (5.1V ) The CIE x = 0.143, y = 0.225 , it exhibited a T (50) = 890hr in 1000nit.
비교예Comparative Example
기판 상에 인듐-틴-옥사이드(ITO)층의 발광 면적이 3mm X 3mm 크기가 되도록 패터닝한 후 세정하였다. 상기 기판을 Spin Coater에 장착한 후 ITO층 위에 하기 화학식4-1 및 4-2로 표시된 PEDOT:PSS를 spin-coating(500Å)한다. 150℃의 Hot plate에 10분간 건조시켜 용매를 제거한 다음, 하기 화학식4-5로 표시된 정공수송물질 2-NPD를 자일렌에 녹여 spin-coating(300Å)한다. 100℃의 Hot plate에 10분간 건조시킨 후, 200℃에서 30분간 가열하여 가교결합시킨다. 하기 화학식4-3으로 표시된 호스트 AND와 하기 화학식4-4로 표시된 도펀트 DPAVBi(4%)를 자일렌에 녹인 용액을 spin-coating하고 (300Å) 100℃의 Hot plate에 10분간 건조시킨 후, 진공 챔버에 장착하고 base pressure가 1X10-6torr가 되도록 한 후, Alq3(350Å), LiF(5Å), Al(500Å)의 순서로 성막하였다. The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After the solvent was removed by drying on a hot plate at 150 ° C for 10 minutes, the hole transport material 2-NPD represented by the following chemical formula 4-5 was dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 -6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.
9mA/cm2에서 422cd/m2(5.5V)를 나타내었으며 이때 CIE x = 0.137, y = 0.241, 1000nit에서 T(50)=640hr를 나타내었다.
Exhibited a 9mA / in cm 2 422cd / m 2 (5.5V ) The CIE x = 0.137, y = 0.241 , it exhibited a T (50) = 640hr in 1000nit.
화학식4Formula 4 -1-One
화학식4Formula 4 -2-2
화학식4Formula 4 -3-3
화학식4Formula 4 -4-4
화학식4Formula 4 -5-5
상술한 실험예1 내지 실험예3과 비교예의 비교결과를 아래 표에 나타내었다. 여기서 전압의 단위는 V, 전류의 단위는 mA, 휘도의 단위는 cd/m2, 전류효율의 단위는 cd/A, 전력효율의 단위는 lm/W, T(50)의 단위는 시간(hr)이다.The comparison results of the above-described Experimental Examples 1 to 3 and Comparative Examples are shown in the following table. The unit of voltage is V, the unit of current is mA, the unit of luminance is cd / m2, the unit of current efficiency is cd / A, the unit of power efficiency is lm / W, the unit of T (50) to be.
표1에서 알 수 있는 바와 같이, 실험예1 내지 실험예3은 카바졸 중심부 유도체를 도입함으로써 비교예에 비해 약 5~30% 정도 효율이 향상되었다. 즉, 정공수송 특성이 향상되었다. 또한 수명이 15~40%정도 향상되었다. 따라서 본 발명의 정공수송물질를 이용하여 코팅 방법에 의해 대면적 소자의 제조가 가능하며 발광효율이 뛰어나고 수명이 향상된 유기전계발광소자를 제공할 수 있다.
As can be seen from Table 1, the efficiency of Experiments 1 to 3 was improved by about 5 to 30% as compared with Comparative Example by introducing the carbazole core derivative. That is, the hole transporting property was improved. Also, the life span was improved by 15 ~ 40%. Accordingly, it is possible to provide an organic electroluminescent device capable of manufacturing a large-area device by a coating method using the hole transporting material of the present invention, and having excellent luminous efficiency and improved lifetime.
상기한 정공수송물질을 포함하여 이루어지는 유기전계발광소자에 대한 일 실시예를 도 1에 도시하였다.An embodiment of an organic electroluminescent device including the above hole transporting material is shown in FIG.
도시한 바와 같이, 유기전계발광소자는 서로 마주보는 제 1 및 제 2 기판(미도시)과, 상기 제 1 및 제 2 기판(미도시) 사이에 형성되어 있는 유기발광다이오드(E)를 포함한다.As shown, the organic electroluminescent device includes first and second substrates (not shown) facing each other, and an organic light emitting diode (E) formed between the first and second substrates (not shown) .
상기 유기발광다이오드(E)는 양극 역할을 하는 제 1 전극(110), 음극 역할을 하는 제 2 전극(130) 및 상기 제 1 및 제 2 전극(110, 130) 사이에 형성되는 유기발광층(120)으로 이루어진다. The organic light emitting diode E includes a first electrode 110 serving as an anode, a
상기 제 1 전극(110)은 일함수 값이 비교적 높은 물질, 예를 들어, 인듐-틴-옥사이드(ITO)로 이루어지며, 상기 제 2 전극(130)은 일함수 값이 비교적 낮은 물질, 예를 들어, 알루미늄(Al) 또는 알루미늄 합금(AlNd)로 이루어진다. 또한, 상기 유기발광층(120)은 적색, 녹색, 청색은 유기발광패턴으로 이루어진다.The first electrode 110 is made of a relatively high work function material such as indium-tin-oxide (ITO), and the
상기 유기발광층(120)은 발광효율을 극대화하기 위해, 다중층 구조 즉, 제 1 전극(110)으로부터 순차적으로 정공주입층(hole injection layer; HTL) (121), 정공수송층(hole transporting layer; HIL) (122), 발광물질층(emitting material layer; EML) (123), 전자수송층(electron transporting layer)(124) 및 전자주입층(electron injection layer)(125)으로 이루어진다.The organic
여기서, 상기 정공수송층(122)은 상기 화학식1로 표시된 정공수송물질을 포함하여 이루어진다. 전술한 바와 같이, 정공수송물질은 자일렌과 같은 유기 용매에 녹여 스핀코팅 방법 등에 의해 상기 정공수송층(122)을 형성하게 되고 열 또는 빛에 의한 경화 공정에 의해 가교결합이 발생하면 유기 용매에 대한 용해 특성을 갖지 않게 된다. 따라서 상기 정공수송층(122) 형성 후 상기 발광물질층(123)을 스핀코팅 방법에 의해 형성하는 경우, 유기 용매에 의해 상기 정공수송층(122)에 손상이 발생하는 것이 방지된다. 예를 들어, 상기 정공수송층(122)은 스핀코팅(spin-coating) 공정, 노즐프린팅(nozzle-printing) 공정, 잉크젯프린팅(inkjet-printing) 공정, 슬롯코팅(slot-coating) 공정, 딥코팅(dip-coating) 공정, 롤투롤(roll-to-roll) 공정 등에 의해 형성될 수 있다.Here, the
이와 같은 구성의 유기전계발광소자는 정공수송물질을 코팅하여 상기 정공수송층(122)을 형성하기 때문에, 대면적 유기전계발광소자의 제조에 장점을 갖는다. 또한, 발광효율이 향상되어 저전력구동이 가능하며 수명이 향상되는 장점을 갖는다.
The organic electroluminescent device having such a structure has advantages in manufacturing a large area organic electroluminescent device because the hole transporting material is coated to form the
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 본 발명의 기술적 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It can be understood that
110: 제 1 전극
120: 유기발광층
121: 정공주입층
122: 정공수송층
123: 발광물질층
124: 전자수송층
125: 전자주입층
130: 제 2 전극110: first electrode
120: organic light emitting layer
121: Hole injection layer
122: hole transport layer
123: luminescent material layer
124: electron transport layer
125: electron injection layer
130: second electrode
Claims (14)
R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택되며, L은 탄소(C), 산소(O)또는 황(S)에서 선택되며, m은 0또는 1의 정수이고, n은 1~3의 정수이며, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes) 중 적어도 하나를 포함하여 가교 결합 특성을 갖는 것이 특징인 유기전계발광소자용 정공수송물질.
Is represented by the following formula,
R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A polycyclic aromatic group or polycyclic heterocyclic group of C30 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 a cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, and R2, R3, R7, R8 Each independently represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted arylene group of C5 to C30, a hetero-arylene group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C30 An alkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30, L is selected from the group consisting of carbon (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and at least two of R5, R6, R10 and R11 are selected from the group consisting of vinyl wherein the organic electroluminescent material has cross-linking properties including at least one of acryloyl group, methacyloyl group, cyclic ethers, and siloxanes. Hole transport material for devices.
상기 C1~C20까지의 치환 또는 비치환된 알킬기 그룹은 메틸기, 에틸기, 프로필기, 아이스프로필기, 뷰틸기, sec-뷰틸기, tert-뷰틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 데카닐기, 옥타데카닐기, 스테아릴기, 2-페닐아이소프로필기, 트라이클로로메틸기, 트라이플루오로메틸기, 벤질기, α-페녹시벤질기, α-다이메틸벤질기, α-메틸페닐벤질기, α-다이트라이플루오로메틸벤질기, 트라이페닐메틸기, α-벤질옥시벤질기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The C1 to C20 substituted or unsubstituted alkyl group group is preferably a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -dithifluoromethylbenzyl group, a triphenylmethyl group,? -benzyloxybenzyl group, and a hole transporting material for an organic electroluminescence device.
상기 C5~C30의 치환 또는 비치환된 아릴기 그룹은 페닐기, 2-메틸페닐기, 3-메틸페닐기, 4-메틸페닐기, 펜타듀트륨페닐기, 2-트리메틸실릴페닐기, 3-트리메틸실릴페닐기, 4-트리메틸실릴페닐기, 3,5-다이플루오로페닐기, 4-에틸페닐기, 바이페닐기, 4-메닐바이페닐기, 4-에틸바이페닐기, 4-사이클로헥실바이페닐기, 터페닐기, 3,5-다이클로로페닐기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A 4-ethylhexylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, a 3,5-dichlorophenyl group, Transporting material for an organic electroluminescence element.
상기 C3~C30의 다환성 방향족 또는 이형고리 그룹은 나프틸기, 1-메틸나프틸기, 2-메틸나프틸기, 아세나프틸기, 안트라세닐기, 풀루오레닐기, 페날닐기, 페난스레닐기, 파이렌닐기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The C3 to C30 polycyclic aromatic or aliphatic ring group is preferably a naphthyl group, a 1-methylnaphthyl group, a 2-methylnaphthyl group, an acenaphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group, a phenanthrenyl group, Transporting material for an organic electroluminescence element.
상기 C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹은 벤질기, 1-페닐에틸기, 2-페닐에틸기, 1-페닐아이소프로필기, 2-페닐아이소프로필기, 페닐-t-뷰틸기, α-나프틸메틸기, 1-α-나프틸에틸기, 2-α-나프틸에틸기, 1-α-나프틸아이소프로필기, 2-α-나프틸아이소프로필기, β-나프틸메틸기, 1-β-나프틸에틸기, 2-β-나프틸에틸기, 1-β-나프틸아이소프로필기, 2-β-나프틸아이소프로필기, 1-피롤릴메틸기, 2-(1-피롤릴)에틸기, p-메틸벤질기, m-메틸벤질기, o-메틸벤질기, p-클로로벤질기, m-클로로벤질기, o-클로로벤질기, p-브로모벤질기, m-브로모벤질기, o-브로모벤질기, p-아이오도벤질기, m-아이오도벤질기, o-아이오도벤질기, p-하이드록시벤질기, m-하이드록시벤질기, o-하이드록시벤질기, p-아미노벤질기, m-아미노벤질기, o-아미노벤질기, p-나이트로벤질기, m-나이트로벤질기, o-나이트로벤질기, p-사이아노벤질기, m-사이아노벤질기, o-사이아노벤질기, 1-하이드록시-2-페닐아이소프로필기, 1-클로로-2-페닐아이소프로필기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, o-methylbenzyl group, A p-hydroxybenzyl group, an m-hydroxybenzyl group, an o-hydroxybenzyl group, a p-iodobenzyl group, a p-iodobenzyl group, Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitro Benzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy- Wherein the electron transporting material comprises a propyl group.
상기 C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹은 사이클로프로필기, 사이클로뷰틸기, 사이클로펜틸기, 사이클로헥실기, 노보넨기, 아다만틸기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The substituted or unsubstituted cycloalkyl group of C3 to C30 includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group, and an adamantyl group. .
상기 C1~C20의 치환 또는 비치환된 알콕시기 그룹은 메톡시기, 에톡시기, 프로폭시기, 아이소프로폭시기, 뷰톡시기, 아이소뷰톡시기, sec-뷰톡시기, tert-뷰톡시기, 헵틸옥시기, 헥실옥시기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
The substituted or unsubstituted C1-C20 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, A hole transporting material for an organic electroluminescence device, and a hexyloxy group.
상기 C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹은 페녹시기, 톨릴옥시기, 나프틸옥시기를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
Wherein the C6 to C20 substituted or unsubstituted aryloxy group group comprises a phenoxy group, a tolyloxy group, and a naphthyloxy group.
상기 R5, R6, R10, R11 중 적어도 두개는 비닐페닐기(4-vinylphenyl), 비닐벤질옥시메타페닐기(4-(4-vinylbenzyl)oxymethylphenyl) 중 적어도 어느 하나의 치환체를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
Wherein at least two of R5, R6, R10 and R11 include at least one substituent selected from the group consisting of 4-vinylphenyl and 4- (4-vinylbenzyl) oxymethylphenyl. Hole transport material for devices.
상기 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 중에서 상기 R5, R6, R10, R11 중 적어도 두개를 제외한 나머지는 메틸(methyl), 에틸(ethyl), n-프로필(n-propyl), i-프로필(i-propyl), n-부틸(n-butyl), i-부틸(i-butyl) 및 t-부틸(t-butyl) 등과 같은 C1~C6 의 알킬 그룹(alkyl)과 시아닐(cyanyl), 트리메틸실릴(trimethylsilyl), 플루오린(fluorine), 트리플루오로메틸 (trifluoromethyl), 중수소(deuterium) 중 어느 하나의 치환체를 포함하는 것이 특징인 유기전계발광소자용 정공수송물질.
The method according to claim 1,
R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10 and R 11 are other than methyl, ethyl, n- A C1 to C6 alkyl group such as n-propyl, i-propyl, n-butyl, i-butyl and t- wherein the organic compound contains a substituent selected from the group consisting of alkyl and cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium. Hole transport material.
상기 제 1 전극과 마주보는 제 2 전극과;
상기 제 1 및 제 2 전극 사이에 위치하는 발광물질층과;
상기 제 1 전극과 상기 발광물질층 사이에 위치하는 정공수송층을 포함하고,
상기 정공수송층은, 하기 화학식으로 표시되며,
R1, R4, R5, R6, R9, R10, R11은 각각 C1~C20까지의 치환 또는 비치환된 알킬기 그룹(alkyl group), C5~C30의 치환 또는 비치환된 아릴기 그룹(aryl group), C3~C30의 다환성 방향족 또는 이형고리 그룹(polycyclic aromatic group or polycyclic heterocyclic group), C6~C30까지의 치환 또는 비치환된 아르알킬기 그룹(arylalkyl group), C3~C30의 치환 또는 비치환된 사이클로알킬기 그룹 (cycloalkyl group), C1~C20의 치환 또는 비치환된 알콕시기 그룹 (alkoxy group), C6 ~C20의 치환 또는 비치환된 아릴옥시기 그룹 (aryloxy group)로부터 선택되고, R2, R3, R7, R8은 각각 C1~C20까지의 치환 또는 비치환된 알킬렌기 그룹, C5~C30의 치환 또는 비치환된 아릴렌기 그룹, C3~C30의 헤테로-아릴렌기 그룹, C6~C30까지의 치환 또는 비치환된 아릴알킬렌기 그룹, C3~C30의 치환 또는 비치환된 사이클로알킬렌기 그룹로부터 선택되며, L은 탄소(C), 산소(O)또는 황(S)에서 선택되며, m은 0또는 1의 정수이고, n은 1~3의 정수이며, R5, R6, R10, R11 중 적어도 두개는 비닐기(vinyl group), 아크릴로일(acryloyl group), 메타아크릴로일(methacyloyl group), 사이크릭이서(cyclic ethers), 실로세인(siloxanes) 중 적어도 하나를 포함하여 가교 결합 특성을 갖는 정공수송물질로 이루어지는 것이 특징인 유기전계발광소자.
A first electrode;
A second electrode facing the first electrode;
A light emitting material layer disposed between the first and second electrodes;
And a hole transport layer disposed between the first electrode and the light emitting material layer,
The hole transport layer is represented by the following formula,
R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A polycyclic aromatic group or polycyclic heterocyclic group of C30 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 a cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, and R2, R3, R7, R8 Each independently represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted arylene group of C5 to C30, a hetero-arylene group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C30 An alkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30, L is selected from the group consisting of carbon (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and at least two of R5, R6, R10 and R11 are selected from the group consisting of vinyl a hole transporting material having at least one of acryloyl group, methacyloyl group, cyclic ethers and siloxanes and having crosslinking properties, Organic electroluminescent device.
상기 R5, R6, R10, R11 중 적어도 두개는 비닐페닐기(4-vinylphenyl), 비닐벤질옥시메타페닐기(4-(4-vinylbenzyl)oxymethylphenyl) 중 적어도 어느 하나의 치환체를 포함하는 것이 특징인 유기전계발광소자.
12. The method of claim 11,
Wherein at least two of R5, R6, R10 and R11 include at least one substituent selected from the group consisting of 4-vinylphenyl and 4- (4-vinylbenzyl) oxymethylphenyl. device.
상기 정공수송층은 스핀코팅 공정, 노즐프린팅 공정, 잉크젯프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정 중 어느 하나에 의해 형성되는 것이 특징인 유기전계발광소자.
12. The method of claim 11,
Wherein the hole transport layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
상기 제 1 전극과 상기 정공수송층 사이에 위치하는 정공주입층과;
상기 발광물질층과 상기 제 2 전극 사이에 위치하는 전자수송층과;
상기 전자수송층과 상기 제 2 전극 사이에 위치하는 전자주입층을 포함하는 것이 특징인 유기전계발광소자.12. The method of claim 11,
A hole injection layer disposed between the first electrode and the hole transport layer;
An electron transport layer positioned between the light emitting material layer and the second electrode;
And an electron injection layer disposed between the electron transport layer and the second electrode.
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