KR102360221B1 - Organic electro luminescence device - Google Patents
Organic electro luminescence device Download PDFInfo
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- KR102360221B1 KR102360221B1 KR1020150002812A KR20150002812A KR102360221B1 KR 102360221 B1 KR102360221 B1 KR 102360221B1 KR 1020150002812 A KR1020150002812 A KR 1020150002812A KR 20150002812 A KR20150002812 A KR 20150002812A KR 102360221 B1 KR102360221 B1 KR 102360221B1
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- South Korea
- Prior art keywords
- group
- aryl
- alkyl
- host
- formula
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- 238000005401 electroluminescence Methods 0.000 title 1
- 239000011368 organic material Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims description 73
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 125000004429 atom Chemical group 0.000 claims description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- 125000004104 aryloxy group Chemical group 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 16
- 125000005264 aryl amine group Chemical group 0.000 claims description 15
- 125000005104 aryl silyl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 14
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 13
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 13
- 229910052805 deuterium Inorganic materials 0.000 claims description 13
- 239000002019 doping agent Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- -1 metal complex compound Chemical class 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
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- H—ELECTRICITY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract
본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중에서 적어도 하나는 제1 호스트 및 제2 호스트를 포함하는 유기 전계 발광 소자를 제공한다.The present invention is a positive electrode; cathode; and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers provides an organic electroluminescent device comprising a first host and a second host.
Description
본 발명은 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to an organic electroluminescent device comprising one or more organic material layers.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이, 음극에서는 전자가 유기물층으로 주입되는 소자이다. 주입된 정공과 전자가 만났을 때 엑시톤(Exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 발생한다. 이때, 유기물층으로 사용되는 물질은 그 기능에 따라, 발광 물질, 정공주입 물질, 정공수송 물질, 전자수송 물질, 전자주입 물질 등으로 분류될 수 있다.An organic electroluminescent device is a device in which holes are injected into the organic material layer at the anode and electrons at the cathode when a voltage is applied between two electrodes. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is generated. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.
상기 정공주입 물질, 정공수송 물질, 전자수송 물질로는 NPB, BCP, Alq3 등이 알려져 있고, 상기 발광 물질로는 안트라센 유도체와, Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물 등이 알려져 있다.NPB, BCP, Alq 3 and the like are known as the hole injection material, hole transport material, and electron transport material, and as the light emitting material, an anthracene derivative, Firpic, Ir(ppy) 3 , (acac)Ir(btp) 2 Metal complex compounds containing Ir such as etc. are known.
그러나, 이러한 물질들은 유리전이온도가 낮아 열적 안정성이 좋지 않으며 삼중항 에너지도 낮아, 이들이 유기물층에 도입된 유기 전계 발광 소자는 만족할 만한 수준의 전류효율 및 수명 특성을 나타내지 못하고 있다. However, these materials have poor thermal stability due to low glass transition temperature and low triplet energy, so that the organic electroluminescent device introduced into the organic material layer does not exhibit satisfactory current efficiency and lifespan characteristics.
상기한 문제점을 해결하기 위해, 본 발명은 유기 전계 발광 소자의 구동전압, 전류효율 및 수명 등을 향상시킬 수 있는 유기 화합물을 포함하는 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide an organic electroluminescent device including an organic compound capable of improving the driving voltage, current efficiency, and lifespan of the organic electroluminescent device.
상기한 목적을 달성하기 위해, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중에서 적어도 하나는 제1 호스트와 제2 호스트를 포함하되, 상기 제1 호스트는 하기 화학식 1로 표시되는 화합물이며, 상기 제2 호스트는 하기 화학식 2로 표시되는 화합물인 유기 전계 발광 소자를 제공한다.In order to achieve the above object, the present invention is a positive electrode; cathode; and one or more organic material layers interposed between the positive electrode and the negative electrode, wherein at least one of the one or more organic material layers includes a first host and a second host, wherein the first host is represented by the following formula (1) and the second host provides an organic electroluminescent device, which is a compound represented by the following formula (2).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 내지 R6는 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, C1~C40의 알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,R 1 To R 6 Are the same or different, and are each independently selected from the group consisting of hydrogen, deuterium, a C 1 ~ C 40 alkyl group and a C 6 ~ C 60 aryl group,
a, f는 각각 0 내지 5의 정수이고,a and f are each an integer from 0 to 5,
b, e는 각각 0 내지 4의 정수이고,b and e are each an integer from 0 to 4,
c, d는 각각 0 내지 3의 정수이고,c and d are each an integer from 0 to 3,
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
Ra 및 Rb는 동일하거나 상이하며, 각각 독립적으로 C1~C40의 알킬기 또는 C6~C60의 아릴기이거나, 서로 결합하여 축합 고리를 형성하고,R a and R b are the same or different, and are each independently a C 1 ~ C 40 alkyl group or C 6 ~ C 60 aryl group, or combine with each other to form a condensed ring,
R7 내지 R9는 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접하는 기와 서로 결합하여(구체적으로, 인접하는 R7끼리 결합, 인접하는 R8끼리 결합, 인접하는 R9끼리 결합, 또는 R7과 R8의 결합) 축합 고리를 형성하고,R 7 To R 9 are the same or different, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 of Alkyloxy group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 of an aryl boron group, a C 1 ~ C 40 phosphine group, a C 1 ~ C 40 phosphine oxide group and a C 6 ~ C 60 arylamine group, or adjacent groups bonded to each other (specifically, A bond between adjacent R 7 , a bond between adjacent R 8 , a bond between adjacent R 9 , or a bond between R 7 and R 8 ) forms a condensed ring,
L은 단일결합, C6~C18의 아릴렌기 및 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택되고,L is a single bond, C 6 ~ C 18 is selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
Z1 내지 Z5는 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R10)이고, 이때, 적어도 하나는 N이며, C(R10)이 복수인 경우 복수의 R10은 동일하거나 상이하고,Z 1 to Z 5 are the same or different, and each independently is N or C(R 10 ), wherein at least one is N, and when C(R 10 ) is plural, a plurality of R 10 are the same or different,
g, h, i는 각각 0 내지 4의 정수이고,g, h, i are each an integer from 0 to 4,
m, n은 각각 1 내지 3의 정수이고,m and n are each an integer of 1 to 3,
상기 R10은 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접한 기와 서로 결합하여(구체적으로, 인접하는 R10끼리 결합) 축합 고리를 형성하고,Wherein R 10 is hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 of a cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyloxy group, C 6 to C 60 of Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 1 ~ C 40 of a phosphine group, a C 1 ~ C 40 phosphine oxide group and a C 6 ~ C 60 arylamine group, or combine with an adjacent group (specifically, adjacent R 10 bonds) to form a condensed ring do,
상기 Ra, Rb의 알킬기, 아릴기와, 상기 R1 내지 R10의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기와, 상기 L의 아릴렌기, 헤테로아릴렌기는 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 상기 치환기가 복수일 경우 복수의 치환기는 동일하거나 상이하다.An alkyl group, an aryl group of R a and R b , an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkyl group of R 1 to R 10 A silyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group, and an arylamine group, and the arylene group and heteroarylene group of L are each independently deuterium, a halogen group, a cyano group, a nitro group , amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 Aryl group, nuclear atom number 5 to 60 heteroaryl group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 1 ~ C 40 phosphine group, C 1 ~ C 40 phosphine oxide group and C 6 ~ C 60 It is substituted or unsubstituted with one or more substituents selected from the group consisting of an arylamine group, and when the substituents are plural, the plural substituents are the same or different.
본 발명의 유기 전계 발광 소자는 제1 호스트로서 상기 화학식 1로 표시되는 화합물과 제2 호스트로서 상기 화학식 2로 표시되는 화합물을 유기물층에 적용함으로써, 구동전압, 전류효율 및 수명 등이 향상될 수 있다. 이에 따라, 유기 전계 발광 소자는 성능 및 수명이 향상된 디스플레이 패널을 제공할 수 있다.In the organic electroluminescent device of the present invention, by applying the compound represented by Formula 1 as a first host and the compound represented by Formula 2 as a second host to an organic material layer, driving voltage, current efficiency, and lifespan can be improved. . Accordingly, the organic electroluminescent device can provide a display panel with improved performance and lifespan.
이하, 본 발명을 설명한다.
Hereinafter, the present invention will be described.
본 발명의 유기 전계 발광 소자는 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중에서 적어도 하나는 제1 호스트와 제2 호스트를 포함하되, 상기 제1 호스트는 상기 화학식 1로 표시되는 화합물이며, 상기 제2 호스트는 상기 화학식 2로 표시되는 화합물로서, 이에 대해 구체적으로 설명하면 다음과 같다.The organic electroluminescent device of the present invention includes an anode; cathode; and one or more organic material layers interposed between the positive electrode and the negative electrode, wherein at least one of the one or more organic material layers includes a first host and a second host, wherein the first host is represented by Formula 1 and the second host is a compound represented by Chemical Formula 2, which will be described in detail as follows.
본 발명의 유기 전계 발광 소자에 포함되는 양극은 정공을 유기물층으로 주입하는 역할을 한다. 이러한 양극 물질은 특별히 한정되지 않으나, 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등을 사용할 수 있다.The anode included in the organic electroluminescent device of the present invention serves to inject holes into the organic material layer. Such anode material is not particularly limited, but metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole or polyaniline; and carbon black.
본 발명의 유기 전계 발광 소자에 포함되는 음극은 전자를 유기물층으로 주입하는 역할을 한다. 이러한 음극 물질은 특별히 한정되지 않으나, 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등을 사용할 수 있다.The cathode included in the organic electroluminescent device of the present invention serves to inject electrons into the organic material layer. The anode material is not particularly limited, but a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or an alloy thereof; and a multi-layered material such as LiF/Al or LiO2/Al.
본 발명의 유기 전계 발광 소자에 포함되는 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 수명 개선층, 전자 수송층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층은 제1 호스트 및 제2 호스트를 포함할 수 있다. 구제적으로, 상기 제1 호스트 및 제2 호스트를 포함하는 유기물층은 발광층, 또는 발광 보조층인 것이 바람직하다.One or more organic material layers included in the organic electroluminescent device of the present invention may be any one or more of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, a life improvement layer, an electron transport layer, and an electron injection layer, and at least one of them The organic material layer may include a first host and a second host. Specifically, the organic material layer including the first host and the second host is preferably a light emitting layer or a light emitting auxiliary layer.
본 발명의 유기물층에 포함되는 발광층은 주입된 정공과 전자에 의해, 제1 호스트 및 제2 호스트가 결합하여 들뜬상태 전하이동 복합체인 엑시플렉스(Exciplex)를 생성한다.In the light emitting layer included in the organic material layer of the present invention, the first host and the second host combine by the injected holes and electrons to generate an exciplex, which is an excited state charge transfer complex.
본 발명에서 제 1 호스트로 사용되는 화합물은 비스카바졸(Biscarbazole) 모이어티의 질소 원자에 각각 방향족 고리(구체적으로, 페닐기)가 결합되는 구조를 이루는 화합물로, 상기 화학식 1로 표시된다. The compound used as the first host in the present invention is a compound having a structure in which an aromatic ring (specifically, a phenyl group) is bonded to a nitrogen atom of a biscarbazole moiety, and is represented by Formula 1 above.
상기 비스카바졸 모이어티는 전자 공여성 및 정공 수송성이 큰 전자주게기(Electron Donating Group, EDG) 특성을 갖는 카바졸 모이어티가 2개 포함된 구조로 인해, 높은 정공 수송성을 가진다. 또한, 상기 비스카바졸 모이어티는 카바졸 모이어티가 1개인 경우 보다 분자량이 유의적으로 증가하여 높은 열적 안정성을 가진다. 이러한 비스카바졸 모이어티는 3,3' 결합으로 인해 2개의 카바졸 모이어티가 견고하게 연결되어 분자 자체의 열적/전기적 안정성이 강화될 수 있다.The biscarbazole moiety has a high hole transport property due to a structure including two carbazole moieties having electron donating group (EDG) characteristics with high electron donating and hole transport properties. In addition, the biscarbazole moiety has a higher thermal stability due to a significant increase in molecular weight than when the carbazole moiety is one. In this biscarbazole moiety, the two carbazole moieties are tightly linked due to a 3,3' bond, thereby enhancing the thermal/electrical stability of the molecule itself.
또한, 본 발명의 화학식 1로 표시되는 화합물은 전자 공여성 및 정공 수송성을 가지는 알킬기 또는 아릴기가 결합되면서, 분자 내의 강화된 전자 주게기(EDG) 특성을 가진다. In addition, the compound represented by Formula 1 of the present invention has an enhanced electron donor (EDG) characteristic in the molecule while an alkyl group or an aryl group having electron donating and hole transporting properties is combined.
상기 화학식 1로 표시되는 화합물에서, R1 내지 R6는 동일하거나 상이하며, 각각 독립적으로 수소, 메틸기, 에틸기, 프로필기, iso-프로필기, t-부틸기, 페닐기 및 비페닐기로 이루어진 군에서 선택되는 것이 바람직하고, 페닐기 또는 비페닐기인 것이 더욱 바람직하다.In the compound represented by Formula 1, R 1 to R 6 are the same or different, and each independently from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a t-butyl group, a phenyl group and a biphenyl group It is preferable that it is selected, and it is more preferable that it is a phenyl group or a biphenyl group.
이러한 본 발명의 화학식 1로 표시되는 화합물은 하기 화합물들(A-1 내지 A-52)로 보다 구체화될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Formula 1 of the present invention may be more specific to the following compounds (A-1 to A-52), but is not limited thereto.
본 발명에서 제2 호스트로 사용되는 화합물은 플루오렌(Fluorene) 모이어티와 6원 헤테로고리가 링커기(페닐 또는 비페닐)에 의해 결합되는 구조를 기본 골격으로 이루는 화합물로, 상기 화학식 2로 표시된다. The compound used as the second host in the present invention is a compound having a basic skeleton in which a fluorene moiety and a 6-membered heterocycle are bonded by a linker group (phenyl or biphenyl), and is represented by Formula 2 do.
상기 플루오렌 모이어티는 전자 공여성이 큰 전자 주게기(EDG) 특성을 가진다. 이러한 플루오렌 모이어티가 링커기에 의해 전자 흡수성이 큰 전자 끌개기(Electron Withdrawing Group, EWG)인 6원 헤테로고리(예컨대, 피리딘기, 피리미딘기, 트리아진기 등)와 결합할 경우, 분자 전체가 바이폴라(bipolar) 특성을 갖기 때문에 정공과 전자의 결합력을 높일 수 있다. 따라서, 화학식 2로 표시되는 화합물을 유기 전계 발광 소자의 유기물층 재료로 사용할 경우, 캐리어 수송성 및 전류효율을 높일 수 있다.The fluorene moiety has a large electron donating electron donor (EDG) property. When this fluorene moiety is bonded to a 6-membered heterocycle (eg, pyridine group, pyrimidine group, triazine group, etc.) that is an electron withdrawing group (EWG) with high electron absorption by a linker group, the entire molecule is Since it has a bipolar characteristic, it is possible to increase the bonding force between holes and electrons. Therefore, when the compound represented by Formula 2 is used as an organic material layer of an organic electroluminescent device, carrier transport properties and current efficiency can be improved.
이러한 본 발명의 화학식 2로 표시되는 화합물은 하기 화학식 3 내지 5로 표시되는 화합물 중 어느 하나로 구체화될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Chemical Formula 2 of the present invention may be embodied as any one of the compounds represented by Chemical Formulas 3 to 5, but is not limited thereto.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 3 내지 5에서,In Formulas 3 to 5,
Ra, Rb, R7 내지 R9, Z1 내지 Z5, g, h 및 i는 각각 상기 화학식 2에서 정의한 바와 같다.R a , R b , R 7 to R 9 , Z 1 to Z 5 , g, h and i are each as defined in Formula 2 above.
한편 유기 전계 발광 소자의 특성을 고려할 때, 본 발명의 화학식 2로 표시되는 화합물에서, Ra 및 Rb는 동일하거나 상이하며, 각각 독립적으로 메틸기 또는 페닐기이거나, 서로 결합하여 
상기 R7 내지 R9는 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 것이 바람직하다.The R 7 To R 9 Are the same or different, and each independently hydrogen, deuterium, a C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group, a heteroaryl group of 5 to 60 nuclear atoms, and C 6 ~ It is preferably selected from the group consisting of a C 60 arylamine group.
상기 m, n은 각각 1 내지 3의 정수인데, m은 1인 것이 바람직하고, n은 1 또는 2인 것이 바람직하다. Each of m and n is an integer of 1 to 3, m is preferably 1, and n is preferably 1 or 2.
상기 L은 단일결합, 페닐렌기 또는 비페닐렌기인 것이 바람직하다.It is preferable that L is a single bond, a phenylene group or a biphenylene group.
상기 화학식 2에서 
상기 C-1 내지 C-15에서,In C-1 to C-15,
R10는 상기 화학식 2에서 정의한 바와 같고,R 10 is as defined in Formula 2 above,
R11는 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택되거나, 인접하는 기와 서로 결합하여(구체적으로, 인접하는 R11끼리 결합 또는 R10과 R11의 결합) 축합 고리를 형성하고,R 11 is hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, A heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 6 to C 60 aryloxy group, a C 1 to C 40 alkyloxy group , C 6 ~ C 60 Arylamine group, C 1 ~ C 40 Alkylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Arylphosphine group , C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 Selected from the group consisting of an arylsilyl group, or bonded to an adjacent group (specifically, adjacent R 11 bonding or R 10 and R 11 bonding) to form a condensed ring,
p는 1 내지 4의 정수이고,p is an integer from 1 to 4,
상기 R11의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 이때 상기 치환기가 복수일 경우 복수의 치환기는 동일하거나 상이하다.An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, Aryl phosphine group, aryl phosphine oxide group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alky Nyl group, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 1 ~ C 40 alkylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron Group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 Unsubstituted or substituted with one or more substituents selected from the group consisting of an arylsilyl group, wherein the When there are a plurality of substituents, the plurality of substituents are the same or different.
이러한 본 발명의 화학식 2로 표시되는 화합물은 하기 화합물들(B-1 내지 B-173)로 구체화될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Formula 2 of the present invention may be embodied as the following compounds (B-1 to B-173), but is not limited thereto.
한편, 본 발명에서의 알킬은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이다. 이러한 알킬의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있다.On the other hand, alkyl in the present invention is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyls include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.
본 발명에서의 알케닐(alkenyl)은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이다. 이러한 알케닐의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있다.Alkenyl in the present invention is a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples of such alkenyl include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl) and the like.
본 발명에서의 알키닐(alkynyl)은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이다. 이러한 알키닐의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있다.Alkynyl in the present invention is a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples of such alkynyl include ethynyl, 2-propynyl, and the like.
본 발명에서의 아릴은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있다.Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form may be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, anthryl, and the like.
본 발명에서의 헤테로아릴은 핵원자수 5 내지 60의 모노헤테로시클릭 또는 폴리헤테로시클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 아릴기와 축합된 형태도 포함할 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노시클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리시클릭 고리, 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있다.Heteroaryl in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with a heteroatom such as N, O, S or Se. In addition, two or more rings may be simply attached to each other (pendant) or may include a condensed form, and may include a condensed form with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
본 발명에서의 아릴옥시는 RO-로 표시되는 1가의 치환기로 상기 R은 탄소수 5 내지 60의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있다.Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, and diphenyloxy.
본 발명에서의 알킬옥시는 R'O-로 표시되는 1가의 치환기로 상기 R'는 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 시클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있다.Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R' means 1 to 40 alkyl, and includes a linear, branched or cyclic structure. interpreted as Examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서의 아릴아민은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
본 발명에서의 시클로알킬은 탄소수 3 내지 40의 모노시클릭 또는 폴리시클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 시클로알킬의 예로는 시클로프로필, 시클로펜틸, 시클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있다.Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서의 헤테로시클로알킬은 핵원자수 3 내지 40의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있다.Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with a hetero atom such as N, O, S or Se. Examples of such heterocycloalkyl include morpholine, piperazine, and the like.
본 발명에서의 알킬실릴은 탄소수 1 내지 40의 알킬로 치환된 실릴을 의미하고, 아릴실릴은 탄소수 5 내지 40의 아릴로 치환된 실릴을 의미한다.In the present invention, alkylsilyl means silyl substituted with alkyl having 1 to 40 carbon atoms, and arylsilyl means silyl substituted with aryl having 5 to 40 carbon atoms.
본 발명에서의 축합 고리는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.The condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
이러한 제1 호스트 및 제2 호스트를 적용한 유기 전계 발광 소자는 주입되는 정공과 전자의 균형을 맞출 수 있기 때문에 고수명을 가질 수 있다. 본 발명의 유기물층 제조시 제1 호스트와 제2 호스트의 혼합비율은 특별히 한정되지 않으나, 제1 호스트:제2 호스트가 1:99 내지 99:1의 중량비율로 혼합되는 것이 바람직하고, 25:75 내지 75:25의 중량비율로 혼합되는 것이 더욱 바람직하다.The organic electroluminescent device to which the first host and the second host are applied can have a long lifespan because the injected holes and electrons can be balanced. When preparing the organic material layer of the present invention, the mixing ratio of the first host and the second host is not particularly limited, but the first host: the second host is preferably mixed in a weight ratio of 1:99 to 99:1, and 25:75 It is more preferable to mix in a weight ratio of 75:25.
본 발명의 유기 전계 발광 소자는 정공 수송층과 전자 수송층 사이에 복수 개의 발광층을 순차적으로 적층하여 전압 및 전류 인가시 이들의 혼합색을 구현할 수 있으며, 발광층의 수만큼 발광효율을 증가시킬 수 있다.In the organic electroluminescent device of the present invention, a plurality of light emitting layers are sequentially stacked between the hole transport layer and the electron transport layer to implement a mixed color thereof when voltage and current are applied, and the luminous efficiency can be increased by the number of light emitting layers.
한편, 본 발명의 발광층은 제1 호스트 및 제2 호스트와 함께 금속 착체 화합물계의 도펀트를 포함할 수 있다.Meanwhile, the light emitting layer of the present invention may include a metal complex compound-based dopant together with the first host and the second host.
이러한 본 발명의 발광층을 제조하는 방법은 특별히 한정되지 않으나, 비제한적인 예로는 공증착법, 진공 증착법, 용액 도포법 등을 들 수 있다. 이 중 상기 공증착법은 제1 호스트 및 제2 호스트를 각각 제1 열원 및 제2 열원에 배치하고, 제3 열원에 도펀트를 배치하여 동시에 열을 가해 공증착시키는 과정으로 발광층을 제조한다. The method of manufacturing the light emitting layer of the present invention is not particularly limited, but non-limiting examples include a co-evaporation method, a vacuum deposition method, a solution coating method, and the like. Among them, in the co-deposition method, a first host and a second host are respectively disposed at a first heat source and a second heat source, a dopant is disposed at a third heat source, and the light emitting layer is prepared by co-deposition by applying heat at the same time.
구체적으로, 1×10-06 torr 이하의 진공도에서, 정공 이동도(Hole mobility)가 높고 정공 주입효율이 좋은 제1 호스트를 제 1 열원에 배치하고, 전자 이동도(Electron mobility)가 높고 전자 주입효율이 좋은 제2 호스트를 제2 열원에 배치하며, 제3 열원에 도펀트를 배치한 다음, 각 물질의 초당 증발속도를 동시에 조절하여 적정비율로 공증착시키는 방법이다. 이때 공증착되는 호스트의 개수는 발광층의 특성에 따라 2개 이상이 될 수 있다. Specifically, at a vacuum degree of 1×10 -06 torr or less, a first host having high hole mobility and good hole injection efficiency is disposed in the first heat source, and electron mobility is high and electron injection This is a method in which a second host with good efficiency is disposed in a second heat source, a dopant is disposed in a third heat source, and then the evaporation rate per second of each material is simultaneously controlled to co-deposit at an appropriate ratio. In this case, the number of hosts to be co-deposited may be two or more depending on the characteristics of the light emitting layer.
이때, 발광층 제조시 제 1 호스트, 제 2 호스트 및 도펀트의 사용량은 특별히 한정되지 않으나, 혼합된 제 1 호스트 및 제 2 호스트를 70~99 중량%, 도펀트를 1~30 중량%로 사용하는 것이 바람직하고, 혼합된 제 1 호스트와 제 2 호스트를 80~95 중량%, 도펀트를 5~20 중량%로 사용하는 것이 더욱 바람직하다. At this time, the amount of the first host, the second host, and the dopant used in the production of the light emitting layer is not particularly limited, but it is preferable to use the mixed first host and second host in an amount of 70 to 99% by weight and the dopant in an amount of 1 to 30% by weight. And, it is more preferable to use the mixed first host and second host in an amount of 80 to 95% by weight and a dopant in an amount of 5 to 20% by weight.
이외에, 호스트 중 증착 온도가 유사한 호스트를 적정비율로 혼합하여 하나의 열원에 배치하고 열을 가해 공증착시키는 과정으로 발광층을 제조할 수도 있다. In addition, the light emitting layer may be prepared by mixing a host having a similar deposition temperature among the hosts in an appropriate ratio, placing it in one heat source, and co-depositing by applying heat.
구체적으로, 1×10-06 이하의 진공도에서 제1 열원에 혼합된 호스트(제 1 호스트+제 2 호스트)를 배치하고, 제2 열원에 도펀트를 배치한 다음, 각 물질의 초당 증발속도를 동시에 조절하며 발광층을 제조한다. Specifically, a host (first host + second host) mixed in a first heat source is disposed at a vacuum degree of 1×10 -06 or less, a dopant is disposed in a second heat source, and the evaporation rate per second of each material is simultaneously increased and to prepare a light emitting layer.
이와 같이, 제1 열원에 혼합된 호스트를 배치하여 발광층을 제조할 경우, 1종 이상의 호스트 혼합비율의 오차를 줄일 수 있고, 적은 수의 열원을 사용하여 발광층을 형성할 수 있다. 구체적으로 제1 호스트 및 제2 호스트의 증착 온도가 ±10 ℃일 경우 혼합하여 하나의 열원에 위치시킬 수 있다.In this way, when the light emitting layer is manufactured by disposing a host mixed with the first heat source, an error in the mixing ratio of one or more hosts can be reduced, and the light emitting layer can be formed using a small number of heat sources. Specifically, when the deposition temperature of the first host and the second host is ±10 °C, they may be mixed and placed in one heat source.
이때, 발광층 제조시 제 1 호스트, 제 2 호스트 및 도펀트의 사용량은 특별히 한정되지 않으나, 혼합된 제1 호스트 및 제2 호스트를 70~99 중량%, 도펀트를 1~30 중량%로 사용하는 것이 바람직하고, 혼합된 제1 호스트와 제2 호스트를 80~95 중량%, 도펀트를 5~20 중량%로 사용하는 것이 더욱 바람직하다.In this case, the amount of the first host, the second host, and the dopant used is not particularly limited when preparing the light emitting layer, but it is preferable to use the mixed first host and second host in an amount of 70 to 99% by weight and the dopant in an amount of 1 to 30% by weight. And, it is more preferable to use the mixed first host and second host in an amount of 80 to 95% by weight and a dopant in an amount of 5 to 20% by weight.
본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 기판, 양극, 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 수명 개선층, 전자 수송층 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 상기 전자 수송층 위에는 전자 주입층이 추가로 적층될 수 있다. 또한, 상기 전극(음극, 또는 양극)과 유기물층 계면에 절연층 또는 접착층이 더 적층될 수 있다.The structure of the organic electroluminescent device of the present invention is not particularly limited, but may have a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a life improvement layer, an electron transport layer and a cathode are sequentially stacked. In this case, an electron injection layer may be additionally stacked on the electron transport layer. In addition, an insulating layer or an adhesive layer may be further laminated at the interface between the electrode (cathode or anode) and the organic material layer.
본 발명의 유기 전계 발광 소자 제조시 사용되는 기판은 특별히 한정되지 않으나, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 등을 사용할 수 있다.The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, but a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, and the like may be used.
또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질을 사용할 수 있다.
In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and common materials known in the art may be used.
이하, 본 발명을 실시예를 통하여 상세히 설명하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail through examples, but the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.
[준비예 1] 화합물 I-1 의 합성[Preparation Example 1] Synthesis of compound I-1
질소 기류 하에서 3-Bromo-9H-carbazole (27.8 g, 113 mmol), (9H-Carbazol-3-yl)boronic acid (23.8 g, 113 mmol), K2CO3 (46.8g, 339 mmol) 및 THF/H2O(400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (6.53 g, 5.65 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-Bromo-9H-carbazole (27.8 g, 113 mmol), (9H-Carbazol-3-yl)boronic acid (23.8 g, 113 mmol), K 2 CO 3 (46.8 g, 339 mmol) and THF under a nitrogen stream /H 2 O (400 ml/100 ml) was mixed, and then Pd(PPh 3 ) 4 (6.53 g, 5.65 mmol) was added and stirred at 80° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 I-1 (30 g, 수율 80%)을 얻었다. After completion of the reaction, extraction was performed with methylene chloride, MgSO 4 was added, and filtration was performed. After removing the solvent from the obtained organic layer, it was purified by column chromatography (Hexane:MC = 5:1 (v/v)) to obtain Compound I-1 (30 g, yield 80%).
1H-NMR: δ 7.29-7.50 (m, 5H), 7.94(d, 1H), 8.01(s, 1H), 10.1(s, 1H)
1 H-NMR: δ 7.29-7.50 (m, 5H), 7.94 (d, 1H), 8.01 (s, 1H), 10.1 (s, 1H)
[준비예 2] 화합물 I-2 의 합성[Preparation Example 2] Synthesis of compound I-2
질소 기류 하에서 3-Bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (6-Phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K2CO3 (32.0g, 232 mmol) 및 THF/H2O(400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (4.47 g, 3.86 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-Bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (6-Phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K 2 CO 3 ( 32.0 g, 232 mmol) and THF/H 2 O (400 ml/100 ml) were mixed, and then Pd(PPh 3 ) 4 (4.47 g, 3.86 mmol) was added and stirred at 80° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 I-2 (30 g, 수율 80%)을 얻었다. After completion of the reaction, extraction was performed with methylene chloride, MgSO 4 was added, and filtration was performed. After removing the solvent from the obtained organic layer, it was purified by column chromatography (Hexane:MC = 5:1 (v/v)) to obtain Compound I-2 (30 g, yield 80%).
1H-NMR: δ 7.29-7.50 (m, 10H), 7.92(s, 1H), 8.00(s, 1H), 10.1(s, 1H)
1 H-NMR: δ 7.29-7.50 (m, 10H), 7.92(s, 1H), 8.00(s, 1H), 10.1(s, 1H)
[준비예 3] 화합물 I-3 의 합성[Preparation Example 3] Synthesis of compound I-3
<단계 1> 3-Bromo-6,9-diphenyl-9H-carbazole의 합성<Step 1> Synthesis of 3-Bromo-6,9-diphenyl-9H-carbazole
질소 기류 하에서 3-Bromo-6-phenyl-9H-carbazole (35.9 g, 111 mmol), Iodobenzene (22.7 g, 111 mmol), Pd(OAc)2 (1.25 g, 5.57 mmol), NaO(t-Bu) (21.4 g, 223 mmol), P(t-Bu)3 (50wt%) (4.51 g, 11.1 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 3-Bromo-6-phenyl-9H-carbazole (35.9 g, 111 mmol), Iodobenzene (22.7 g, 111 mmol), Pd(OAc) 2 (1.25 g, 5.57 mmol), NaO(t-Bu) under a nitrogen stream (21.4 g, 223 mmol), P(t-Bu) 3 (50wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 3-Bromo-6,9-diphenyl-9H-carbazole (31.7g, 수율 60%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound 3-Bromo-6,9-diphenyl- 9H-carbazole (31.7 g, yield 60%) was obtained.
1H-NMR: δ 7.07-7.35(m, 14H), 7.92(s, 1H), 7.98 (s, 1H)
1 H-NMR: δ 7.07-7.35 (m, 14H), 7.92 (s, 1H), 7.98 (s, 1H)
<단계 2> 화합물 I-3의 합성<Step 2> Synthesis of compound I-3
질소 기류 하에서 준비예 3의 <단계 1>에서 얻은 3-Bromo-6,9-diphenyl-9H-carbazole (26.6 g, 66.9 mmol), (6-Phenyl-9H-carbazol-3-yl)boronic acid (19.2 g, 66.9 mmol), K2CO3 (27.7 g, 200 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4(3.86 g, 3.34 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-Bromo-6,9-diphenyl-9H-carbazole (26.6 g, 66.9 mmol) obtained in <Step 1> of Preparation Example 3 under a nitrogen stream, (6-Phenyl-9H-carbazol-3-yl)boronic acid ( 19.2 g, 66.9 mmol), K 2 CO 3 (27.7 g, 200 mmol) and THF/H 2 O (400 ml/100 ml) were mixed, followed by Pd(PPh 3 ) 4 (3.86 g, 3.34 mmol) and stirred at 80 °C for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 I-3 (30 g, 수율 80%)을 얻었다.After completion of the reaction, extraction was performed with methylene chloride, MgSO 4 was added, and filtration was performed. After removing the solvent from the obtained organic layer, it was purified by column chromatography (Hexane:MC = 5:1 (v/v)) to obtain Compound I-3 (30 g, yield 80%).
1H-NMR : δ 7.05-7.33(m, 15H), 7.38-7.42(m, 8H), 7.92(s, 1H), 7.94(s, 1H), 8.00(s, 1H), 8.03(s, 1H), 10.3(s, 1H)
1 H-NMR: δ 7.05-7.33(m, 15H), 7.38-7.42(m, 8H), 7.92(s, 1H), 7.94(s, 1H), 8.00(s, 1H), 8.03(s, 1H) ), 10.3(s, 1H)
[준비예 4][Preparation Example 4] 화합물 I-4의 합성Synthesis of compound I-4
질소 기류 하에서 3-Bromo-7-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (9-Phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K2CO3 (32.1 g, 232 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (4.47 g, 3.87 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-Bromo-7-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (9-Phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K 2 CO 3 ( 32.1 g, 232 mmol) and THF/H 2 O (400 ml/100 ml) were mixed, and then Pd(PPh 3 ) 4 (4.47 g, 3.87 mmol) was added and stirred at 80° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 I-4 (30 g, 수율 80%)을 얻었다.After completion of the reaction, extraction was performed with methylene chloride, MgSO 4 was added, and filtration was performed. After removing the solvent from the obtained organic layer, it was purified by column chromatography (Hexane:MC = 5:1 (v/v)) to obtain Compound I-4 (30 g, yield 80%).
1H-NMR : δ 7.04-7.30(m, 10H), 7.39-7.43(m, 9H), 7.75(s, 1H), 7.84(s, 1H), 7.96(s, 1H), 7.98(s, 1H), 8.01(s, 1H), 10.2(s, 1H)
1 H-NMR: δ 7.04-7.30(m, 10H), 7.39-7.43(m, 9H), 7.75(s, 1H), 7.84(s, 1H), 7.96(s, 1H), 7.98(s, 1H) ), 8.01(s, 1H), 10.2(s, 1H)
[준비예 5] 화합물 I-5 의 합성[Preparation Example 5] Synthesis of compound I-5
<단계 1> 9-(Biphenyl-3-yl)-3-bromo-9H-carbazole의 합성<Step 1> Synthesis of 9-(Biphenyl-3-yl)-3-bromo-9H-carbazole
질소 기류 하에서 3-Iodobiphenyl (39.7 g, 111 mmol), 3-Bromo-9H-carbazole (27.4 g, 111 mmol), Pd(OAc)2 (1.25 g, 5.57 mmol), NaO(t-Bu) (21.4 g, 223 mmol), P(t-Bu)3 (50wt%) (4.51 g, 11.1 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 3-Iodobiphenyl (39.7 g, 111 mmol), 3-Bromo-9H-carbazole (27.4 g, 111 mmol), Pd(OAc) 2 (1.25 g, 5.57 mmol), NaO(t-Bu) (21.4 under a nitrogen stream) g, 223 mmol), P(t-Bu) 3 (50wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 9-(Biphenyl-3-yl)-3-bromo-9H-carbazole (26.9g, 수율 61%)을 얻었다.After completion of the reaction, extraction was performed with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound 9-(Biphenyl-3-yl)- 3-bromo-9H-carbazole (26.9 g, yield 61%) was obtained.
1H-NMR: δ 7.25-7.52(m, 12H), 7.94(d, 1H), 8.07 (m, 2H), 8.55 (d, 1H)
1 H-NMR: δ 7.25-7.52 (m, 12H), 7.94 (d, 1H), 8.07 (m, 2H), 8.55 (d, 1H)
<단계 2> 화합물 I-5의 합성<Step 2> Synthesis of compound I-5
질소 기류 하에서 준비예 5의 <단계 1>에서 얻은 9-(Biphenyl-3-yl)-3-bromo-9H-carbazole (26.9g, 67.7mmol), (9H-carbazol-3-yl)boronic acid (14.1 g, 66.9 mmol), K2CO3 (27.7 g, 200 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 9-(Biphenyl-3-yl)-3-bromo-9H-carbazole (26.9g, 67.7mmol), (9H-carbazol-3-yl)boronic acid ( 14.1 g, 66.9 mmol), K 2 CO 3 (27.7 g, 200 mmol) and THF/H 2 O (400 ml/100 ml) were mixed, followed by Pd(PPh 3 ) 4 (3.86 g, 3.34 mmol) and stirred at 80 °C for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 I-5 (24.6 g, 수율 75%)을 얻었다.After completion of the reaction, extraction was performed with methylene chloride, MgSO 4 was added, and filtration was performed. After removing the solvent from the obtained organic layer, it was purified by column chromatography (Hexane:MC = 5:1 (v/v)) to obtain Compound I-5 (24.6 g, yield 75%).
1H-NMR : δ 7.29(t, 2H), 7.46-7.69(m, 13H), 7.77(s, 2H), 7.87-8.18(m, 6H), 10.1(s, 1H)
1 H-NMR: δ 7.29 (t, 2H), 7.46-7.69 (m, 13H), 7.77 (s, 2H), 7.87-8.18 (m, 6H), 10.1 (s, 1H)
[합성예 1] 화합물 A-2의 합성[Synthesis Example 1] Synthesis of compound A-2
질소 기류 하에서 준비예 1에서 얻은 I-1 (5 g, 15.0 mmol), 4-Bromo-1,1'-biphenyl (7.01 g, 30.1 mmol), Pd(OAc)2 (338 mg, 1.50 mmol), NaO(t-Bu) (5.78 g, 60.2 mmol), P(t-Bu)3 (50 wt%) (1.22 g, 3.01 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. I-1 obtained in Preparation Example 1 under a nitrogen stream (5 g, 15.0 mmol), 4-Bromo-1,1'-biphenyl (7.01 g, 30.1 mmol), Pd(OAc) 2 (338 mg, 1.50 mmol), NaO(t-Bu) (5.78 g, 60.2 mmol), P(t-Bu) 3 (50 wt%) (1.22 g, 3.01 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours. .
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 A-2 (6.70 g, 수율 70%)을 얻었다.After completion of the reaction, extraction was performed with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound A-2 (6.70 g, yield 70%). ) was obtained.
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)
Mass (theoretical: 636.78 g/mol, measured: 636 g/mol)
[합성예 2] 화합물 A-3의 합성[Synthesis Example 2] Synthesis of compound A-3
4-Bromo-1,1'-biphenyl 대신 3-Bromo-1,1'-biphenyl (7.02 g, 30.1 mmol)을 사용한 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 A-3 (6.70 g, 수율 70%)를 얻었다.Except for using 3-Bromo-1,1'-biphenyl (7.02 g, 30.1 mmol) instead of 4-Bromo-1,1'-biphenyl, Compound A-3 ( 6.70 g, yield 70%) was obtained.
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)
Mass (theoretical: 636.78 g/mol, measured: 636 g/mol)
[합성예 3][Synthesis Example 3] 화합물 A-5의 합성Synthesis of compound A-5
4-Bromo-1,1'-biphenyl 대신 5'-Bromo-1,1':3',1''-terphenyl (9.30 g, 30.1 mmol)을 사용한 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 A-5 (8.31 g, 수율 70%)을 얻었다.
The same procedure as in Synthesis Example 1, except that 5'-Bromo-1,1':3',1''-terphenyl (9.30 g, 30.1 mmol) was used instead of 4-Bromo-1,1'-biphenyl was carried out to obtain compound A-5 (8.31 g, yield 70%).
[합성예 4] 화합물 A-11의 합성[Synthesis Example 4] Synthesis of compound A-11
질소 기류 하에서 준비예 2에서 얻은 I-2 (5 g, 10.3 mmol), Iodobenzene (4.21 g, 20.6 mmol), Pd(OAc)2 (232 mg, 1.03 mmol), NaO(t-Bu) (3.96 g, 41.2 mmol), P(t-Bu)3 (50wt%) (836 mg, 2.06 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. I-2 (5 g, 10.3 mmol), Iodobenzene (4.21 g, 20.6 mmol), Pd(OAc) 2 (232 mg, 1.03 mmol), NaO(t-Bu) (3.96 g) obtained in Preparation Example 2 under a nitrogen stream , 41.2 mmol), P(t-Bu) 3 (50wt%) (836 mg, 2.06 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 A-11 (4.60 g, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound A-11 (4.60 g, yield 70%). ) was obtained.
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)
Mass (theoretical: 636.78 g/mol, measured: 636 g/mol)
[합성예 5][Synthesis Example 5] 화합물 A-12의 합성Synthesis of compound A-12
질소 기류 하에서 준비예 3에서 얻은 I-3 (5 g, 8.92 mmol), 4-Bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50 wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. I-3 (5 g, 8.92 mmol), 4-Bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc) 2 (100 mg, 0.446 mmol) obtained in Preparation Example 3 under a nitrogen stream, NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu) 3 (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours. .
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 A-12 (4.45 g, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound A-12 (4.45 g, yield 70%). ) was obtained.
Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)
Mass (theoretical: 712.88 g/mol, measured: 712 g/mol)
[합성예 6][Synthesis Example 6] 화합물 A-16의 합성Synthesis of compound A-16
질소 기류 하에서 준비예 4에서 얻은 I-4 (4.31 g, 8.92 mmol), Iodobenzene (2.00 g, 9.81 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50 wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. I-4 obtained in Preparation Example 4 under a nitrogen stream (4.31 g, 8.92 mmol), Iodobenzene (2.00 g, 9.81 mmol), Pd(OAc) 2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g , 17.8 mmol), P(t-Bu) 3 (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 A-16 (4.30 g, 수율 87%)를 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound A-16 (4.30 g, yield 87%). ) was obtained.
Mass (이론치: 560.69 g/mol, 측정치: 560 g/mol)
Mass (theoretical value: 560.69 g/mol, measured value: 560 g/mol)
[합성예 7] 화합물 A-30의 합성[Synthesis Example 7] Synthesis of compound A-30
질소 기류 하에서 준비예 5에서 얻은 I-5 (4.31 g, 8.92 mmol), 4-Bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. I-5 (4.31 g, 8.92 mmol), 4-Bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc) 2 (100 mg, 0.446 mmol) obtained in Preparation Example 5 under a nitrogen stream, NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu) 3 (50wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 화합물 A-30 (3.68 g, 수율 65%)를 얻었다.After completion of the reaction, extraction was performed with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography (Hexane:MC = 5:1 (v/v)) to compound A-30 (3.68 g, yield 65%). ) was obtained.
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)
Mass (theoretical: 636.78 g/mol, measured: 636 g/mol)
[합성예 8] 화합물 B-1의 합성[Synthesis Example 8] Synthesis of compound B-1
질소 기류 하에서 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine (10.0 g, 0.026 mol), 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd(PPh3)4 (0.95 g, 0.001 mol) 및 Potassium carbonate (7.65 g, 0.078 mol)을 혼합한 다음, 1,4-Dioxane (80 ㎖) 및 H2O (20 ㎖)에서 환류 교반하였다. 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine (10.0 g, 0.026 mol), 9,9-Dimethyl-9H-fluoren-2-yl-boronic under nitrogen stream acid (7.9 g, 0.033 mol), Pd(PPh 3 ) 4 (0.95 g, 0.001 mol) and Potassium carbonate (7.65 g, 0.078 mol) were mixed, followed by 1,4-Dioxane (80 mL) and H 2 O (20 mL) under reflux stirring.
반응 종료 후, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 상기 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane: MC = 5:1 (v/v))로 정제하여 화합물 B-1 (8.2 g, 수율 63%)를 얻었다. After completion of the reaction, the organic layer was separated with methylene chloride, and water was removed from the organic layer using MgSO 4 . After removing the solvent from the organic layer from which water was removed, it was purified by column chromatography (Hexane: MC = 5:1 (v/v)) to obtain Compound B-1 (8.2 g, yield 63%).
HRMS [M]+: 501.62
HRMS [M]+: 501.62
[합성예 9] 화합물 B-3의 합성[Synthesis Example 9] Synthesis of compound B-3
9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 대신 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 화합물 B-3 (9.8 g, 수율 75%)을 얻었다. Except for using 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid, the above synthesis example 8 was carried out to obtain compound B-3 (9.8 g, yield 75%).
HRMS [M]+: 501.62
HRMS [M]+: 501.62
[합성예 10] 화합물 B-70의 합성[Synthesis Example 10] Synthesis of compound B-70
9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 대신 (9,9-Diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol)를 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 화합물 B-70 (12.2g, 수율 76%)을 얻었다. Except for using (9,9-Diphenyl-9H-fluoren-2-yl)-boronic acid (11.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid, the above In the same manner as in Synthesis Example 8, compound B-70 (12.2 g, yield 76%) was obtained.
HRMS [M]+: 625.76
HRMS [M]+: 625.76
[합성예 11] 화합물 B-134의 합성[Synthesis Example 11] Synthesis of compound B-134
9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 대신 9,9'-Spirobi[9H-fluorene]-2-boronic acid (11.88g, 0.033 mol)를 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 화합물 B-134 (12.5 g, 수율 78%)을 얻었다. The above synthesis example, except that 9,9'-Spirobi[9H-fluorene]-2-boronic acid (11.88 g, 0.033 mol) was used instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 8 was carried out to obtain compound B-134 (12.5 g, yield 78%).
HRMS [M]+: 623.74
HRMS [M]+: 623.74
[합성예 12] 화합물 B-21의 합성[Synthesis Example 12] Synthesis of compound B-21
<단계 1> 화합물 II-1의 합성<Step 1> Synthesis of compound II-1
질소 기류 하에서 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine (12.0 g, 0.031 mol), 3-Chlorophenylboronic acid (6.3 g, 0.040 mol), Pd(PPh3)4 (1.13 g, 0.002 mol) 및 Potassium carbonate (9.1 g, 0.093 mol)을 혼합한 다음, 1,4-Dioxane (100 ㎖) 및 H2O (30 ㎖)에서 환류 교반하였다. 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine (12.0 g, 0.031 mol), 3-Chlorophenylboronic acid (6.3 g, 0.040 mol), Pd(PPh) under a nitrogen stream 3 ) 4 (1.13 g, 0.002 mol) and Potassium carbonate (9.1 g, 0.093 mol) were mixed, followed by stirring under reflux in 1,4-Dioxane (100 mL) and H 2 O (30 mL).
반응 종료 후, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 상기 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane: MC = 5:1 (v/v))로 정제하여 화합물 II-1 (11.0 g, 수율 83%)를 얻었다.
After completion of the reaction, the organic layer was separated with methylene chloride, and water was removed from the organic layer using MgSO 4 . After removing the solvent from the organic layer from which water was removed, it was purified by column chromatography (Hexane: MC = 5:1 (v/v)) to obtain Compound II-1 (11.0 g, yield 83%).
<단계 2> 화합물 B-21의 합성 <Step 2> Synthesis of compound B-21
질소 기류 하에서 합성예 12의 <단계 1>에서 얻은 II-1 (11.0 g, 0.026 mol), 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd(OAc)2 (0.58 g, 2.6 mmol), XPhos (2.5 g, 5.2 mmol) 및 Cesium carbonate (16.9 g, 0.052 mol)을 혼합한 다음, Toluene (200 ㎖), Ethanol (100 ㎖) 및 H2O (50 ㎖)에서 환류 교반하였다. II-1 (11.0 g, 0.026 mol), 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid (7.9 g, 0.033 mol), Pd ( OAc) 2 (0.58 g, 2.6 mmol), XPhos (2.5 g, 5.2 mmol) and Cesium carbonate (16.9 g, 0.052 mol) were mixed, followed by Toluene (200 mL), Ethanol (100 mL) and H 2 O ( 50 mL) and stirred at reflux.
반응 종료 후, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 상기 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane: MC = 5:1 (v/v)]로 정제하여 화합물 B-21 (11.6 g, 수율 77%)를 얻었다. After completion of the reaction, the organic layer was separated with methylene chloride, and water was removed from the organic layer using MgSO 4 . After removing the solvent from the organic layer from which water was removed, it was purified by column chromatography (Hexane: MC = 5:1 (v/v)] to obtain Compound B-21 (11.6 g, yield 77%).
HRMS [M]+: 577.72
HRMS [M]+: 577.72
[합성예 13] 화합물 B-23의 합성[Synthesis Example 13] Synthesis of compound B-23
9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 대신 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol)을 사용한 것을 제외하고는, 상기 합성예 12와 동일한 과정을 수행하여 화합물 B-23 (10.8 g, 수율 72%)을 얻었다. Except for using 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid, the above synthesis example 12 was carried out to obtain compound B-23 (10.8 g, yield 72%).
HRMS [M]+: 577.72
HRMS [M]+: 577.72
[합성예 14] 화합물 B-31의 합성[Synthesis Example 14] Synthesis of compound B-31
<단계 1> 화합물 II-2의 합성<Step 1> Synthesis of compound II-2
2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine 대신 4-(3-Bromo-phenyl)-2,6-diphenyl-pyrimidine (12.0g, 0.031 mol)를 사용한 것을 제외하고는, 상기 합성예 12의 <단계 1>과 동일한 과정을 수행하여 화합물 II-2 (11.0 g, 수율 85%)를 얻었다.
Use 4-(3-Bromo-phenyl)-2,6-diphenyl-pyrimidine (12.0 g, 0.031 mol) instead of 2-(3-Bromo-phenyl)-4,6-diphenyl-[1,3,5]triazine Except for the use, the same procedure as in <Step 1> of Synthesis Example 12 was performed to obtain Compound II-2 (11.0 g, yield 85%).
<단계 2> 화합물 B-31의 합성 <Step 2> Synthesis of compound B-31
I-1 대신 합성예 12의 <단계 1>에서 얻은 II-2를 사용한 것을 제외하고는, 상기 합성예 12의 <단계 2>와 동일한 과정을 수행하여 화합물 B-31 (11.3g, 수율 75%)을 얻었다. Except for using II-2 obtained in <Step 1> of Synthesis Example 12 instead of I-1, the same procedure as in <Step 2> of Synthesis Example 12 was performed, and Compound B-31 (11.3 g, yield 75%) ) was obtained.
HRMS [M]+: 576.73
HRMS [M]+: 576.73
[합성예 15] 화합물 B-35의 합성[Synthesis Example 15] Synthesis of compound B-35
9,9-Dimethyl-9H-fluoren-2-yl-boronic acid 대신 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol)을 사용한 것을 제외하고는, 상기 합성예 14와 동일한 과정을 수행하여 화합물 B-35 (10.9 g, 수율 72%)을 얻었다. Except for using 9,9-Dimethyl-9H-fluoren-3-yl-boronic acid (7.9 g, 0.033 mol) instead of 9,9-Dimethyl-9H-fluoren-2-yl-boronic acid, the above synthesis example In the same manner as in 14, compound B-35 (10.9 g, yield 72%) was obtained.
HRMS [M]+: 576.73
HRMS [M]+: 576.73
[실시예 1 내지 56] 유기 전계 발광 소자의 제조[Examples 1 to 56] Preparation of organic electroluminescent devices
합성예에서 합성된 화합물을 통상적으로 알려진 방법으로 고순도 승화 정제를 한 후, 하기와 같이 유기 전계 발광 소자를 제조하였다.After high-purity sublimation purification of the compound synthesized in Synthesis Example by a commonly known method, an organic electroluminescent device was prepared as follows.
ITO(Indium tin oxide)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.A glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was ultrasonically cleaned with distilled water. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 기판(전극) 위에, 합성예 1 내지 7에서 합성된 각각의 화합물을 호스트 A로, 합성예 8 내지 15에서 합성된 각각의 화합물을 각각 호스트 B로 이용하여, m-MTDATA(60 nm) / TCTA(80 nm) / 90 %의 호스트 A와 호스트 B + 10 %의 Ir(ppy)3(30 nm) / BCP(10 nm) / Alq3(30 nm) / LiF(1 nm) / Al(200 nm) 순으로 적층하여 유기 전계 발광 소자를 제조하였다.On the ITO transparent substrate (electrode) prepared as described above, using each compound synthesized in Synthesis Examples 1 to 7 as Host A and each compound synthesized in Synthesis Examples 8 to 15 as Host B, respectively, m-MTDATA (60 nm) / TCTA (80 nm) / 90% Host A and Host B + 10% Ir(ppy) 3 (30 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) ) / Al (200 nm) were stacked in the order to prepare an organic electroluminescent device.
이때, 사용된 m-MTDATA, TCTA, Ir(ppy)3 및 BCP의 구조는 하기와 같으며, 호스트 A와 호스트 B의 혼합비율은 50:50으로 하였다.At this time, the structures of m-MTDATA, TCTA, Ir(ppy) 3 and BCP used were as follows, and the mixing ratio of host A and host B was 50:50.
[실시예 57 내지 59] 유기 전계 발광 소자의 제조[Examples 57 to 59] Preparation of organic electroluminescent devices
실시예 1과 같이 준비된 ITO 투명 기판(전극) 위에, 합성예 4에서 합성된 화합물(A-11)을 호스트 A로, 합성예 8에서 합성된 화합물(B-1)을 호스트 B로 이용하여, m-MTDATA(60 nm) / TCTA(80 nm) / 90 %의 A-11와 B-1 + 10 %의 Ir(ppy)3(30 nm) / BCP(10 nm) / Alq3(30 nm) / LiF(1 nm) / Al(200 nm) 순으로 적층하여 유기 전계 발광 소자를 제조하였다.Example 1 On the same prepared ITO transparent substrate (electrode), using the compound (A-11) synthesized in Synthesis Example 4 as host A and the compound (B-1) synthesized in Synthesis Example 8 as host B, m-MTDATA ( 60 nm) / TCTA (80 nm) / 90 % A-11 and B-1 + 10 % Ir(ppy) 3 (30 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in the order to prepare an organic electroluminescent device.
이때, 호스트 A와 호스트 B의 혼합비율은 하기 표 1과 같이 조정하였다.
At this time, the mixing ratio of host A and host B was adjusted as shown in Table 1 below.
[비교예 1] 유기 전계 발광 소자의 제조[Comparative Example 1] Preparation of organic electroluminescent device
발광층 형성시 90 %의 CBP + 10 %의 Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% of CBP + 10% of Ir(ppy) 3 was used to form the emission layer.
이때, 사용된 CBP의 구조는 하기와 같다.At this time, the structure of the CBP used is as follows.
[비교예 2] 유기 전계 발광 소자의 제조[Comparative Example 2] Preparation of organic electroluminescent device
발광층 형성시 90 %의 Com-1 + 10 % Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제조하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% of Com-1 + 10% Ir(ppy) 3 was used when the light emitting layer was formed.
이때, 사용된 Com-1의 구조는 하기와 같다.In this case, the structure of Com-1 used is as follows.
[비교예 3] 유기 전계 발광 소자의 제조[Comparative Example 3] Preparation of organic electroluminescent device
발광층 형성시 90 %의 A-11 + 10 %의 Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제조하였다.
An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% of A-11 + 10% of Ir(ppy) 3 was used to form the emission layer.
[실험예][Experimental example]
실시예 1 내지 59 및 비교예 1 내지 3에서 제조된 각각의 유기 전계 발광 소자에 대하여 전류밀도 10mA/㎠에서 구동전압 및 전류효율을 측정하였고, 그 결과를 하기 표 1에 나타내었다.For each of the organic electroluminescent devices prepared in Examples 1 to 59 and Comparative Examples 1 to 3, the driving voltage and current efficiency were measured at a current density of 10 mA/cm 2 , and the results are shown in Table 1 below.
상기 표 1에서 나타낸 바와 같이, 본 발명의 화합물 A와 화합물 B를 혼합하여 발광층에 적용할 경우(실시예 1 내지 59)가 종래 CBP만을 적용한 경우(비교예 1), Com-1만을 적용한 경우(비교예 2) 또는 화합물 A만을 적용한 경우(비교예 3)보다 구동전압 및 전류효율이 우수한 것을 확인할 수 있다.As shown in Table 1, in the case of applying to the light emitting layer by mixing Compound A and Compound B of the present invention (Examples 1 to 59), when only CBP was applied (Comparative Example 1), when only Com-1 was applied ( It can be confirmed that the driving voltage and current efficiency are superior to those of Comparative Example 2) or when only Compound A was applied (Comparative Example 3).
Claims (8)
상기 1층 이상의 유기물층 중에서 적어도 하나는 제1 호스트와 제2 호스트를 포함하되,
상기 제1 호스트는 하기 화학식 1로 표시되는 화합물이며,
상기 제2 호스트는 하기 화학식 2로 표시되는 화합물인 유기 전계 발광 소자.
[화학식 1]
상기 화학식 1에서,
R1 내지 R6는 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, C1~C40의 알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,
a, f는 각각 0 내지 5의 정수이고,
b, e는 각각 0 내지 4의 정수이고,
c, d는 각각 0 내지 3의 정수이고,
[화학식 2]
상기 화학식 2에서,
Ra 및 Rb는 동일하거나 상이하며, 각각 독립적으로 C1~C40의 알킬기 및 C6~C60의 아릴기이거나, 서로 결합하여 축합 고리를 형성하고,
R7 내지 R9는 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접하는 기와 서로 결합하여 축합 고리를 형성하고,
L은 단일결합, C6~C18의 아릴렌기 및 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택되고,
Z1 내지 Z5는 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R10)이고, 이때, 적어도 하나는 N이며, C(R10)이 복수인 경우 복수의 C(R10)은 동일하거나 상이하고,
g, h, i는 각각 0 내지 4의 정수이고,
m, n은 각각 1 내지 3의 정수이고,
상기 R10은 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접한 기와 서로 결합하여 축합 고리를 형성하고,
상기 Ra, Rb의 알킬기, 아릴기와, 상기 R1 내지 R10의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기와, 상기 L의 아릴렌기, 헤테로아릴렌기는 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 또는 비치환되고, 상기 치환기가 복수일 경우 복수의 치환기는 동일하거나 상이하다.anode; cathode; and one or more organic material layers interposed between the positive electrode and the negative electrode,
At least one of the one or more organic material layers includes a first host and a second host,
The first host is a compound represented by the following formula (1),
The second host is an organic electroluminescent device of a compound represented by the following formula (2).
[Formula 1]
In Formula 1,
R 1 To R 6 Are the same or different, and are each independently selected from the group consisting of hydrogen, deuterium, a C 1 ~ C 40 alkyl group and a C 6 ~ C 60 aryl group,
a and f are each an integer from 0 to 5,
b and e are each an integer from 0 to 4,
c and d are each an integer from 0 to 3,
[Formula 2]
In Formula 2,
R a and R b are the same or different, and each independently a C 1 ~ C 40 alkyl group and a C 6 ~ C 60 aryl group, or combine with each other to form a condensed ring,
R 7 To R 9 are the same or different, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 of Alkyloxy group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 of an aryl boron group, a C 1 to C 40 phosphine group, a C 1 to C 40 phosphine oxide group, and a C 6 to C 60 arylamine group, or combine with adjacent groups to form a condensed ring do,
L is a single bond, C 6 ~ C 18 is selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
Z 1 to Z 5 are the same or different, and each independently is N or C(R 10 ), wherein at least one is N, and when C(R 10 ) is plural, a plurality of C(R 10 ) is the same or different,
g, h, i are each an integer from 0 to 4,
m and n are each an integer of 1 to 3,
Wherein R 10 is hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 of a cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyloxy group, C 6 to C 60 of Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 1 ~ C 40 of a phosphine group, a C 1 ~ C 40 phosphine oxide group and a C 6 ~ C 60 arylamine group, or combine with an adjacent group to form a condensed ring,
An alkyl group, an aryl group of R a and R b , an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkyl group of R 1 to R 10 A silyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group and an arylamine group, and the arylene group and heteroarylene group of L are each independently deuterium, a halogen group, a cyano group, a nitro group , amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 Aryl group, nuclear atom number 5 to 60 heteroaryl group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 1 ~ C 40 phosphine group, C 1 ~ C 40 phosphine oxide group and C 6 ~ C 60 It is unsubstituted or substituted with one or more substituents selected from the group consisting of an arylamine group, and when the substituents are plural, the plural substituents are the same or different.
상기 R1 내지 R6는 각각 독립적으로 페닐기 또는 비페닐기인 유기 전계 발광 소자.The method of claim 1,
The R 1 To R 6 Are each independently a phenyl group or a biphenyl group.
상기 화학식 2로 표시되는 화합물은 하기 화학식 3 내지 5로 표시되는 화합물로 이루어진 군에서 선택되는 유기 전계 발광 소자.
[화학식 3]
[화학식 4]
[화학식 5]
상기 화학식 3 내지 5에서,
Ra, Rb, R7 내지 R9, Z1 내지 Z5, g, h 및 i는 각각 상기 제1항에서 정의한 바와 같다.The method of claim 1,
The compound represented by Formula 2 is an organic electroluminescent device selected from the group consisting of compounds represented by Formulas 3 to 5.
[Formula 3]
[Formula 4]
[Formula 5]
In Formulas 3 to 5,
R a , R b , R 7 to R 9 , Z 1 to Z 5 , g, h and i are each as defined in claim 1 above.
상기 Ra 및 Rb는 동일하거나 상이하며, 각각 독립적으로 메틸기 또는 페닐기이거나, 서로 결합하여
Wherein R a and R b are the same or different, each independently a methyl group or a phenyl group, or bonded to each other
상기 화학식 2에서
상기 C-1 내지 C-15에서,
R10는 제1항에서 정의한 바와 같고,
R11는 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택되거나, 인접하는 기와 서로 결합하여 축합 고리를 형성하고,
p는 1 내지 4의 정수이고,
상기 R11의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되고, 상기 치환기가 복수일 경우 복수의 치환기는 동일하거나 상이하다.The method of claim 1,
In the above formula (2)
In C-1 to C-15,
R 10 is as defined in claim 1,
R 11 is hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, A heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 6 to C 60 aryloxy group, a C 1 to C 40 alkyloxy group , C 6 ~ C 60 Arylamine group, C 1 ~ C 40 Alkylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Arylphosphine group , C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylsilyl group, or is combined with an adjacent group to form a condensed ring,
p is an integer from 1 to 4,
An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, Aryl phosphine group, aryl phosphine oxide group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alky Nyl group, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 1 ~ C 40 alkylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron Group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 Unsubstituted or substituted with one or more substituents selected from the group consisting of an arylsilyl group, the substituent When is plural, the plural substituents are the same or different.
상기 제1 호스트와 제2 호스트의 혼합비율은 25:75 내지 75:25의 중량비율인 유기 전계 발광 소자.The method of claim 1,
The mixing ratio of the first host and the second host is an organic electroluminescent device in a weight ratio of 25:75 to 75:25.
상기 제1 호스트와 제2 호스트를 포함하는 유기물층은 인광 발광층인 유기 전계 발광 소자.The method of claim 1,
The organic material layer including the first host and the second host is an organic electroluminescent device that is a phosphorescent light emitting layer.
상기 발광층은 도펀트를 포함하되, 상기 도펀트는 금속 착체 화합물인 유기 전계 발광 소자.8. The method of claim 7,
The light emitting layer includes a dopant, wherein the dopant is an organic electroluminescent device of a metal complex compound.
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| EP4198103A1 (en) | 2021-12-14 | 2023-06-21 | Novaled GmbH | Organic light emitting diode and device comprising the same |
| EP4199125A1 (en) | 2021-12-14 | 2023-06-21 | Novaled GmbH | Organic light emitting diode, method for preparing the same and device comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013201153A (en) * | 2010-06-08 | 2013-10-03 | Idemitsu Kosan Co Ltd | Organic electroluminescent element |
| KR101429035B1 (en) * | 2013-05-16 | 2014-08-12 | 롬엔드하스전자재료코리아유한회사 | Organic Electroluminescent Compounds and Organic Electroluminescent Device Comprising the Same |
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| CN107501244B (en) * | 2011-11-22 | 2022-05-03 | 出光兴产株式会社 | Aromatic heterocyclic derivative, material for organic electroluminescent element, and organic electroluminescent element |
| KR101497134B1 (en) * | 2011-12-29 | 2015-03-02 | 제일모직 주식회사 | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode |
| KR20130094903A (en) * | 2012-02-17 | 2013-08-27 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescent compounds |
| KR101423067B1 (en) * | 2012-10-04 | 2014-07-29 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescence compounds and organic electroluminescence device comprising the same |
| KR101593465B1 (en) * | 2013-06-28 | 2016-02-12 | (주)피엔에이치테크 | Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013201153A (en) * | 2010-06-08 | 2013-10-03 | Idemitsu Kosan Co Ltd | Organic electroluminescent element |
| KR101429035B1 (en) * | 2013-05-16 | 2014-08-12 | 롬엔드하스전자재료코리아유한회사 | Organic Electroluminescent Compounds and Organic Electroluminescent Device Comprising the Same |
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