KR101820932B1 - New host material and organic electroluminescent device using the same - Google Patents
New host material and organic electroluminescent device using the same Download PDFInfo
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- KR101820932B1 KR101820932B1 KR1020150135978A KR20150135978A KR101820932B1 KR 101820932 B1 KR101820932 B1 KR 101820932B1 KR 1020150135978 A KR1020150135978 A KR 1020150135978A KR 20150135978 A KR20150135978 A KR 20150135978A KR 101820932 B1 KR101820932 B1 KR 101820932B1
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- organic
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
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- C—CHEMISTRY; METALLURGY
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Abstract
본 발명은 신규한 발광용 호스트 물질 및 이를 이용한 유기 발광 소자에 관한 것으로서, 본 발명에 따른 유기 발광 소자는 발광특성이 뛰어날 뿐만 아니라 구동전압을 강화시켜줌으로써 전력효율의 상승을 유도하여 소비전력이 개선되는 장점을 가진다.The present invention relates to a novel luminescent host material and an organic luminescent device using the same. The organic luminescent device according to the present invention not only excels in luminescence characteristics but also enhances a driving voltage, thereby inducing an increase in power efficiency, .
Description
본 발명은 신규한 발광용 호스트 물질 및 이를 이용한 유기 발광 소자에 관한 것으로, 보다 상세하게는 신규한 발광용 호스트 물질인 벤조퀴놀린 유도체 및 벤조퀴나졸린 유도체, 이를 발광층에 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel luminescent host material and an organic luminescent device using the same, and more particularly, to a novel luminescent host material, a benzoquinoline derivative and a benzoquinazoline derivative, and an organic luminescent device including the luminescent host material .
유기 발광 소자는 전자 주입 전극(음극) 과 정공 주입 전극(양극) 사이에 형성된 유기막에 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 EL 디스플레이에 비해 낮은 전압에서 (10V이하) 구동이 가능하고, 또한 전력 소모가 비교적 적으며, 색감이 뛰어나다는 장점이 있다. An organic light emitting device is a device that injects electric charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to form an electron and a hole. It is possible to form a device on a flexible transparent substrate such as a plastic substrate and to operate at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, It is relatively small and has an advantage of excellent color.
일반적인 유기 전기발광 소자의 구조는 기판, 양극, 정공을 양극으로부터 받아들이는 정공 주입층, 정공을 이송하는 정공 수송층, 정공과 전자가 결합하여 빛을 내는 발광층, 전자를 음극으로부터 받아들여 발광층으로 전달하는 전자 수송층, 및 음극으로 구성되어 있다. 경우에 따라서는 별도의 발광층 없이 전자 수송층이나 정공 수송층에 소량의 형광 또는 인광성 염료를 도핑하여 발광층을 구성할 수도 있으며, 고분자를 사용할 경우에는 일반적으로 정공 수송층과 발광층, 및 전자 수송층의 역할을 하나의 고분자가 동시에 수행할 수 있다. 두 전극 사이의 유기물 박막층들은 진공증착법 또는 스핀코팅, 잉크젯프린팅, 롤코팅 등의 방법으로 형성되며, 음극으로부터 전자의 효율적인 주입을 위해 별도의 전자 주입층을 삽입하는 경우도 있다.The structure of a general organic electroluminescent device includes a substrate, a cathode, a hole injecting layer for receiving holes from the anode, a hole transporting layer for transporting holes, a light emitting layer for emitting light by combining holes and electrons, An electron transport layer, and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of a fluorescent or phosphorescent dye to an electron transporting layer or a hole transporting layer without a separate light emitting layer. In the case of using a polymer, a hole transporting layer, a light emitting layer, and an electron transporting layer Can be performed simultaneously. The organic thin film layers between the two electrodes are formed by a vacuum deposition method, a spin coating method, an ink jet printing method, a roll coating method, or the like, and a separate electron injection layer may be inserted to efficiently inject electrons from the cathode.
전극과 유기물사이의 계면을 안정화시키거나, 또는 유기 물질의 경우 정공과 전자의 이동속도가 크게 차이가 나므로 적절한 정공 수송층과 전자 수송층을 사용하면 정공과 전자가 발광층으로 효과적으로 전달될 수 있고 발광층에서 정공과 전자의 밀도가 균형을 이루도록 하여 발광효율을 높이기 위하여 유기 발광 소자를 다층 박막 구조로 제작한다. Since the interface between the electrode and the organic material is stabilized, or the organic material has a large difference in moving speed between the hole and the electron, if a suitable hole transporting layer and electron transporting layer are used, holes and electrons can be effectively transferred to the light emitting layer. And the electron density are balanced so as to increase the luminous efficiency, the organic light emitting device is fabricated as a multilayer thin film structure.
유기 발광 소자에서 발광효율을 결정하는 가장 중요한 요인은 발광 재료이다. 발광 재료로는 현재 형광 재료가 널리 사용되고 있으나, 발광 메커니즘 상 인광 재료의 개발이 이론적으로 발광 효율을 보다 개선시킬 수 있는 방법 중의 하나이고, 이에 따라 현재까지 다양한 인광 재료에 대해서 개발이 이루어지고 있으며, 특히 인광 발광 호스트 재료로는 현재까지 CBP가 가장 널리 알려져 있고, BAlq 유도체를 호스트로 이용한 유기전계발광소자가 공지되어 있다. 그러나, 인광 발광 재료를 사용한 유기전계발광소자는 형광 발광 재료를 사용한 소자에 비해 전류 효율이 상당히 높으나, 인광 발광 재료의 호스트로 BAlq, CBP 등의 재료를 사용할 경우, 형광재료를 사용한 소자에 비해 구동 전압이 높아서 전력 효율면에서 큰 이점이 없고, 또한, 소자의 수명 측면에서도 만족할만한 수준이 되질 못하여 더욱 안정적이고, 고성능의 호스트 재료의 개발이 요구되고 있다. The most important factor determining the luminous efficiency in an organic light emitting device is a light emitting material. However, the development of a phosphorescent material on a light-emitting mechanism is one of the ways that the luminous efficiency can be improved more theoretically. Accordingly, a variety of phosphorescent materials have been developed to date, In particular, CBP is the most widely known phosphorescent host material, and an organic electroluminescent device using a BAlq derivative as a host is known. However, an organic electroluminescent device using a phosphorescent material has a significantly higher current efficiency than a device using a fluorescent material. However, when a material such as BAlq or CBP is used as a host of a phosphorescent material, There is no significant advantage in terms of power efficiency due to a high voltage and satisfactory level of life of the device can not be achieved, and development of a more stable and high-performance host material is required.
이에 본 발명자들은 상기 종래 기술의 문제점을 고려하여 발광 호스트 재료에 대한 연구를 거듭한 결과, 발광효율, 안정성 및 소자 수명을 크게 향상시킬 수 있는 신규한 발광용 호스트 물질인 벤조퀴놀린 유도체 및 벤조퀴나졸린 유도체, 이를 이용한 유기 발광 소자를 제공하고자 본 발명을 완성하였다.Accordingly, the inventors of the present invention have conducted studies on a light emitting host material in consideration of the problems of the prior art, and as a result, they have found that a novel luminescent host material, benzoquinoline derivative and benzoquinazoline And an organic light emitting device using the same.
본 발명은 신규한 발광용 호스트 물질인 벤조퀴놀린 유도체 및 벤조퀴나졸린 유도체를 제공하는데 목적이 있다.It is an object of the present invention to provide a novel benzoquinoline derivative and a benzoquinazoline derivative which are host materials for luminescence.
또한, 본 발명은 상기 신규한 발광용 호스트 물질을 이용하여 발광특성이 뛰어날 뿐만 아니라 구동전압을 강화시켜줌으로서, 전력효율의 상승을 유도하여 소비전력이 개선된 유기 발광 소자를 제공하는데 다른 목적이 있다. Another object of the present invention is to provide an organic light emitting device having improved light emitting characteristics and a driving voltage by using the novel light emitting host material, thereby improving power efficiency and improving power consumption .
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
[상기 화학식 1에서, [In the above formula (1)
R1 내지 R6는 서로 독립적으로 수소, 중수소 또는 (C1-C30)알킬이고; R 1 to R 6 are independently of each other hydrogen, deuterium or (C 1 -C 30) alkyl;
X 및 Y는 서로 독립적으로 N 및 CH에서 선택되고, 적어도 하나 이상은 N이며;X and Y are independently selected from N and CH, and at least one is N;
L1 및 L2 는 서로 독립적으로 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고, 적어도 하나 이상은 아릴렌 또는 헤테로아릴렌이며;L 1 and L 2 independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene and at least one is arylene or heteroarylene;
V1 및 V2 는 서로 독립적으로 수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고;V 1 and V 2 independently of one another are hydrogen, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl;
상기 R1 내지 R6의 알킬, L1 및 L2의 아릴렌 및 헤테로아릴렌, V1 및 V2 의 알킬, 아릴 및 헤테로아릴은 (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, (C1-C30)알콕시, (C6-C30)아릴옥시, (C6-C30)아릴, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;Wherein R 1 alkyl of 1 to R 6, L 1 arylene and a and L 2 heteroarylene, alkyl, aryl and heteroaryl groups of V 1 and V 2 are (C1-C30) alkyl, halo (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) aryl, (C3-C30) aryl (C3-C30) heteroaryl, (C3-C30) heteroaryl substituted with (C6-C30) arylsilyl, di (C1-C30) alkylsilyl, di (C1-C30) alkylsilyl, mono- or di (C6-C30) arylsilyl, nitro, and hydroxy;
상기 헤테로아릴렌 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함된다.]Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
본 발명의 일 실시예에 따른, 상기 L1 및 L2 는 서로 독립적으로 단일결합 또는 하기 구조에서 선택되는 것인 화합물일 수 있다.According to an embodiment of the present invention, L < 1 > and L < 2 > may be a single bond or a compound selected from the following structures.
[상기 구조에서, [In the above structure,
R21 내지 R25는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이다.] R 21 to R 25 independently of one another are hydrogen, deuterium, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl.
본 발명의 일 실시예에 따른, 상기 V1 및 V2 는 서로 독립적으로 수소 또는 하기 구조에서 선택되는 것인 화합물일 수 있다.According to one embodiment of the present invention, V 1 and V 2 are independently of each other hydrogen or a compound selected from the following structures.
[상기 구조에서, [In the above structure,
R11 내지 R14는 서로 독립적으로 수소, 중수소, (C1-C30)알킬 또는 (C6-C30)아릴이다.] R 11 to R 14 independently of one another are hydrogen, deuterium, (C 1 -C 30) alkyl or (C 6 -C 30) aryl.
본 발명의 일 실시예에 따른, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 또는 하기 화학식 3으로 표시되는 화합물일 수 있다.According to one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by Formula 2 or 3.
[화학식 2](2)
[화학식 3](3)
[상기 화학식 2 및 화학식 3에서, [In the formulas (2) and (3)
R1 내지 R6는 서로 독립적으로 수소, 중수소, (C1-C30)알킬이고; R 1 to R 6 independently from each other are hydrogen, deuterium, (C 1 -C 30) alkyl;
L1 및 L2 는 서로 독립적으로 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고, 적어도 하나 이상은 아릴렌 또는 헤테로아릴렌이며;L 1 and L 2 independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene and at least one is arylene or heteroarylene;
V1 및 V2 는 서로 독립적으로 수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고;V 1 and V 2 independently of one another are hydrogen, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl;
상기 헤테로아릴렌 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함된다.]Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
본 발명의 일 실시예에 따른, 화합물은 바람직하게 하기 화합물로부터 선택되는 것일 수 있다.According to one embodiment of the present invention, the compound may be preferably selected from the following compounds.
본 발명의 일 실시예에 따른 화합물은 보다 바람직하게 하기 화합물로부터 선택될 수 있다.The compounds according to one embodiment of the present invention may be more preferably selected from the following compounds.
본 발명에 따른 발광용 호스트 물질은 휘도가 높고 발광효율이 우수할 뿐만 아니라 구동전압을 강화시켜줌으로써 전력효율의 상승을 유도하여 소비전력이 개선된 유기 발광 소자를 제작할 수 있는 장점이 있다.The host material for luminescence according to the present invention has advantages of high brightness and excellent luminous efficiency as well as enhancing the driving voltage to induce an increase in power efficiency and to manufacture an organic light emitting device having improved power consumption.
도 1은 실시예 4 내지 실시예6 및 비교예 1을 이용한 유기 발광 소자의 발광효율을 나타낸 그래프이며,
도 2는 실시예 4 내지 실시예6 및 비교예 1을 이용한 유기 발광 소자의 전력효율을 나타낸 그래프이며,
도 3은 실시예 4 내지 실시예6 및 비교예 1을 이용한 유기 발광 소자의 소자 수명을 나타낸 그래프이며,
도 4는 실시예 1 내지 실시예3 및 비교예 1을 이용한 유기 발광 소자의 발광효율을 나타낸 그래프이며,
도 5는 실시예 1 내지 실시예3 및 비교예 1을 이용한 유기 발광 소자의 전력효율을 나타낸 그래프이며,
도 6은 실시예 1 내지 실시예3 및 비교예 1을 이용한 유기 발광 소자의 소자 수명을 나타낸 그래프이다.1 is a graph showing the luminous efficiency of an organic luminescent device using Examples 4 to 6 and Comparative Example 1,
FIG. 2 is a graph showing power efficiency of the organic light emitting device using the fourth through sixth embodiments and the first comparative example,
3 is a graph showing lifetime of a device of an organic light emitting device using Examples 4 to 6 and Comparative Example 1,
4 is a graph showing the luminous efficiency of the organic luminescent device using Examples 1 to 3 and Comparative Example 1,
FIG. 5 is a graph showing power efficiency of the organic light emitting device using the embodiment 1 to 3 and the comparative example 1,
6 is a graph showing lifetime of a device of an organic light emitting device using Examples 1 to 3 and Comparative Example 1. FIG.
본 발명에 따른, 신규한 발광용 호스트 물질 및 이를 이용한 유기 발광 소자에 대하여 이하 상술하나, 이때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.The novel host material for luminescence and the organic light emitting device using the same according to the present invention will be described below. However, unless otherwise defined in technical terms and scientific terms used herein, And the description of known functions and configurations which may unnecessarily obscure the gist of the present invention will be omitted in the following description.
본 발명은 하기 화학식 1로 표시되는 발광용 호스트 물질 및 이를 포함하는 유기 발광 소자에 관한 것으로서, 본 발명에 따른 발광용 호스트 물질을 이용함으로서, 발광특성이 뛰어날 뿐만 아니라 구동전압을 강화시켜줌으로써 전력효율의 상승을 유도하여 소비전력이 개선된 유기 발광 소자를 제조할 수 있는 장점이 있다.The present invention relates to a luminescent host material represented by the following general formula (1) and an organic luminescent device including the luminescent host material. The luminescent host material according to the present invention is excellent in light emission characteristics, And thus an organic light emitting device having improved power consumption can be manufactured.
또한 본 발명에 따른 하기 화학식 1로 표시되는 화합물을 발광층에 포함하는 유기 발광 소자는 벤조퀴놀린 또는 벤조퀴나졸린을 반드시 포함함으로서, 증착 또는 용액공정으로 용이하게 적용될 수 있으며, 열적안정성이 뛰어나며, 높은 전자밀도를 가져 발광효율이 높다.Further, the organic light emitting device comprising the compound represented by the following formula (1) according to the present invention in the light emitting layer necessarily includes benzoquinoline or benzoquinazoline, which can be easily applied in a deposition or solution process, has excellent thermal stability, The density is high and the luminous efficiency is high.
[화학식 1][Chemical Formula 1]
[상기 화학식 1에서, [In the above formula (1)
R1 내지 R6는 서로 독립적으로 수소, 중수소 또는 (C1-C30)알킬이고; R 1 to R 6 are independently of each other hydrogen, deuterium or (C 1 -C 30) alkyl;
X 및 Y는 서로 독립적으로 N 및 CH에서 선택되고, 적어도 하나 이상은 N이며;X and Y are independently selected from N and CH, and at least one is N;
L1 및 L2 는 서로 독립적으로 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고, 적어도 하나 이상은 아릴렌 또는 헤테로아릴렌이며;L 1 and L 2 independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene and at least one is arylene or heteroarylene;
V1 및 V2 는 서로 독립적으로 수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고;V 1 and V 2 independently of one another are hydrogen, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl;
상기 R1 내지 R6의 알킬, L1 및 L2의 아릴렌 및 헤테로아릴렌, V1 및 V2 의 알킬, 아릴 및 헤테로아릴은 (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, (C1-C30)알콕시, (C6-C30)아릴옥시, (C6-C30)아릴, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;Wherein R 1 alkyl of 1 to R 6, L 1 arylene and a and L 2 heteroarylene, alkyl, aryl and heteroaryl groups of V 1 and V 2 are (C1-C30) alkyl, halo (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) aryl, (C3-C30) aryl (C3-C30) heteroaryl, (C3-C30) heteroaryl substituted with (C6-C30) arylsilyl, di (C1-C30) alkylsilyl, di (C1-C30) alkylsilyl, mono- or di (C6-C30) arylsilyl, nitro, and hydroxy;
상기 헤테로아릴렌 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함된다.]Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
본 발명에 기재된 「알킬」, 「알콕시」 및 그 외 「알킬」부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하고, 「시클로알킬」은 단일 고리계 뿐만 아니라 치환 또는 비치환된 아다만틸 또는 치환 또는 비치환된 (C7-C30)바이시클로알킬과 같은 여러 고리계 탄화수소도 포함한다. 본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로서 페닐, 나프틸, 비페닐, 터페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴, 트리페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등이 있다. 본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P(=O), Si 및 P로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연결된 형태도 포함한다. 상기 헤테로아릴기는 고리내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적인 예로서 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴, 다이벤조퓨란닐, 다이벤조싸이오페닐 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 들수 있다.The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms, and "cycloalkyl" includes both single ring systems as well as substituted or unsubstituted adamantyl Or a plurality of cyclic hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. &Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, . Heteroaryl " as used in the present invention includes 1 to 4 hetero atoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon An aryl group, a 5- to 6-membered monocyclic heteroaryl, and a polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, Monocyclic heteroaryl such as tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoiso Benzothiazolyl, benzothiazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), polycyclic heteroaryls such as benzyloxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, Quaternary salts and the like.
본 발명의 일 실시예에 따른 상기 화학식 1에서 우수한 발광효율을 얻기 위한 측면에서, 상기 L1 및 L2 는 서로 독립적으로 단일결합 또는 하기 구조에서 선택될 수 있으나 이에 한정되는 것은 아니다.In order to obtain excellent luminous efficiency in the formula 1 according to an embodiment of the present invention, L 1 and L 2 may be independently selected from a single bond or the following structure, but are not limited thereto.
[상기 구조에서, [In the above structure,
R21 내지 R25는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이다.] R 21 to R 25 independently of one another are hydrogen, deuterium, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl.
바람직하게 본 발명에 따른 상기 화학식 1에서, 용이한 전자이동이 가능하여 우수한 발광효율을 가지며, 향상된 소자의 구동 수명을 얻기 위한 측면에서, 상기 V1 및 V2 는 서로 독립적으로 수소 또는 하기 구조에서 선택될 수 있으나 이에 한정되는 것은 아니다. Preferably, V 1 and V 2 are independently hydrogen or a group of the following formulas (1) and (2), respectively, in order to facilitate electron transfer and excellent luminous efficiency, But is not limited thereto.
[상기 구조에서, [In the above structure,
R11 내지 R14는 서로 독립적으로 수소, 중수소, (C1-C30)알킬 또는 (C6-C30)아릴이다.] R 11 to R 14 independently of one another are hydrogen, deuterium, (C 1 -C 30) alkyl or (C 6 -C 30) aryl.
본 발명에 따른 상기 화학식 1에서, 탁월한 용액상 박막형성능을 가지는 측면에서, 보다 바람직하게는 하기 화학식 2 또는 하기 화학식 3으로 표시되는 화합물 일 수 있다.In the formula (1) according to the present invention, the compound represented by the following formula (2) or (3) may be more preferable from the viewpoint of having excellent solution phase thin film type performance.
[화학식 2](2)
[화학식 3](3)
[상기 화학식 2 및 화학식 3에서, [In the formulas (2) and (3)
R1 내지 R6는 서로 독립적으로 수소, 중수소, (C1-C30)알킬이고; R 1 to R 6 independently from each other are hydrogen, deuterium, (C 1 -C 30) alkyl;
L1 및 L2 는 서로 독립적으로 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고, 적어도 하나 이상은 아릴렌 또는 헤테로아릴렌이며;L 1 and L 2 independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene and at least one is arylene or heteroarylene;
V1 및 V2 는 서로 독립적으로 수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고;V 1 and V 2 independently of one another are hydrogen, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl;
상기 헤테로아릴렌 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함된다.]Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
본 발명에 따른 발광용 호스트 물질은, 전자 이동도 향상 및 소자의 효율 향상 측면에서 바람직하게 하기 화합물로 예시될 수 있으나, 이에 한정되는 것은 아니다.The host material for luminescence according to the present invention can be exemplified by the following compounds in view of the improvement of the electron mobility and the improvement of the efficiency of the device, but the present invention is not limited thereto.
본 발명에 따른 화합물은, 우수한 열적 안정성을 가지며, 증착 또는 용액공정으로 다양한 기능층의 용도로 적용할 수 있는 측면에서 더욱 바람직하게 하기 화합물로 예시될 수 있으나, 이에 한정되는 것은 아니다.The compounds according to the present invention may be exemplified by the following compounds in view of their excellent thermal stability and applicability to various functional layers by vapor deposition or solution processes, but the present invention is not limited thereto.
본 발명의 화합물은 하기 반응식 1로 예시되는 방법으로 제조될 수 있으나, 이에 한정되는 것은 아니며, 공지의 유기반응을 통하여 제조될 수 있음을 물론이다.The compound of the present invention can be prepared by the method illustrated by the following Reaction Scheme 1, but it is not limited thereto and can be prepared through a known organic reaction.
[반응식 1][Reaction Scheme 1]
[상기 반응식 1에서,[Reaction Scheme 1]
R1 내지 R6는 서로 독립적으로 수소, 중수소 또는 (C1-C30)알킬이고; R 1 to R 6 are independently of each other hydrogen, deuterium or (C 1 -C 30) alkyl;
X 및 Y는 서로 독립적으로 N 및 CH에서 선택되고, 적어도 하나 이상은 N이며;X and Y are independently selected from N and CH, and at least one is N;
L1 및 L2 는 서로 독립적으로 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이고, 적어도 하나 이상은 아릴렌 또는 헤테로아릴렌이며;L 1 and L 2 independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene and at least one is arylene or heteroarylene;
V1 및 V2 는 서로 독립적으로 수소, (C1-C30)알킬, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고;V 1 and V 2 independently of one another are hydrogen, (C 1 -C 30) alkyl, mono (C 6 -C 30) arylamino, di (C 6 -C 30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) aryl or (C3-C30) heteroaryl;
상기 R1 내지 R6의 알킬, L1 및 L2의 아릴렌 및 헤테로아릴렌, V1 및 V2 의 알킬, 아릴 및 헤테로아릴은 (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, (C1-C30)알콕시, (C6-C30)아릴옥시, (C6-C30)아릴, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;Wherein R 1 alkyl of 1 to R 6, L 1 arylene and a and L 2 heteroarylene, alkyl, aryl and heteroaryl groups of V 1 and V 2 are (C1-C30) alkyl, halo (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) aryl, (C3-C30) aryl (C3-C30) heteroaryl, (C3-C30) heteroaryl substituted with (C6-C30) arylsilyl, di (C1-C30) alkylsilyl, di (C1-C30) alkylsilyl, mono- or di (C6-C30) arylsilyl, nitro, and hydroxy;
상기 헤테로아릴렌 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함되며;Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;
A1 및 A2 은 각각 독립적으로 할로겐, 
B1 및 B2 는 각각 독립적으로 수소, 할로겐, 
또한, 본 발명은 유기 발광 소자를 제공하며, 본 발명에 따른 유기 발광 소자는 제1전극; 제2전극; 및 상기 제1전극 및 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 1층으로 이루어진 단층 구조일 수도 있으나, 발광층을 포함하는 2층 이상의 다층 구조일 수도 있다. 상기 유기 발광 소자의 유기물층이 다층 구조인 경우, 이는 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층 등이 적층된 구조일 수 있다. 그러나, 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기물층을 포함할 수 있다. In addition, the present invention provides an organic light emitting device, wherein the organic light emitting device according to the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode. The organic material layer may have a single-layer structure including one layer, or a multilayer structure including two or more layers including a light-emitting layer. When the organic material layer of the organic light emitting device has a multilayer structure, it may have a structure in which a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer are stacked. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.
이때, 상기 화학식 1의 발광용 호스트 물질은 상기 유기물층에 포함될 수 있으며, 상술한 본 발명에 따른 화합물은 큰 밴드갭을 가져, 선명한 황색을 구현할 수 있는 인광 호스트 물질일 수 있다. 또한 추가적으로 도판트 물질과 혼합되어 발광층에 포함될 수 있다. 상술한 본 발명에 따른 발광용 호스트 물질을 발광층에 사용함으로서, 높은 색순도를 발현할 수 있다. 상기 도판트 물질은 형광도판트, 인광도판트 또는 이들의 혼합된 물질일 수 있으며, 본 발명의 유기 발광 소자에 적용되는 형광도판트 또는 인광도판트는 특별히 제한되지는 않는다. 또한 본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.At this time, the luminescent host material of Formula 1 may be included in the organic material layer, and the compound of the present invention may be a phosphorescent host material having a large band gap and capable of realizing a clear yellow color. In addition, it may be mixed with the dopant material and included in the light emitting layer. By using the above-described light emitting host material according to the present invention in the light emitting layer, high color purity can be exhibited. The dopant material may be a fluorescent dopant, a phosphorescent dopant, or a mixed material thereof. The fluorescent dopant or phosphorescent dopant applied to the organic light emitting device of the present invention is not particularly limited. Further, the organic light emitting diode according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
본 발명에 따른 발광용 호스트 물질은 유기 전자 소자인 유기 태양 전지, 유기 감광체 또는 유기 트랜지스터에서도 유기 발광 소자에 적용되는 것과 유사한 원리로 작용될 수 있다.The host material for luminescence according to the present invention may be applied to organic solar cells, organic photoconductors or organic transistors, which are organic electronic devices, on a principle similar to that applied to organic light emitting devices.
본 발명은 상술한 본 발명에 따른 유기 전자 소자를 포함하는 발광 장치를 제공한다. 상기 발광 장치의 비한정적인 일예로는 유기 박막 트랜지스터(OＴＦＴ), 유기센서 등일 수 있으며, 상기 발광 장치는 본 발명에 따른 발광용 호스트 물질을 포함하여 제작됨으로서, 색순도가 우수할 뿐만 아니라 발광 효율이 뛰어나고 수명이 긴 발광 장치를 구현할 수 있다.The present invention provides a light emitting device including the above-described organic electronic device according to the present invention. The light emitting device may be an organic thin film transistor (OTFT), an organic sensor, or the like, and the light emitting device may be manufactured by including the light emitting host material according to the present invention, A light emitting device having excellent performance and long lifetime can be realized.
또한 본 발명은 상기 발광 장치를 포함하는 전자 기기를 제공한다. 상기 전자 기기의 비한정적인 일예로는 텔레비전, 핸드폰, 카메라, 센서 등일 수 있으며, 본 발명에 따른 발광용 호스트 물질을 사용함에 따라 색채 재현성이 뛰어나고 고순도의 색발현이 가능하며, 소비 전력이 낮아, 장기 수명화의 실현이 가능하다는 장점을 가진다.The present invention also provides an electronic apparatus including the light emitting device. Examples of the electronic device include a television, a mobile phone, a camera, a sensor, and the like. By using the host material for luminescence according to the present invention, color reproducibility, high color purity, low power consumption, It is possible to realize a long life span.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나, 하기의 실시예는 본 발명을 예시하기 위한 것이며, 이에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
[ 실시예 1] 화합물 6 의 제조 [ Example 1] Preparation of Compound 6
Core 1-1의 제조Manufacture of Core 1-1
3,5-Dibromobenzaldehyde (20.0 g, 75.8 mmol)을 에탄올 400 mL에 완전히 용해시킨 후 1-Tetralone (15.5 g, 106.1 mmol)을 첨가하고 온도를 0 ℃로 냉각하였다. 0 내지 5 ℃를 유지하며, 8.5 M NaOH 수용액 20 mL를 천천히 떨어뜨렸다. 첨가 종료 후, 1시간 동안 추가 교반 후 생성된 고체 화합물을 여과하였다. 여과된 고체 화합물을 에탄올로 2회 세척 후 건조하였다. 건조 후 연한 노랑색 고체 화합물 Core 1-1 (22.0 g, 74.0 %)을 얻었다. 3,5-Dibromobenzaldehyde (20.0 g, 75.8 mmol) was completely dissolved in 400 mL of ethanol, followed by addition of 1-Tetralone (15.5 g, 106.1 mmol) and the temperature was cooled to 0 ° C. 20 mL of 8.5 M NaOH aqueous solution was slowly dropped while maintaining the temperature at 0 to 5 占 폚. After completion of the addition, the resulting solid compound was filtered after further stirring for 1 hour. The filtered solid compound was washed twice with ethanol and then dried. After drying, pale yellow solid compound Core 1-1 (22.0 g, 74.0%) was obtained.
1H-NMR(CDCl3)δ [ppm]: 7.88 [s, 1H], 7.73 [d, 1H], 7.68 [t, 1H], 7.61 [s, 1H], 7.51 [s, 2H], 7.46-7.48 [m, 2H], 3.10-2.90 [m, 4H]. 1 H-NMR (CDCl 3) δ [ppm]: 7.88 [s, 1H], 7.73 [d, 1H], 7.68 [t, 1H], 7.61 [s, 1H], 7.51 [s, 2H], 7.46- 7.48 [m, 2H], 3.10-2.90 [m, 4H].
Core 1-2의 제조Manufacture of Core 1-2
피리딘 120 mL를 반응기에 첨가 후, 교반을 시키면서 Phenacyl bromide (12.0 g, 60.3 mmol)를 천천히 첨가하였다. 첨가 종료 후, 1시간 동안 추가 교반 후 생성된 고체 화합물을 여과하였다. 여과된 고체 화합물을 디에틸 에테르로 2회 세척 후 건조하였다. 건조 후 흰색 고체 화합물 Core 1-2 (13.0 g, 77.5 %)를 얻었다. 120 mL of pyridine was added to the reactor, and Phenacyl bromide (12.0 g, 60.3 mmol) was added slowly while stirring. After completion of the addition, the resulting solid compound was filtered after further stirring for 1 hour. The filtered solid compound was washed twice with diethyl ether and dried. After drying, a white solid compound Core 1-2 (13.0 g, 77.5%) was obtained.
1H-NMR(CDCl3)δ [ppm]: 9.05 [d, 2H], 8.75 [t, 1H], 8.29 [t, 2H], 8.08 [d, 2H], 7.78 [t, 1H], 7.67 [t, 2H], 6.74 [s, 2H]. 1 H-NMR (CDCl 3) δ [ppm]: 9.05 [d, 2H], 8.75 [t, 1H], 8.29 [t, 2H], 8.08 [d, 2H], 7.78 [t, 1H], 7.67 [ t, 2 H], 6.74 [s, 2 H].
Core 1-3의 제조Manufacture of Core 1-3
Core 1-2 (12.8 g, 45.9 mmol)을 아세트산 150 mL에 완전히 용해시킨 후, Core 1-1 (15.0 g, 38.3 mmol)을 첨가하여 완전히 용해가 될 때까지 가열 교반하였다. 암모늄아세테이트 (14.7 g, 191.3 mmol)를 소분하여 첨가하였다. 첨가 종료 후 12 시간 동안 환류 교반하였다. 반응 종료 후 온도를 상온(20 ℃)으로 식히고 여과하였다. 여과된 고체 화합물을 메탄올과 물로 씻어 준 후 이를 톨루엔에 용해시킨 후 메탄올로 결정을 석출하였다. 석출된 고체 화합물을 여과 후 건조하여 연한 노랑색 고체 화합물 Core 1-3 (12.3 g, 65.4 %)을 얻었다. Core 1-2 (12.8 g, 45.9 mmol) was completely dissolved in 150 mL of acetic acid, Core 1-1 (15.0 g, 38.3 mmol) was added, and the mixture was heated and stirred until completely dissolved. Ammonium acetate (14.7 g, 191.3 mmol) was added in small portions. After completion of the addition, the mixture was refluxed and stirred for 12 hours. After completion of the reaction, the temperature was cooled to room temperature (20 캜) and filtered. The filtered solid compound was washed with methanol and water, dissolved in toluene, and then crystals were precipitated with methanol. The precipitated solid compound was filtered and dried to obtain a pale yellow solid compound Core 1-3 (12.3 g, 65.4%).
1H-NMR(CDCl3)δ [ppm]: 8.30 [d, 2H], 8.14 [d, 1H], 7.96 [s, 2H], 7.54 [t, 2H], 7.45-7.35 [m, 6H], 2.99 [s, 4H]. 1 H-NMR (CDCl 3) δ [ppm]: 8.30 [d, 2H], 8.14 [d, 1H], 7.96 [s, 2H], 7.54 [t, 2H], 7.45-7.35 [m, 6H], 2.99 [s, 4 H].
Core 1-4의 제조Manufacture of Core 1-4
Core 1-3 (12.0 g, 24.4 mmol)과 2,3-디클로로-5,6-디시아노벤조퀴논(DDQ) (12.2 g, 53.7 mmol), 1,4-다이옥산 180 mL를 첨가 후 12 시간 동안 환류 교반하였다. 반응 종료 후 온도를 상온(20 ℃)으로 냉각하고, 반응기에 물을 첨가 후 1시간 동안 교반하였다. 메틸렌클로라이드를 이용하여 추출하고 농축 후 컬럼을 실시하여 고체 화합물 Core 1-4 (8.10 g, 67.8 %)를 얻었다. After adding Core 1 - 3 (12.0 g, 24.4 mmol), 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (12.2 g, 53.7 mmol) and 1,4- And the mixture was refluxed and stirred. After completion of the reaction, the temperature was cooled to room temperature (20 캜), water was added to the reactor, and the mixture was stirred for 1 hour. The reaction mixture was extracted with methylene chloride, concentrated, and then subjected to column chromatography to obtain solid compound Core 1-4 (8.10 g, 67.8%).
1H-NMR(CDCl3)δ [ppm]: 8.51 [d, 1H], 8.30 [m, 2H], 8.16 [d, 1H], 8.06 [d, 1H], 7.92 [s, 1H], 7.81 [d, 1H], 7.70-7.60 [m, 3H] 7.55-7.40 [m 5H]. 1 H-NMR (CDCl 3) δ [ppm]: 8.51 [d, 1H], 8.30 [m, 2H], 8.16 [d, 1H], 8.06 [d, 1H], 7.92 [s, 1H], 7.81 [ d, 1 H], 7.70-7.60 [m, 3H] 7.55-7.40 [m 5H].
화합물 6의 제조Preparation of Compound 6
Core 1-4 (8.00 g, 16.4 mmol)와 Carbazole (6.02 g, 36.0 mmol), CuI (0.16 g, 0.8 mmol), Ethylenediamine (0.10 g, 1.6 mmol), K3PO4 (10.4 g, 49.1 mmol)을 톨루엔 200 ml에 용해시킨 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 500 ml를 첨가하여 고체 화합물을 석출하였다. 여과 후 물과 메탄올로 석출된 고체 화합물을 씻어주고 컬럼을 실시하여 고체 화합물 6 (8.2 g, 75.8 %)을 얻었다. (0.10 g, 0.8 mmol), Ethylenediamine (0.10 g, 1.6 mmol), K 3 PO 4 (10.4 g, 49.1 mmol), Carbazole (6.02 g, 36.0 mmol) Was dissolved in 200 ml of toluene, and the mixture was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 500 ml of methanol was added thereto to precipitate a solid compound. After filtration, the solid compound precipitated with water and methanol was washed and subjected to column chromatography to obtain solid compound 6 (8.2 g, 75.8%).
1H-NMR(CDCl3)δ [ppm]: 8.55 [d, 2H], 8.51 [m, 1H], 8.30 [d, 2H], 8.16-8.05 [m, 6H], 7.94 [d, 2H], 7.81 [d, 1H], 7.69-7.60 [m, 5H], 7.54-7.47 [m, 5H], 7.40 [s, 1H], 7.35-7.20 [m, 6H]. 1 H-NMR (CDCl 3) δ [ppm]: 8.55 [d, 2H], 8.51 [m, 1H], 8.30 [d, 2H], 8.16-8.05 [m, 6H], 7.94 [d, 2H], 7.81 [d, 1H], 7.69-7.60 [m, 5H], 7.54-7.47 [m, 5H], 7.40 [s, 1H], 7.35-7.20 [
MALDI-TOF MS: m/z 662.02, cal. 661.79.MALDI-TOF MS: m / z 662.02, cal. 661.79.
[ 실시예 2] 화합물 41 의 제조 [ Example 2] Preparation of Compound 41
화합물 41-1의 제조Preparation of Compound 41-1
Core 1-4 (54.0g, 110mmol)와 dibenzo[b,d]thiophen-4-ylboronic acid (12.54g, 55mmol), Pd(pph3)4(12.6g,55.2mmol),2MK2CO3500ml를 톨루엔 1500 ml에 용해한 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 1000 ml를 첨가하여 고체를 석출하였다. 여과 후 물과 메탄올로 씻어주고 컬럼을 실시하여 고체 화합물 41-1 (12.4g, 36%)을 얻었다. (12.54 g, 55 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (12.54 g, 55 mmol), Pd (pph 3 ) 4 (12.6 g, 55.2 mmol) and 2 MK 2 CO 3 Dissolved in 1,500 ml of toluene, and refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 1000 ml of methanol was added to precipitate a solid. Filtered, washed with water and methanol, and subjected to column chromatography to obtain solid compound 41-1 (12.4 g, 36%).
1H-NMR(CDCl3): 8.51[1H, t], 8.45[1H, d], 8.41[1H, d], 8.30[2H, t], 8.20[1H, d], 8.16[1H, t], 8.06[1H, d], 7.98[1H, d], 7.81[1H, t], 7.52-7.65[4H, m], 7.55-7.45[9H, m], 7.40-7.32[5H, m]. 1 H-NMR (CDCl 3 ): 8.51 [1H, t], 8.45 [1H, d], 8.41 , 8.06 [1H, d], 7.98 [1H, d], 7.81 [1H, t], 7.52-7.65 [4H, m], 7.55-7.45 [9H, m], 7.40-7.32 [
화합물 41의 제조Preparation of Compound 41
화합물 41-1 (12.4 g, 20.98 mmol)와 4,4,5,5-Tetramethyl-2-(triphenylene-2-yl)-1,3,2-dioxaborolane(8.2 g, 23.1 mmol), Pd(pph3)4(0.73 g,0.63 mmol),2M K2CO3 50 ml를 톨루엔 250 ml에 용해한 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 500 ml를 첨가하여 고체 화합물을 석출하였다. 석출된 고체 화합물을 여과 후 물과 메탄올로 씻어주고 컬럼을 실시하여 고체 화합물 41 (11.4 g, 73%)을 얻었다.Compound 41-1 (12.4 g, 20.98 mmol), 4,4,5,5-Tetramethyl-2- (triphenylene-2-yl) -1,3,2-dioxaborolane (8.2 g, 23.1 mmol), Pd 3 ) 4 (0.73 g, 0.63 mmol), 2M K 2 CO 3 50 ml were dissolved in 250 ml of toluene, and the mixture was refluxed and stirred for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 500 ml of methanol was added thereto to precipitate a solid compound. The precipitated solid compound was filtered out, washed with water and methanol, and subjected to column chromatography to obtain a solid compound 41 (11.4 g, 73%).
1H-NMR(CDCl3): 9.15 [s, 1H]. 8.93 [d, 2H], 8.55-8.40 [m, 4H], 8.30 [s, 2H], 8.25-7.85 [m 8H], 7.75-7.65 [m, 10H], 7.60-7.45 [m, 6H]. 1 H-NMR (CDCl 3) : 9.15 [s, 1H]. 8.93 [d, 2H], 8.55-8.40 [m, 4H], 8.30 [s, 2H], 8.25-7.85 [m 8H], 7.75-7.65 [m, 10H], 7.60-7.45 [m, 6H].
MALDI-TOF MS: m/z 740.55, cal. 739.92MALDI-TOF MS: m / z 740.55, cal. 739.92
[ 실시예 3] 화합물 51 의 제조 [ Example 3] Preparation of Compound 51
Core 2-2의 제조Manufacture of Core 2-2
Core 1-1 (35.0 g, 89.3 mmol)과 Benzamidine hydrochloride (16.8 g, 107.1 mmol), 에탄올 180 mL를 첨가 후 용해하였다. 여기에 KOH (12.5 g, 223.2 mmol)을 에탄올 450 ml에 녹인 용액을 서서히 첨가하였다. 첨가 종료 후, 24 시간 동안 환류하였다. 반응 종료 후, 상온으로 식히고 물을 첨가 후 MC로 추출하였다. 유기층을 농축한 후, 컬럼을 실시하여 고체 화합물 Core 2-2 (14.5 g, 28 %)을 얻었다.Core 1-1 (35.0 g, 89.3 mmol), Benzamidine hydrochloride (16.8 g, 107.1 mmol) and ethanol (180 mL) were added and dissolved. A solution of KOH (12.5 g, 223.2 mmol) in 450 ml of ethanol was slowly added thereto. After completion of the addition, the mixture was refluxed for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was extracted with MC. The organic layer was concentrated and then subjected to column chromatography to obtain a solid compound Core 2-2 (14.5 g, 28%).
1H-NMR(CDCl3)δ [ppm]: 8.30 [d, 2H], 7.96 [s, 2H], 7.54 [t, 2H], 7.45-7.35 [m, 6H], 2.99 [s, 4H]. 1 H-NMR (CDCl 3 )? [Ppm]: 8.30 [d, 2H], 7.96 [s, 2H], 7.54 [t, 2H], 7.45-7.35 [m, 6H], 2.99 [s, 4H].
Core 2-3의 제조Manufacture of Core 2-3
Core 2.2 (12.8 g, 26 mmol)과 DDQ (12.2 g, 53.7 mmol), 1,4-다이옥산 180 mL를 첨가 후 12 시간 동안 환류 교반하였다. 반응 종료 후 온도를 상온으로 냉각하고, 반응기에 물을 첨가 후 1시간 동안 교반하였다. 메틸렌클로라이드를 이용하여 추출하고 농축 후 컬럼을 실시하여 고체 화합물 (10.7 g, 84%)을 얻었다. Core 2.2 (12.8 g, 26 mmol), DDQ (12.2 g, 53.7 mmol) and 180 mL of 1,4-dioxane were added, followed by reflux stirring for 12 hours. After completion of the reaction, the temperature was cooled to room temperature, water was added to the reactor, and the mixture was stirred for 1 hour. The mixture was extracted with methylene chloride, concentrated, and then subjected to column chromatography to obtain a solid compound (10.7 g, 84%).
1H-NMR(CDCl3)δ [ppm]: 8.51 [d, 1H], 8.30 [m, 2H], 8.16 [d, 1H], 8.06 [d, 1H], 7.81 [d, 1H], 7.70-7.60 [m, 3H] 7.55-7.40 [m 5H]. 1 H-NMR (CDCl 3) δ [ppm]: 8.51 [d, 1H], 8.30 [m, 2H], 8.16 [d, 1H], 8.06 [d, 1H], 7.81 [d, 1H], 7.70- 7.60 [m, 3 H] 7.55 - 7.40 [m 5 H].
화합물 51의 제조Preparation of Compound 51
Core 2-3 (8.00 g, 16.4 mmol)와 Carbazole (6.02 g, 36.0 mmol), CuI (0.16 g, 0.8 mmol), Ethylenediamine (0.10 g, 1.6 mmol), K3PO4 (10.4 g, 49.1 mmol)을 톨루엔 200 ml에 용해한 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온으로 식히고 메탄올 500 ml를 첨가하여 고체를 석출하였다. 여과 후 물과 메탄올로 씻어주고 컬럼을 실시하여 고체 화합물 51 (7.5 g, 69.0 %)을 얻었다. Ethylenediamine (0.10 g, 1.6 mmol) and K 3 PO 4 (10.4 g, 49.1 mmol) were added to a solution of Core 2-3 (8.00 g, 16.4 mmol), Carbazole (6.02 g, 36.0 mmol) Was dissolved in 200 ml of toluene, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and 500 ml of methanol was added to precipitate a solid. Filtered, washed with water and methanol, and subjected to column chromatography to obtain a solid compound 51 (7.5 g, 69.0%).
1H-NMR(CDCl3)δ [ppm]: 8.55 [d, 2H], 8.51 [m, 1H], 8.28 [d, 2H], 8.16-8.05 [m, 5H] 7.94 [d, 2H], 7.84 [d, 1H], 7.70-7.20 [m, 17H] 1 H-NMR (CDCl 3) δ [ppm]: 8.55 [d, 2H], 8.51 [m, 1H], 8.28 [d, 2H], 8.16-8.05 [m, 5H] 7.94 [d, 2H], 7.84 [d, 1H], 7.70-7.20 [m, 17H]
MALDI-TOF MS: m/z 663.02, cal. 662.78MALDI-TOF MS: m / z 663.02, calc. 662.78
[ 실시예 4] 화합물 94 의 제조 [ Example 4] Preparation of Compound 94
화합물 94-1의 제조Preparation of Compound 94-1
3000 mL-2구 둥근바닥플라스크에 페닐하이드라진 하이드로클로라이드 (100 g, 691 mmol), 2-Tetralone (101.1 g, 691 mmol), 아세트산 (8.3 g, 138.3 mmol)과 에탄올 1300 mL를 넣고 환류하면서 가열 교반하였다. 12 시간 반응 후, 반응물을 상온으로 냉각하였다. 석출된 고체를 감압 여과하고, 메탄올로 세정하여 연한노란색의 고체 화합물 94-1 (121.3 g , 80 %) 을 얻었다. (100 g, 691 mmol), 2-Tetralone (101.1 g, 691 mmol), acetic acid (8.3 g, 138.3 mmol) and ethanol (1300 mL) were added to a 3000 mL-2-necked round bottom flask, Respectively. After reaction for 12 hours, the reaction product was cooled to room temperature. The precipitated solid was filtered under reduced pressure, and washed with methanol to obtain a pale yellow solid compound 94-1 (121.3 g, 80%).
1H-NMR(CDCl3) δ[ppm]: 7.52 [d, 1H], 7.42 [t, 1H], 7.35-7.29 [m, 2H], 7.24-7.21 [m, 2H], 7.16 [t, 1H], 7.02 [d, 1H], 6.92 [d, 1H], 3.09 [t, 2H], 2.95 [t, 2H]. 1 H-NMR (CDCl 3) δ [ppm]: 7.52 [d, 1H], 7.42 [t, 1H], 7.35-7.29 [m, 2H], 7.24-7.21 [m, 2H], 7.16 [t, 1H ], 7.02 [d, IH], 6.92 [d, IH], 3.09 [t, 2H], 2.95 [t, 2H].
화합물 94-2의 제조Preparation of Compound 94-2
화합물 94-1 (10 g, 45.6 mmol)과 2,3-디클로로-5,6-디시아노벤조퀴논(DDQ) (22.7 g, 10352 mmol), 1,4-다이옥산 150 mL를 첨가 후 12 시간 동안 환류 교반하였다. 반응 종료 후 온도를 상온(20 ℃)으로 냉각하고, 반응기에 물을 첨가 후 1시간 동안 교반하였다. 메틸렌클로라이드를 이용하여 추출하고 농축 후 컬럼을 실시하여 고체 화합물 94-2 (5.1 g, 51.8 %)를 얻었다. After addition of compound 94-1 (10 g, 45.6 mmol), 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (22.7 g, 10352 mmol) and 1,4- And the mixture was refluxed and stirred. After completion of the reaction, the temperature was cooled to room temperature (20 캜), water was added to the reactor, and the mixture was stirred for 1 hour. The mixture was extracted with methylene chloride, concentrated, and then subjected to column chromatography to obtain a solid compound 94-2 (5.1 g, 51.8%).
1H-NMR(CDCl3)δ [ppm]: 7.95 [d, 1H], 7.81 [d, 1H], 7.74 [d, 1H], 7.55 [d, 1H], 7.45-7.35 [m, 4H], 7.2-7.12 [m, 3H]. 1 H-NMR (CDCl 3 )? [Ppm]: 7.95 [d, 1H], 7.81 [d, 1H], 7.74 7.2-7.12 [m, 3H].
화합물 94의 제조Preparation of Compound 94
Core 1-4 (15 g, 30.7 mmol)와 화합물 94-2 (14.6 g, 67.5 mmol), CuI (0.6 g, 3.1 mmol), Ethylenediamine (0.4 g, 6.1 mmol), K3PO4 (13 g, 61.3 mmol)을 톨루엔 450 ml에 용해시킨 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 500 ml를 첨가하여 고체 화합물을 석출하였다. 여과 후 물과 메탄올로 석출된 고체 화합물을 씻어주고 컬럼을 실시하여 고체 화합물 94 (17 g, 73 %)을 얻었다. Core 1-4 (15 g, 30.7 mmol ) and compound 94-2 (14.6 g, 67.5 mmol) , CuI (0.6 g, 3.1 mmol), Ethylenediamine (0.4 g, 6.1 mmol), K 3 PO 4 (13 g, 61.3 mmol) were dissolved in 450 ml of toluene, and the mixture was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 500 ml of methanol was added thereto to precipitate a solid compound. After filtration, the solid compound precipitated with water and methanol was washed out and column was carried out to obtain solid compound 94 (17 g, 73%).
1H-NMR(CDCl3)δ [ppm]: 8.39 [s, 1H], 8.04-7.91 [m, 13H], 7.86 [s, 1H], 7.72-7.67 [m, 3H], 7.6-7.47 [m, 9H], 7.41 [t, 1H], 7.33 [d, 1H], 7.24 [t, 2H], 7.17 [t, 2H], 6.96 [t, 1H], 6.91 [t, 1H]. 1 H-NMR (CDCl 3 )? [Ppm]: 8.39 [s, 1H], 8.04-7.91 [m, 13H], 7.86 [s, 1H], 7.72-7.67 [m, 3H], 7.6-7.47 [ , 9H], 7.41 [t, IH], 7.33 [d, IH], 7.24 [t, 2H], 7.17 [t, 2H], 6.96 [
MALDI-TOF MS: m/z 761.91, cal. 761.12.MALDI-TOF MS: m / z 761.91, cal. 761.12.
[ 실시예 5] 화합물 127 의 제조 [ Example 5] Preparation of Compound 127
화합물 127의 제조Preparation of Compound 127
화합물 41-1 (12.00 g, 20.3 mmol)와 화합물 94-2 (9.7 g, 44.6 mmol), CuI (0.4 g, 2 mmol), Ethylenediamine (0.2 g, 4.1 mmol), K3PO4 (8.6 g, 40.5 mmol)을 톨루엔 200 ml에 용해시킨 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 500 ml를 첨가하여 고체 화합물을 석출하였다. 여과 후 물과 메탄올로 석출된 고체 화합물을 씻어주고 컬럼을 실시하여 고체 화합물 127 (13 g, 88 %)을 얻었다. (9.6 g, 44.6 mmol), CuI (0.4 g, 2 mmol), Ethylenediamine (0.2 g, 4.1 mmol), K 3 PO 4 (8.6 g, 40.5 mmol) was dissolved in 200 ml of toluene, and the mixture was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 500 ml of methanol was added thereto to precipitate a solid compound. After filtration, the solid compound precipitated with water and methanol was washed out and column was carried out to obtain solid compound 127 (13 g, 88%).
1H-NMR(CDCl3)δ [ppm]: 8.22 [s, 1H], 8.19 [s, 1H], 8.13 [s, 1H], 8.08-8.01 [m, 7H], 7.99-7.95 [m, 3H], 7.87-7.83 [m, 3H], 7.77 [t, 3H], 7.6 [t, 1H], 7.53-7.38 [m, 10H], 7.26 [t, 1H], 7.2 [t, 1H], 1 H-NMR (CDCl 3 )? [Ppm]: 8.22 [s, 1H], 8.19 [s, 1H], 8.13 [s, 1H], 8.08-8.01 [m, 7H], 7.99-7.95 [ ], 7.87-7.83 [m, 3H], 7.77 [t, 3H], 7.6 [t, 1H], 7.53-7.38 [m, 10H], 7.26
MALDI-TOF MS: m/z 728.9, cal. 728.15.MALDI-TOF MS: m / z 728.9, cal. 728.15.
[ 실시예 6] 화합물 130 의 제조 [ Example 6] Preparation of Compound 130
화합물 130의 제조Preparation of Compound 130
Core 2-3 (16 g, 32.6 mmol)와 화합물 94-2 (15.6 g, 71.8 mmol), CuI (0.6 g, 3.3 mmol), Ethylenediamine (0.4 g, 6.5 mmol), K3PO4 (13.9 g, 65.3 mmol)을 톨루엔 480 ml에 용해시킨 후 12 시간 동안 환류 교반하였다. 반응 종료 후, 상온(20 ℃)으로 식히고 메탄올 500 ml를 첨가하여 고체 화합물을 석출하였다. 여과 후 물과 메탄올로 석출된 고체 화합물을 씻어주고 컬럼을 실시하여 고체 화합물 130 (18 g, 72 %)을 얻었다. (15 g, 71.8 mmol), CuI (0.6 g, 3.3 mmol), Ethylenediamine (0.4 g, 6.5 mmol), K 3 PO 4 (13.9 g, 65.3 mmol) was dissolved in 480 ml of toluene, and the mixture was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature (20 캜), and 500 ml of methanol was added thereto to precipitate a solid compound. After filtration, the solid compound precipitated with water and methanol was washed and subjected to column chromatography to obtain solid compound 130 (18 g, 72%).
1H-NMR(CDCl3)δ [ppm]: 8.29 [s, 1H], 8.19 [d, 1H], 8.1-7.98 [m, 8H], 7.83-7.7 [m, 6H], 7.64 [d, 1H], 7.59-7.45 [m, 10H], 7.32 [d, 1H], 7.26 [t, 2H], 7.18 [t, 2H], 7.02 [t, 1H], 6.88 [t, 1H]. 1 H-NMR (CDCl 3) δ [ppm]: 8.29 [s, 1H], 8.19 [d, 1H], 8.1-7.98 [m, 8H], 7.83-7.7 [m, 6H], 7.64 [d, 1H ], 7.59-7.45 [m, 10H], 7.32 [d, IH], 7.26 [t, 2H], 7.18 [t, 2H], 7.02 [t, IH], 6.88 [t, IH].
MALDI-TOF MS: m/z 762.9, cal. 762.22.MALDI-TOF MS: m / z 762.9, cal. 762.22.
[[ 실시예Example 7] 본 발명에 따른 발광용 호스트 물질인 화합물 6( 7] The light emitting host material Compound 6 ( 실시예Example 1)을1) to 이용한 유기 발광 소자의 제작 Fabrication of organic light emitting device using
박막 두께가 150 nm인 ITO(인듐 주석 산화물) 투명 전극 라인을 갖는, 25 mm × 25 mm × 0.7 mm 크기의 유리기판을 세제가 용해된 증류수 속에서 10분 동안 초음파로 세정하고, 증류수에서 10분 동안 1 회 반복 세정하였다. 증류수 세정이 끝나면 이소프로필알코올, 아세톤, 메탄올의 용제를 사용하여 기판을 순차적으로 10 분씩 초음파세척하고 건조시켰다. 이어, 산소/아르곤 플라즈마를 이용하여 건식 세정한 후, 투명 전극 라인을 갖는 유리 기판을 진공 증착 장치의 기판 홀더에 장착하고 투명 전극 라인이 형성되어 있는 면상에, 상기 투명 전극을 덮도록 막 두께 60 nm의 정공 주입층(N1,N1'-(biphenyl-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine))으로서 성막하였다. 다음에, 정공 주입층 재료 막상에 막 두께 30 nm의 H-1(tetrakis-N-biphenyl-4-yl-benzidine, 이하 H-1 막)을 정공 수송층으로서 성막하였다. 다음에, H-1 막상에 도판트로서 AYPD를, 발광호스트로서 발명 화합물 재료에 5%의 중량비로 증착하여 막 두께 20 nm의 발광층으로서 성막하였다. 이어, Alq3를 전자 수송층으로 성막 후 그 위에 Liq (lithium quinolate)을 증착시켜 전자 주입층을 형성하였다. 이 Liq 막상에 금속 알루미늄을 증착시켜 금속 음극을 형성하여 유기 발광 소자를 제작하였다.A glass substrate of 25 mm x 25 mm x 0.7 mm, having an ITO (indium tin oxide) transparent electrode line with a thin film thickness of 150 nm, was ultrasonically cleaned for 10 minutes in distilled water containing detergent dissolved therein, Lt; / RTI > After the distilled water was cleaned, the substrate was ultrasonically cleaned by using a solvent of isopropyl alcohol, acetone, and methanol for 10 minutes sequentially and dried. Subsequently, the substrate was dry-cleaned with oxygen / argon plasma, and then a glass substrate having a transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus. On the surface where the transparent electrode line was formed, a film thickness of 60 (biphenyl-4,4'-diyl) bis (N1- (naphthalen-1-yl) -N4, N4-diphenylbenzene-1,4-diamine). Next, H-1 (tetrakis-N-biphenyl-4-yl-benzidine, hereinafter referred to as H-1 film) with a film thickness of 30 nm was formed as a hole transporting layer on the hole injection layer material film. Next, AYPD was deposited as a dopant on the H-1 film and a light-emitting host was deposited on the inventive compound material at a weight ratio of 5% to form a light emitting layer having a thickness of 20 nm. Next, Alq 3 was formed into an electron transport layer, and Liq (lithium quinolate) was deposited thereon to form an electron injection layer. Metal aluminum was deposited on the Liq film to form a metal cathode, thereby fabricating an organic light emitting device.
상기와 같이 제작된 유기 발광 전자소자에 0 ~ 15V의 전압을 인가하여 발광시험을 실시하였으며, 하기 표 1 및 도 4 내지 6에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.A voltage of 0 to 15 V was applied to the thus fabricated organic luminescent electronic device, and a luminescence test was performed. The electroluminescence characteristics and basic physical property measurement results are shown in Table 1 and Figs. 4 to 6.
[실시예 8] 본 발명에 따른 화합물 41(실시예 2)을 이용한 유기 발광 소자의 제작[Example 8] Production of organic light emitting device using compound 41 (Example 2) according to the present invention
상기 실시예 7에서 발광층의 재료로서 화합물 6 대신에 화합물 41을 사용한 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 4 내지 6에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7, except that Compound 41 was used instead of Compound 6 as the material of the light emitting layer in Example 7. The results are shown in Table 1 and FIGS. 4 to 6, The measurement results are shown.
[실시예 9] 본 발명에 따른 화합물 51(실시예 3)을 이용한 유기발광소자의 제작[Example 9] Fabrication of organic light emitting device using compound 51 (Example 3) according to the present invention
상기 실시예 7에서 발광층의 재료로서 화합물 6 대신에 화합물 51를 사용한 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 4 내지 6에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7 except that the compound 51 was used instead of the compound 6 as the material of the light emitting layer in Example 7. The following Table 1 and Figures 4 to 6 show the electroluminescent characteristics and basic properties The measurement results are shown.
[실시예 10] 본 발명에 따른 화합물 94(실시예 4)을 이용한 유기 발광 소자의 제작[Example 10] Fabrication of organic light emitting device using Compound 94 (Example 4) according to the present invention
상기 실시예 7에서 발광층의 재료로서 화합물 6 대신에 화합물 94을 사용한 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 1 내지 3에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7, except that the compound 94 was used instead of the compound 6 as the material of the light emitting layer in Example 7. The following Table 1 and Figs. 1 to 3 show electroluminescent characteristics and basic properties The measurement results are shown.
[실시예 11] 본 발명에 따른 화합물 127(실시예 5)을 이용한 유기발광소자의 제작[Example 11] Fabrication of organic light emitting device using compound 127 (Example 5) according to the present invention
상기 실시예 7에서 발광층의 재료로서 화합물 6 대신에 화합물 127를 사용한 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 1 내지 3에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7 except that the compound 127 was used instead of the compound 6 as the material of the light emitting layer in Example 7. The following Table 1 and Figs. The measurement results are shown.
[실시예 12] 본 발명에 따른 화합물 130(실시예 6)을 이용한 유기발광소자의 제작[Example 12] Fabrication of an organic light emitting device using Compound 130 (Example 6) according to the present invention
상기 실시예 7에서 발광층의 재료로서 화합물 6 대신에 화합물 130를 사용한 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 1 내지 3에 전기 발광 특성 및 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7 except that Compound 130 was used in place of Compound 6 as a material of the light emitting layer in Example 7. The following Table 1 and Figs. The measurement results are shown.
[비교예 1] 화합물 CBP를 이용한 유기발광소자의 제작[Comparative Example 1] Fabrication of organic light emitting device using compound CBP
상기 실시예 7에서 전자 수송층의 재료로서 화합물 6 대신에 하기 구조의 화합물 CBP를 사용하는 것을 제외하고는 실시예 7과 동일한 조건 하에서 유기 발광 소자를 제작하였으며, 하기 표 1 및 도 1 내지 도 6에 전기 발광 특성 및 소자의 기초 물성 측정 결과를 나타내었다.An organic light emitting device was fabricated under the same conditions as in Example 7, except that the compound CBP having the following structure was used instead of the compound 6 as the electron transport layer material in Example 7, and as shown in Table 1 and Figs. 1 to 6 Electroluminescence characteristics and fundamental properties of the device.
상기 표 1 내지 2에 나타난 바와 같이, 본 발명에 따른 화합물을 발광용 호스트 물질로서 발광층에 포함하는 유기 발광 소자는 종래의 재료 대비하여, 우수한 소자 특성을 보이는 것을 확인할 수 있었으며, 본 발명에 따른 화합물을 발광용 호스트 물질로서 발광층으로 사용한 유기 발광 소자는 우수한 휘도와 높은 효율로 뛰어난 발광 특성을 가질 뿐만 아니라 구동전압을 강화시켜 소비 전력을 개선시킬 수 있음을 확인하였다. As shown in Tables 1 and 2, it was confirmed that the organic luminescent device comprising the compound according to the present invention as a luminescent host material in the light emitting layer exhibited excellent device characteristics as compared with the conventional materials, Emitting layer as a light emitting host material has excellent light emission characteristics with excellent luminance and high efficiency, and it is confirmed that power consumption can be improved by enhancing driving voltage.
또한 본 발명에 따른 상기 발광용 호스트 물질을 함유하는 유기 발광 소자는 높은 수명특성을 가질 수 있음을 확인할 수 있었다.It was also confirmed that the organic light emitting device containing the light emitting host material according to the present invention can have high lifetime characteristics.
Claims (10)
[화학식 1]
[상기 화학식 1에서,
R1 내지 R6는 서로 독립적으로 수소, 또는 중수소이고;
X 및 Y는 서로 독립적으로 N 및 CH에서 선택되고, 적어도 하나 이상은 N이며;
L1 및 L2 는 서로 독립적으로 단일결합, 및 하기 구조에서 선택되며, 하기 구조의 R21 내지 R25는 서로 독립적으로 수소, 중수소, 모노 (C6-C30)아릴아미노, 디(C6-C30)아릴아미노, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;
V1 및 V2 는 서로 독립적으로 수소, 및 하기 구조에서 선택되며;
상기 L1-V1 및 L2-V2는 수소가 아니며;
상기 L1 및 V1이 동시에 카바졸인 경우와 L2 및 V2가 동시에 카바졸인 경우는 제외된다]A compound represented by the following formula (1).
[Chemical Formula 1]
[In the above formula (1)
R 1 to R 6 are independently of each other hydrogen, or deuterium;
X and Y are independently selected from N and CH, and at least one is N;
L 1 and L 2 independently of one another are a single bond and are selected from the following structures: R 21 to R 25 in the structures below are independently of each other hydrogen, deuterium, mono (C 6 -C 30) arylamino, di (C 6 -C 30) Arylamino, (C6-C30) aryl or (C3-C30) heteroaryl;
V 1 and V 2 are independently of each other hydrogen, and are selected from the following structures;
Wherein L 1 -V 1 and L 2 -V 2 are not hydrogen;
The case where L 1 and V 1 are simultaneously a carbazole and L 2 and V 2 are simultaneously a carbazole are excluded]
하기 화학식 2 또는 하기 화학식 3으로 표시되는 화합물;
[화학식 2]
[화학식 3]
[상기 화학식 2 및 화학식 3에서,
R1 내지 R6는 서로 독립적으로 수소, 또는 중수소이고;
L1 및 L2 는 서로 독립적으로 단일결합, 및 하기 구조에서 선택되며;
V1 및 V2 는 서로 독립적으로 수소, 및 하기 구조에서 선택되며;
상기 L1-V1 및 L2-V2는 수소가 아니며;
상기 L1 및 V1이 동시에 카바졸인 경우와 L2 및 V2가 동시에 카바졸인 경우는 제외된다]The method according to claim 1,
A compound represented by the following formula 2 or 3;
(2)
(3)
[In the formulas (2) and (3)
R 1 to R 6 are independently of each other hydrogen, or deuterium;
L 1 and L 2 are independently of each other a single bond, and are selected from the following structures;
V 1 and V 2 are independently of each other hydrogen, and are selected from the following structures;
Wherein L 1 -V 1 and L 2 -V 2 are not hydrogen;
The case where L 1 and V 1 are simultaneously a carbazole and L 2 and V 2 are simultaneously a carbazole are excluded]
하기 화합물로부터 선택되는 것인 화합물.
Lt; / RTI > is selected from the following compounds.
하기 화합물로부터 선택되는 것인 화합물.
Lt; / RTI > is selected from the following compounds.
상기 유기 발광 소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 상기 화합물이 포함된 발광층을 포함하는 유기 발광 소자.8. The method of claim 7,
The organic light emitting device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer comprises a light emitting layer containing the compound.
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