KR102201473B1 - Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device - Google Patents
Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device Download PDFInfo
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- KR102201473B1 KR102201473B1 KR1020200114312A KR20200114312A KR102201473B1 KR 102201473 B1 KR102201473 B1 KR 102201473B1 KR 1020200114312 A KR1020200114312 A KR 1020200114312A KR 20200114312 A KR20200114312 A KR 20200114312A KR 102201473 B1 KR102201473 B1 KR 102201473B1
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- 0 C*(C=*=CN(C)C1*2)C(C*)=C2N(C(C)(C)*)c(cccc2)c2N1C(C)(C)C Chemical compound C*(C=*=CN(C)C1*2)C(C*)=C2N(C(C)(C)*)c(cccc2)c2N1C(C)(C)C 0.000 description 8
- SAQAERNKMHATDZ-UHFFFAOYSA-N Brc1ccc[nH]1 Chemical compound Brc1ccc[nH]1 SAQAERNKMHATDZ-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N [O-][N+](c(cccc1)c1O)=O Chemical compound [O-][N+](c(cccc1)c1O)=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- CEENHVKKNNPTBI-UHFFFAOYSA-N [O-][N+](c(cccc1)c1Oc1ccc[nH]1)=O Chemical compound [O-][N+](c(cccc1)c1Oc1ccc[nH]1)=O CEENHVKKNNPTBI-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
본 발명은 퓨즈드 화합물, 이의 제조방법 및 이를 이용한 유기전자소자의 발전에 기여하고자 하는 기술에 관한 것이다.The present invention relates to a fused compound, a method for manufacturing the same, and a technology to contribute to the development of an organic electronic device using the same.
일반적으로 유기발광 다이오드(OLED: Organic Light Emitting Diodes)는 음극, 양극, 및 음극과 양극 사이에 개재된 유기물 층으로 구성되어 있다. 소자의 구성을 전체적으로 보면 투명 ITO 양극, 정공주입층 (HIL), 정공전달층 (HTL), 발광층 (EL), 정공저지층 (HBL), 전자전달층 (ETL), 전자주입층 (EIL), LiAl 등의 음극으로 형성되며, 필요에 따라 유기물 층의 1~2 개를 생략하는 경우도 있다. 구성된 양 전극 사이에 전계가 인가되면 음극 측으로 부터 전자가 주입되고 양극 측으로 부터 정공이 주입된다. 또한, 이 전자가 발광층에 정공과 재결합하여 여기상태를 생성하고, 여기상태가 기저상태로 되돌아갈 때에 에너지를 빛으로서 방출한다. 이러한 발광 재료는 크게 형광과 인광으로 나뉘며, 발광층 형성방법은 형광 호스트(순수 유기물)에 인광(유기금속)을 도핑하는 방법과 형광 호스트에 형광 도판트(질소 등을 포함하는 유기물)를 도핑하는 방법 및 발광체에 도판트 (DCM, Rubrene, DCJTB 등)를 이용하여 장파장을 구현하는 방법 등이 있다. 이러한 도핑을 통해 발광 파장, 효율, 구동전압, 수명 등을 개선하려 하고 있다. 일반적으로 발광층 및 공동층 형성용 리간드 재료들은 벤젠, 나프탈렌, 플로렌, 스파이로플로렌, 안트라센, 파이렌, 카바졸 등의 중심체와 페닐, 바이페닐, 나프탈렌, 헤테로사이클 등의 리간드 그리고 오르소, 메타, 파라 등의 결합 위치 및 아민, 시안, 불소, 메틸, 트리메틸 등이 치환된 구조들을 갖는다.In general, organic light emitting diodes (OLEDs) are composed of a cathode, an anode, and an organic material layer interposed between the cathode and the anode. Looking at the composition of the device as a whole, transparent ITO anode, hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EL), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), It is formed with a cathode such as LiAl, and one or two of the organic material layers may be omitted if necessary. When an electric field is applied between the configured electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, the electrons recombine with holes in the light emitting layer to create an excited state, and when the excited state returns to the ground state, energy is emitted as light. These light-emitting materials are largely divided into fluorescence and phosphorescence, and the method of forming a light-emitting layer is a method of doping phosphorescence (organic metal) to a fluorescent host (pure organic material) and a method of doping a fluorescent dopant (organic material including nitrogen) to the fluorescent host. And a method of implementing a long wavelength using a dopant (DCM, Rubrene, DCJTB, etc.) in the light emitting body. Through such doping, the emission wavelength, efficiency, driving voltage, and lifetime are being improved. In general, the ligand materials for forming the light emitting layer and the co-layer include central bodies such as benzene, naphthalene, florene, spirofluorene, anthracene, pyrene, carbazole, and ligands such as phenyl, biphenyl, naphthalene, and heterocycle, and ortho and meta. , And have structures in which amine, cyan, fluorine, methyl, trimethyl, etc. are substituted.
현재 디스플레이의 화면이 대형화 방향으로 진행되면서 OLED의 경우 더 섬세하며, 더 선명한 색들의 재료들이 요구되고 있다. 또한 발광파장의 색 좌표 이외에, 소자의 낮은 구동전압에서 높은 발광효율 및 재료의 화학 구조적 열 안정성이 높은 유리전이온도 등을 요구한다. As the screen of the current display is going in the direction of enlargement, materials with more delicate and sharper colors are required for OLED. In addition to the color coordinates of the emission wavelength, a high luminous efficiency at a low driving voltage of the device and a glass transition temperature having high chemical structural and thermal stability of the material are required.
본 발명은 퓨즈드 화합물을 이용하여 성능이 우수한 평면형 구조의 유기발광 성능 향상에 있다. 본 발명은 퓨즈드 화합물을 이용하여, 평면형 구조의 재료 개발을 통해 성능이 우수한 유기전기소자의 제공에 있다.The present invention is to improve the organic light emitting performance of a planar structure excellent in performance by using a fused compound. The present invention is to provide an organic electric device having excellent performance through the development of a material having a planar structure using a fused compound.
본 발명은 퓨즈드 화합물의 유기발광소자 재료 개발에 있다.The present invention is to develop a material for an organic light-emitting device of a fused compound.
본 발명의 퓨즈드 화합물은 하기 화학식 1-1 내지 1-5 중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물이다:The fused compound of the present invention is a fused compound characterized in that it is represented by any one of the following formulas 1-1 to 1-5:
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
상기 X는 각각 서로 독립적으로 N-R1, O, S, CH 및 CH2로부터 선택된 어느 1종이며,The X is each independently from each other NR 1 , O, S, CH and CH 2 Any one selected from,
상기 Ar1 내지 Ar4 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,Ar 1 to Ar 4 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L1 및 L2는 각각 서로 독립적으로 0 또는 1의 정수이다.L 1 and L 2 are each independently an integer of 0 or 1.
본 발명의 퓨즈드 화합물은 상기 퓨즈드 화합물은 하기 화학식 2-1 내지 2-32중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물이다:The fused compound of the present invention is a fused compound, wherein the fused compound is represented by any one of the following Formulas 2-1 to 2-32:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4] [Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 2-6][Formula 2-6]
[화학식 2-7][Formula 2-7]
[화학식 2-8][Formula 2-8]
[화학식 2-9][Formula 2-9]
[화학식 2-10] [Chemical Formula 2-10]
[화학식 2-11] [Chemical Formula 2-11]
[화학식 2-12] [Formula 2-12]
[화학식 2-13] [Formula 2-13]
[화학식 2-14] [Formula 2-14]
[화학식 2-15][Formula 2-15]
[화학식 2-16][Formula 2-16]
[화학식 2-17][Formula 2-17]
[화학식 2-18] [Formula 2-18]
[화학식 2-19][Formula 2-19]
[화학식 2-20][Formula 2-20]
[화학식 2-21][Formula 2-21]
[화학식 2-22][Formula 2-22]
[화학식 2-23][Formula 2-23]
[화학식 2-24] [Chemical Formula 2-24]
[화학식 2-25] [Formula 2-25]
[화학식 2-26] [Chemical Formula 2-26]
[화학식 2-27][Formula 2-27]
[화학식 2-28][Formula 2-28]
[화학식 2-29][Formula 2-29]
[화학식 2-30][Formula 2-30]
[화학식 2-31][Chemical Formula 2-31]
[화학식 2-32][Chemical Formula 2-32]
상기 Ar1 내지 Ar4 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,Ar 1 to Ar 4 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L1 및 L2는 각각 서로 독립적으로 0 또는 1의 정수이다.L 1 and L 2 are each independently an integer of 0 or 1.
본 발명은 퓨즈드 화합물을 이용한 고리형 아민 화합물 등을 통해, 유기전자소자의 성능이 우수한 물질 제공에 있으며, 또한 본 발명의 또 다른 일 측면에서는 상기 화학식 2-1내지 2-32의 퓨즈드 화합물을 포함하는 유기 전자 소자에 제공된다.The present invention is to provide a material having excellent performance of an organic electronic device through a cyclic amine compound using a fused compound, and in another aspect of the present invention, the fused compound of Formulas 2-1 to 2-32 It is provided in an organic electronic device comprising a.
본 발명에 따르는 퓨즈드 화합물은 대칭과 비대칭 및 평면형의 구조를 제공하며, 또한 본 발명의 대칭과 비대칭 및 평면형의 구조는 성능이 우수하며, 본 발명의 구조는 실시예 측면에서 퓨즈드 화합물을 이용한 구조의 성능이 우수한 유기발광 소자 결과를 나타내었다. The fused compound according to the present invention provides a symmetrical, asymmetrical, and planar structure, and the symmetrical, asymmetrical, and planar structure of the present invention is excellent in performance, and the structure of the present invention uses a fused compound in terms of examples. The organic light-emitting device with excellent structural performance was shown.
이하 본 발명을 보다 상세하게 설명한다. 하기의 구체적 설명은 본 발명의 일례를 들어 설명하는 것이므로 본 발명이 이에 한정되지 않는다.Hereinafter, the present invention will be described in more detail. The following specific description is for describing an example of the present invention, so the present invention is not limited thereto.
본 발명의 일 측면에 따라, 퓨즈드 화합물이 제공된다. According to an aspect of the present invention, a fused compound is provided.
본 발명의 퓨즈드 화합물은 하기 화학식 1-1 내지 1-5 중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물이다:The fused compound of the present invention is a fused compound characterized in that it is represented by any one of the following formulas 1-1 to 1-5:
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
상기 X는 각각 서로 독립적으로 N-R1, O, S, CH 및 CH2로부터 선택된 어느 1종이며,The X is each independently from each other NR 1 , O, S, CH and CH 2 Any one selected from,
상기 Ar1 내지 Ar4 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,Ar 1 to Ar 4 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L1 및 L2는 각각 서로 독립적으로 0 또는 1의 정수이다.
특히, 상기 화학식 1-2의 퓨즈드 화합물은 다음과 같이 표시된다:
[화학식 1-2]
상기 X1은 N-R1, O, CH 및 CH2로부터 선택된 어느 1종이고, 상기 X2 및 X3은 각각 서로 독립적으로 N-R1, O, S, CH 및 CH2로부터 선택된 어느 1종이며,
상기 Ar1, Ar2 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,
상기 L1은 0 또는 1의 정수이다.L 1 and L 2 are each independently an integer of 0 or 1.
In particular, the fused compound of Formula 1-2 is represented as follows:
[Formula 1-2]
The X 1 is any one selected from NR 1 , O, CH and CH 2 , and the X 2 and X 3 are each independently any one selected from NR 1 , O, S, CH and CH 2 ,
Ar 1 , Ar 2 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L 1 is an integer of 0 or 1.
본 발명의 퓨즈드 화합물은 상기 퓨즈드 화합물은 하기 화학식 2-1 내지 2-32중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물이다:The fused compound of the present invention is a fused compound, wherein the fused compound is represented by any one of the following Formulas 2-1 to 2-32:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4] [Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 2-6][Formula 2-6]
[화학식 2-7][Formula 2-7]
[화학식 2-8][Formula 2-8]
[화학식 2-9][Formula 2-9]
[화학식 2-10] [Chemical Formula 2-10]
[화학식 2-11] [Chemical Formula 2-11]
[화학식 2-12] [Formula 2-12]
[화학식 2-13] [Formula 2-13]
[화학식 2-14] [Formula 2-14]
[화학식 2-15][Formula 2-15]
[화학식 2-16][Formula 2-16]
[화학식 2-17][Formula 2-17]
[화학식 2-18] [Formula 2-18]
[화학식 2-19][Formula 2-19]
[화학식 2-20][Formula 2-20]
[화학식 2-21][Formula 2-21]
[화학식 2-22][Formula 2-22]
[화학식 2-23][Formula 2-23]
[화학식 2-24] [Chemical Formula 2-24]
[화학식 2-25] [Formula 2-25]
[화학식 2-26] [Chemical Formula 2-26]
[화학식 2-27][Formula 2-27]
[화학식 2-28][Formula 2-28]
[화학식 2-29][Formula 2-29]
[화학식 2-30][Formula 2-30]
[화학식 2-31][Chemical Formula 2-31]
[화학식 2-32][Chemical Formula 2-32]
상기 Ar1 내지 Ar4 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,Ar 1 to Ar 4 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L1 및 L2는 각각 서로 독립적으로 0 또는 1의 정수이다.L 1 and L 2 are each independently an integer of 0 or 1.
상기 화합물은 아래 화합물들 중 어느 하나인 것을 특징으로 하는 화합물이다: The compound is a compound characterized in that it is any one of the following compounds:
본 발명의 일 측면에 따르면, 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 1층 이상의 유기물 층을 포함하는 유기전자소자로서, 상기 유기물층 중 적어도 1층 이상이 상기 화학식 2-1 내지 화학식 2-32의 퓨즈드 화합물을 포함하는 유기전자소자가 제공된다.According to an aspect of the present invention, an organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, wherein at least one or more of the organic material layers are in the formulas 2-1 to An organic electronic device including 2-32 of the fused compound is provided.
상기 퓨즈드 화합물은 단일 물질 또는 서로 다른 물질의 혼합물의 형태로 상기 유기물층에 포함될 수 있다. The fused compound may be included in the organic material layer in the form of a single material or a mixture of different materials.
상기 유기물층은 정공 주입층, 정공 수송층, 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층, 전자 저지층, 발광층, 정공 저지층, 전자 수송층, 전자 주입층 및 전자 수송 기능 및 전자 주입 기능을 동시에 갖는 기능층 중 적어도 하나를 포함할 수 있다. 상기 정공 주입층, 상기 정공 수송층 및 상기 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층 중 적어도 하나는, 통상의 정공 주입 물질, 정공 수송 물질 및 정공 주입 및 수송 기능을 동시에 하는 물질 외에, 전하-생성 물질을 더 포함할 수 있다.The organic material layer has a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function. It may include at least one of the functional layers. At least one of the hole injection layer, the hole transport layer, and the functional layer having both a hole injection function and a hole transport function, in addition to a conventional hole injection material, a hole transport material, and a material simultaneously injecting and transporting holes, is charged- It may further include a product material.
본 명세서 중 "유기물층"은 유기전자소자 중 제1전극과 제2전극 사이에 개재된 모든 층을 가리키는 용어이다.In the present specification, the term "organic material layer" refers to all layers interposed between the first electrode and the second electrode among organic electronic devices.
예를 들어, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광 호스트, 형광 호스트, 인광 도판트 및 형광 도판트 중 하나 이상을 포함할 수 있다. For example, the organic material layer may include an emission layer, and the emission layer may include at least one of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant.
상기 발광층은 적색, 녹색 또는 청색 발광층일 수 있다. The emission layer may be a red, green, or blue emission layer.
상기 전자 수송층에 상기 퓨즈드 화합물이 포함되어 있으며, 고효율, 고휘도, 고색순도, 및 장수명을 갖는 유기전자소자를 제공할 수 있다.The fused compound is included in the electron transport layer, and an organic electronic device having high efficiency, high brightness, high color purity, and long life can be provided.
또한, 상기 퓨즈드 화합물은 상기 발광층, 정공 수송층 및 소자 성능향상의 구조 응용에 포함될 수 있다.In addition, the fused compound may be included in the light emitting layer, the hole transport layer, and structural applications for improving device performance.
상기 유기전자소자는 화학식 2-1 내지 화학식 2-32의 퓨즈드 화합물을 이용하는 것을 제외하고는, 통상의 유기전자소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electronic device may be manufactured by a conventional method and material for manufacturing an organic electronic device, except for using the fused compound of Formulas 2-1 to 2-32.
본 발명의 일 측면에 따른 구체예로써, 상기 유기전자소자는 유기발광소자 (OLED), 유기태양전지 (OSC), 전자종이 (e-Paper), 유기감광체(OPC) 또는 유기트랜지스터 (OTFT)일 수 있다.As a specific example according to an aspect of the present invention, the organic electronic device is an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoreceptor (OPC), or an organic transistor (OTFT). I can.
유기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공전달층, 발광층, 정공저지층 및 전자전달층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착 시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기발광소자를 만들 수도 있다. 상기 유기물 층은 정공주입층, 정공전달층, 발광층, 정공저지층 및 전자전달층 등을 포함하는 다층 구조일 수도 있다. 또한, 상기 유기물 층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic light-emitting device uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer thereon, it can be produced by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, an emission layer, a hole blocking layer, and an electron transport layer. In addition, the organic material layer is made of a variety of polymer materials, and is used in a smaller number of solvent processes, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made in layers.
본 발명에 따른 유기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다. 본 발명에 따른 화합물은 유기태양전지, 조명용 OLED, Flexible OLED, 유기감광체, 유기트랜지스터 등을 비롯한 유기전자소자에서도 유기발광소자에 적용되는 것과 유사한 원리로 작용할 수 있다. The organic light-emitting device according to the present invention may be of a top emission type, a bottom emission type, or a double-sided emission type depending on the material used. The compound according to the present invention can act on a principle similar to that applied to an organic light emitting device in organic electronic devices including organic solar cells, lighting OLEDs, flexible OLEDs, organic photoreceptors, organic transistors, and the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다. Hereinafter, preferred embodiments are presented to aid in understanding the present invention. However, the following examples are provided for easier understanding of the present invention, and the contents of the present invention are not limited thereby.
또한, 본 발명의 각 실시예에서 제조방법이 구체적으로 개시되지 않은 화합물은 당업계에 통상적인 방법으로 제조하거나 또는 다른 실시예에 기재된 제조방법을 참고하여 제조함을 이해한다.In addition, it is understood that the compounds for which the preparation method is not specifically disclosed in each Example of the present invention are prepared by a method conventional in the art or prepared by referring to the preparation methods described in other Examples.
<중간체의 제조><Production of intermediate>
* 중간체 2-bromo-1-phenyl-1H-pyrrole (a-1)의 제조* Preparation of the intermediate 2-bromo-1-phenyl-1H-pyrrole (a-1)
500ml 둥근 바닥 플라스크에 질소 분위기 하에 0℃에서2-bromo-1H-pyrrole（2.2g，15mmol)와 iodobenzene（3.7g ，18mmol)을 N,N-다이메틸포름아마이드 250ml에 녹인 후 소듐하이드라이드 (60% mineral oil)(NaH)（0.8g ，22mmol), 천천히 첨가하고, 0℃를 유지하며 1시간 교반 및 상온에서 3시간 교반한다. 반응이 종결되면 반응액을 물 1L에 부어 고체를 석출시킨 후 여과한다. 고체를 톨루엔을 이용하여 재결정을 하여 A-1（1.7g， 50%)을 얻었다.Dissolve 2-bromo-1H-pyrrole (2.2g, 15mmol) and iodobenzene (3.7g, 18mmol) in 250ml of N,N-dimethylformamide at 0℃ in a nitrogen atmosphere in a 500ml round bottom flask, and then sodium hydride (60 % mineral oil)(NaH) (0.8g ，22mmol), add slowly, keep at 0℃, stir for 1 hour and stir at room temperature for 3 hours. When the reaction is complete, the reaction solution is poured into 1 L of water to precipitate a solid and then filtered. The solid was recrystallized using toluene to obtain A-1 (1.7 g, 50%).
MS : [M]= 222MS: [M]=222
* 중간체 a-2 내지 a-16의 제조* Preparation of intermediates a-2 to a-16
상기 중간체 a-1의 제조 방법으로 하기 [표 1]의 화합물을 얻었다:The compound of the following [Table 1] was obtained by the method for preparing the intermediate a-1:
* 중간체 N-(2-chlorophenyl)-1H-pyrrol-2-amine (b-1)의 제조* Preparation of intermediate N-(2-chlorophenyl)-1H-pyrrol-2-amine (b-1)
2-chloroaniline (6.4g, 50mmol)와 2-bromo-1H-pyrrole (8.0g, 55 mmol), n- 부틸 에테르（50 mL）, K2CO3 (14.51g, 105mmol), Cu (0.75g, 12mmol) 및 CuI (0.50 g, 2.6 mmol)의 혼합물을 120 ℃에서 6시간 가열 후. 반응물을 여과하고, 용매를 진공 증류 및 건조하여, 생성물을 크로마토 시스템으로 구성된 플래시로 정제하였다. 3:1 헥산 / 에틸 아세테이트를 용리액으로 사용한 크로마토 그래피의 화합물을 에탄올로 재결정하여 중간체 b-1 (6.7g, 70 %)을 얻었다. MS : [M]= 1922-chloroaniline (6.4g, 50mmol) and 2-bromo-1H-pyrrole (8.0g, 55 mmol), n-butyl ether (50 mL), K 2 CO 3 (14.51g, 105mmol), Cu (0.75g, 12mmol) and a mixture of CuI (0.50 g, 2.6 mmol) was heated at 120° C. for 6 hours. The reaction was filtered, the solvent was vacuum distilled and dried, and the product was purified by flash consisting of a chromatography system. The compound of chromatography using 3:1 hexane/ethyl acetate as an eluent was recrystallized with ethanol to obtain an intermediate b-1 (6.7 g, 70%). MS: [M]= 192
* 중간체 b-2 내지 b-42의 제조* Preparation of intermediates b-2 to b-42
상기 중간체 b-1의 제조 방법으로 하기 [표 2]의 화합물을 얻었다:The compound of the following [Table 2] was obtained by the method for preparing the intermediate b-1:
* 중간체 2-(2-nitrophenyl)-1H-pyrrole (c-1)의 제조* Preparation of the intermediate 2-(2-nitrophenyl)-1H-pyrrole (c-1)
질소 분위기에서 2-bromo-1H-pyrrole (7.5g, 51.51mmol), (2-nitrophenyl)boronic acid (9.5g, 56.66mmol) 및 아세트산칼륨 (15.2g, 154.53mmol)을 섞고, 디옥산 300ml에 첨가하고 교반하면서 가열하였다. 환류되는 상태에서 비스(디벤질리딘아세톤)팔라듐 (0.9g, 1.55mmol)과 트리사이클로헥실포스핀 (0.9g,1.55mmol)을 넣고 4시간 동안 가열 및 교반하였다. 반응 종료 후, 상온으로 온도를 낮춘 후 여과하였다. 여과액에 물을 넣고 클로로포름으로 추출하고, 유기층을 무수황산마그네슘으로 건조하였다. 감압 증류 후 에탄올로 재결정하여 중간체 c-1 (8.7g, 90%)를 제조하였다. Mix 2-bromo-1H-pyrrole (7.5g, 51.51mmol), (2-nitrophenyl)boronic acid (9.5g, 56.66mmol) and potassium acetate (15.2g, 154.53mmol) in a nitrogen atmosphere, and add to 300ml of dioxane And heated while stirring. In the state of refluxing, bis(dibenzylidineacetone)palladium (0.9g, 1.55mmol) and tricyclohexylphosphine (0.9g, 1.55mmol) were added and heated and stirred for 4 hours. After completion of the reaction, the temperature was lowered to room temperature and then filtered. Water was added to the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure and recrystallized with ethanol, intermediate c-1 (8.7g, 90%) was prepared.
MS : [M]= 188MS: [M]=188
* 중간체 c-2 내지 c-10의 제조* Preparation of intermediates c-2 to c-10
상기 중간체 c-1의 제조 방법으로 하기 [표 3]의 화합물을 얻었다:The compound of the following [Table 3] was obtained by the method for preparing the intermediate c-1:
* 중간체 2-(2-nitrophenoxy)-1H-pyrrole (d-1)의 제조* Preparation of intermediate 2-(2-nitrophenoxy)-1H-pyrrole (d-1)
질소 분위기에서 화합물 2-bromo-1H-pyrrole (4.4g, 30mmol)와 2-nitrophenol (1.7g, 44mmol)를 테트라하이드로퓨란 150ml에 넣고 교반 및 환류 하였다. 이 후 포타슘카보네이트 (12.2g, 59mmol)를 물 60ml에 녹여 투입한 후 11시간동안 반응 후 상온으로 온도를 낮추고 여과하였다. 여과물을 클로로포름과 물로 추출한 후 유기층을 황산마그네슘을 이용해 건조하였다. 이후 유기층을 감압증류 후 에틸 아세테이트를 이용해 재결정하였다. 생성된 고체를 여과 후 건조하여 중간체 d-1 (4.7g, 77%)을 제조하였다. Compound 2-bromo-1H-pyrrole (4.4g, 30mmol) and 2-nitrophenol (1.7g, 44mmol) were added to 150ml of tetrahydrofuran and stirred and refluxed in a nitrogen atmosphere. Thereafter, potassium carbonate (12.2g, 59mmol) was dissolved in 60ml of water, added, reacted for 11 hours, cooled to room temperature, and filtered. The filtrate was extracted with chloroform and water, and the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare intermediate d-1 (4.7g, 77%).
MS : [M]= 204 MS: [M]=204
* 중간체 d-2 내지 d-9의 제조* Preparation of intermediates d-2 to d-9
상기 중간체 d-1의 제조 방법으로 하기 [표 4]의 화합물을 얻었다:The compound of the following [Table 4] was obtained by the method for preparing the intermediate d-1:
* 중간체 2-((2-nitrophenyl)thio)-1H-pyrrole (e-1)의 제조* Preparation of intermediate 2-((2-nitrophenyl)thio)-1H-pyrrole (e-1)
질소 분위기에서 화합물 2-bromo-1H-pyrrole (4.4g, 30mmol)와 2-nitrobenzenethiol (6.8g, 44mmol)를 테트라하이드로퓨란 150ml에 넣고 교반 및환류 하였다. 혼합물에 포타슘카보네이트(12.2g, 59mmol)를 물 60ml에 녹여 투입한 후 11시간 동안 반응 후, 상온으로 온도를 낮추고 여과하였다. 여과물을 클로로포름과 물로 추출한 후 유기층을 황산마그네슘을 이용해 건조하였다. 유기층을 감압증류 후 에틸 아세테이트를 이용해 재결정하였다. 생성된 고체를 여과 후 건조하여 중간체 e-1 (4.0g, 60%)을 제조하였다.Compound 2-bromo-1H-pyrrole (4.4g, 30mmol) and 2-nitrobenzenethiol (6.8g, 44mmol) were added to 150ml of tetrahydrofuran and stirred and refluxed in a nitrogen atmosphere. Potassium carbonate (12.2g, 59mmol) was dissolved in 60ml of water and added to the mixture, followed by reaction for 11 hours, lowering the temperature to room temperature, and filtering. The filtrate was extracted with chloroform and water, and the organic layer was dried over magnesium sulfate. The organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare an intermediate e-1 (4.0 g, 60%).
MS : [M]= 220 MS: [M]= 220
* 중간체 e-2 내지 e-7의 제조* Preparation of intermediates e-2 to e-7
상기 중간체 e-1의 제조 방법으로 하기 [표 5]의 화합물을 얻었다:The compound of the following [Table 5] was obtained by the method for preparing the intermediate e-1:
* 중간체 methyl 2-((1H-pyrrol-2-yl)amino)benzoate (f-1)의 제조* Preparation of the intermediate methyl 2-((1H-pyrrol-2-yl)amino)benzoate (f-1)
500ml 둥근 바닥 플라스크에 가열장치와 수분제거장치를 설치하고 b-12（16.2g，80mol)과 메탄올（400ml）및 일정한 량의 진한 황산을 넣은 후 5시간 동안 회류하였다. 메탄올을 제거하고 중간체 f-1 17.0g (98%)을 얻었다.A heating device and a moisture removal device were installed in a 500ml round bottom flask, and b-12 (16.2g, 80mol), methanol (400ml), and a certain amount of concentrated sulfuric acid were added thereto, and then recirculated for 5 hours. Methanol was removed to obtain 17.0 g (98%) of an intermediate f-1.
MS : [M]= 216MS: [M]=216
* 중간체 f-2 내지 f-21의 제조* Preparation of intermediates f-2 to f-21
상기 중간체 f-1의 제조 방법으로 하기 [표 6]의 화합물을 얻었다:The compound of the following [Table 6] was obtained by the method for preparing the intermediate f-1:
* 중간체 2-(2-((1H-pyrrol-2-yl)amino)phenyl)propan-2-ol (g-1)의 제조 * Preparation of intermediate 2-(2-((1H-pyrrol-2-yl)amino)phenyl)propan-2-ol (g-1)
1000ml 둥근 바닥 플라스크에 질소 상태 하에서 f-1（27g，88mol)과 다이아이소프로필에터（400ml）을 넣고 교반 후, methylmagnesium bromide（35.5ml，308mmol）를 천천히 첨가한 후 50℃에서 교반하였다. 반응이 종결되면, 반응의 결과물을 층 분리하여 하부층을 제거하고 상부 유기층을 분리하여 감압 농축한 후, 컬럼크로마토그래피를 통하여 중간체 g-1 18.7g (98%)을 얻었다. In a 1000ml round bottom flask, f-1 (27g, 88mol) and diisopropyl ether (400ml) were added and stirred under nitrogen, and methylmagnesium bromide (35.5ml, 308mmol) was slowly added, followed by stirring at 50°C. When the reaction was completed, the resultant of the reaction was separated by layer to remove the lower layer, the upper organic layer was separated and concentrated under reduced pressure, and then 18.7 g (98%) of the intermediate g-1 was obtained through column chromatography.
MS : [M]= 216MS: [M]=216
* 중간체 g-2 내지 g-21의 제조* Preparation of intermediates g-2 to g-21
상기 중간체 g-1의 제조 방법으로 하기 [표 7]의 화합물을 얻었다:The compound of the following [Table 7] was obtained by the preparation method of the intermediate g-1:
* 중간체 1,8-dihydropyrrolo[2,3-b]indole (h-1)의 제조* Preparation of the intermediate 1,8-dihydropyrrolo[2,3-b]indole (h-1)
아르곤 분위기에서 b-1(116mg, 0.60mmol) 20mL와 탄산세슘 (390mg, 1.2mmol), 비스(벤조니트릴)디클로로 팔라듐 (9.6mg, 0.025mmol) 및 트리스{3,5-비스(트리플루오로메틸)페닐}-포스핀 (34mg, 0.050mmol) 및 톨루엔 (2.0mL)을 혼합물을 110℃에서 24 시간 동안 교반하였다. 혼합물을 실온으로 냉각시켰다. Hydrochloric acid (1M, 6mL)를 넣고 에틸 아세테이트 (10 mLХ3)로 추출한 후 유기층을 소금물로 세척하고 무수 황산나트륨으로 건조 및 휘발물을 증발시킨 후, 컬럼 크로마토그래피로 중간체 h-1 (74.9mg, 0.48mmol, 80 % 수율)를 얻었다.In an argon atmosphere, b-1 (116mg, 0.60mmol) 20mL and cesium carbonate (390mg, 1.2mmol), bis(benzonitrile)dichloropalladium (9.6mg, 0.025mmol) and tris(3,5-bis(trifluoromethyl) )Phenyl}-phosphine (34mg, 0.050mmol) and toluene (2.0mL) were stirred at 110°C for 24 hours. The mixture was cooled to room temperature. Hydrochloric acid (1M, 6mL) was added and extracted with ethyl acetate (10 mLХ3). The organic layer was washed with brine, dried over anhydrous sodium sulfate, and evaporated from volatiles, and then intermediate h-1 (74.9mg, 0.48mmol) by column chromatography. , 80% yield).
MS : [M]= 156MS: [M]= 156
* 중간체 h-2 내지 h-11의 제조* Preparation of intermediates h-2 to h-11
상기 중간체 h-1의 제조 방법으로 하기 [표 8]의 화합물을 얻었다:The compound of the following [Table 8] was obtained by the method for preparing the intermediate h-1:
* 중간체 4,4-dimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline (i-1)의 제조* Preparation of intermediate 4,4-dimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline (i-1)
1000ml 둥근 바닥 플라스크에 화합물 g-1 （18.8g，87mmol)과 인산 550ml을 넣고 60도에서 교반하였다. 반응이 종결되면, 반응의 결과물에 물을 넣고 교반하였다. 교반 후 여과시켜 물과 메탄올로 씻어주었다. 컬럼 크로마토그래피를 통하여 중간체 i-1 （16.2g，94%)을 얻었다Compound g-1 (18.8g, 87mmol) and 550ml of phosphoric acid were added to a 1000ml round bottom flask and stirred at 60 degrees. When the reaction was completed, water was added to the reaction product and stirred. After stirring, it was filtered and washed with water and methanol. Intermediate i-1 (16.2g, 94%) was obtained through column chromatography.
MS : [M]= 198MS: [M]= 198
* 중간체 i-2 내지 i-22의 제조* Preparation of intermediates i-2 to i-22
상기 중간체 i-1의 제조 방법으로 하기 [표 9]의 화합물을 얻었다:The compound of the following [Table 9] was obtained by the method for preparing the intermediate i-1:
* 중간체 1,4-dihydropyrrolo[3,2-b]indole (j-1)의 제조* Preparation of the intermediate 1,4-dihydropyrrolo[3,2-b]indole (j-1)
THF 용매 400ml에 2-(2-nitrophenyl)-1H-pyrrole（7.0g，37mmol), triphenylphosphine（17g，65mmol), 탄산칼륨을 녹인 후 36시간 동안 환류시켰다. 반응이 종료되면 상온으로 식히고, CH2Cl2와 물로 추출하고, 유기물층을 황산마그네슘으로 건조 및 감압 농축한 후 생성물을 컬럼 크로마토그래피를 이용하여 중간체 j-1 (3.9g， 68%) 수득했다.After dissolving 2-(2-nitrophenyl)-1H-pyrrole (7.0g，37mmol), triphenylphosphine (17g，65mmol), and potassium carbonate in 400ml of THF solvent, the mixture was refluxed for 36 hours. When the reaction was completed, it was cooled to room temperature, extracted with CH 2 Cl 2 and water, the organic layer was dried over magnesium sulfate and concentrated under reduced pressure, and the product was obtained by column chromatography to obtain intermediate j-1 (3.9g, 68%).
MS : [M]= 156MS: [M]= 156
* 중간체 j-2 내지 j-36의 제조* Preparation of intermediates j-2 to j-36
상기 중간체 j-1의 제조 방법으로 하기 [표 10]의 화합물을 얻었다:The compound of the following [Table 10] was obtained by the method for preparing the intermediate j-1:
* 중간체 8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2,3-b]indole (k-1)의 제조* Preparation of intermediate 8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2,3-b]indole (k-1)
질소 분위기에서 2-bromo-4,6-diphenyl-1,3,5-triazine (4.7 g, 15.1mmol), 1,8-dihydropyrrolo[2,3-b]indole (2.6g, 16.6 mmol) 및 sodium tert-butoxide (2.9 g, 30.2mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g,0.3 mmol)을 투입했다. 3시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 컬럼 크로마토그래피로 정제해서 중간체 k-1 (3.8g, 65%)을 얻었다.2-bromo-4,6-diphenyl-1,3,5-triazine (4.7 g, 15.1mmol), 1,8-dihydropyrrolo[2,3-b]indole (2.6g, 16.6 mmol) and sodium in a nitrogen atmosphere tert-butoxide (2.9 g, 30.2mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g,0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by column chromatography to obtain an intermediate k-1 (3.8 g, 65%).
MS : [M]= 387 MS: [M]= 387
* 중간체 k-2 내지 k-102의 제조* Preparation of intermediates k-2 to k-102
상기 중간체 k-1의 제조 방법으로 하기 [표 11]의 화합물을 얻었다:The compound of the following [Table 11] was obtained by the method for preparing the intermediate k-1:
<실시예의 제조><Preparation of Examples>
* 실시예 1-([1,1'-biphenyl]-4-yl)-8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2,3-b]indole 제조 (A-1)* Example 1-([1,1'-biphenyl]-4-yl)-8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2, 3-b]indole preparation (A-1)
500ml 둥근 바닥 플라스크에 질소 분위기 하에 소듐하이드라이드 (60% mineral oil)(NaH)（0.8g ，22mmol), N,N-다이메틸포름아마이드 90.0ml을 넣고 반응액을 0℃로 냉각한다. 0℃에서 8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2,3-b]indole （5.8g，15mmol)을 N,N-다이메틸포름아마이드 90.0ml에 녹인 용액을 천천히 첨가한 후 0℃를 유지하며 1시간 교반한다. 1시간 후 4-bromo-1,1'-biphenyl（4.2g ，18mmol)을 N,N-다이메틸포름아마이드 130ml에 녹인 용액을 천천히 첨가 완료되면 반응액을 상온으로 올린 후 교반한다. 반응이 종결되면 반응액을 물 1L에 부어 고체를 석출시킨 후 여과한다. 고체를 톨루엔을 이용하여 재결정을 하여 A-1（4.7g， 57.8%)을 얻었다.In a 500 ml round bottom flask, sodium hydride (60% mineral oil) (NaH) (0.8 g, 22 mmol) and 90.0 ml of N,N-dimethylformamide were added in a nitrogen atmosphere, and the reaction solution was cooled to 0°C. N,N-die of 8-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,8-dihydropyrrolo[2,3-b]indole (5.8g，15mmol) at 0℃ After slowly adding the solution dissolved in 90.0ml of methylformamide, the mixture is stirred at 0℃ for 1 hour. After 1 hour, a solution obtained by dissolving 4-bromo-1,1'-biphenyl (4.2 g, 18 mmol) in 130 ml of N,N-dimethylformamide is slowly added, and the reaction solution is raised to room temperature and stirred. When the reaction is complete, the reaction solution is poured into 1 L of water to precipitate a solid and then filtered. The solid was recrystallized using toluene to obtain A-1 (4.7 g, 57.8%).
MS : [M]= 539MS: [M]=539
* 실시예 A-2 내지 A-88의 제조* Preparation of Examples A-2 to A-88
상기 실시예 A-1의 제조 방법으로 하기 [표 12]의 화합물을 얻었다:The compound of the following [Table 12] was obtained by the preparation method of Example A-1:
* 실시예 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,4,4-trimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline 제조 (B-1)* Example 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,4,4-trimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline Manufacturing (B-1)
500ml 둥근 바닥 플라스크에 질소 분위기 하에 소듐하이드라이드(60% mineral oil)(NaH)（0.8g ，22mmol), N,N-다이메틸포름아마이드 90.0ml을 넣고 반응액을 0℃로 냉각한다. 0℃에서 1,4,4-trimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline（3.2g，15mmol)을 N,N-다이메틸포름아마이드 （90.0ml）에 녹인 용액을 천천히 첨가한 후 0℃를 유지하며 1시간 교반한다. 1시간 후 2-bromo-4,6-diphenyl-1,3,5-triazine（5.6g ，18mmol)을 N,N-다이메틸포름아마이드 130ml에녹인 용액을 천천히 첨가한다. 첨가 완료되면 반응액을 상온으로 올린 후 교반한다. 반응이 종결되면 반응액을 물 1L에 부어 고체를 석출시킨 후 여과한다. 고체를 톨루엔을 이용하여 재결정을 하여 B-1（4.1g， 60.0%)을 얻었다.In a 500 ml round bottom flask, sodium hydride (60% mineral oil) (NaH) (0.8 g, 22 mmol) and 90.0 ml of N,N-dimethylformamide were added in a nitrogen atmosphere, and the reaction solution was cooled to 0°C. A solution in which 1,4,4-trimethyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoline (3.2g, 15mmol) is dissolved in N,N-dimethylformamide (90.0ml) at 0℃ After slowly adding, the mixture was stirred at 0°C for 1 hour. After 1 hour, a solution of 2-bromo-4,6-diphenyl-1,3,5-triazine (5.6 g, 18 mmol) in 130 ml of N,N-dimethylformamide was slowly added. When the addition is complete, the reaction solution is raised to room temperature and stirred. When the reaction is complete, the reaction solution is poured into 1 L of water to precipitate a solid and then filtered. The solid was recrystallized using toluene to obtain B-1 (4.1 g, 60.0%).
MS : [M]= 443MS: [M]= 443
* 실시예 B-2 내지 B-99의 제조* Preparation of Examples B-2 to B-99
상기 실시예 B-1의 제조 방법으로 하기 [표 13]의 화합물을 얻었다:The compound of the following [Table 13] was obtained by the preparation method of Example B-1:
* 실시예 10-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-1-methyl-1H-pyrrolo[2,3-b]quinoxalin-9(4H)-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine 제조 (C-1)* Example 10-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-1-methyl-1H-pyrrolo[2,3-b]quinoxalin-9(4H )-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine preparation (C-1)
500ml 둥근 바닥 플라스크에 질소 분위기 하에 소듐하이드라이드(60% mineral oil)(NaH)（0.8g ，22mmol), N,N-다이메틸포름아마이드 90.0ml을 넣고 반응액을 0℃로 냉각한다. 0℃에서 4-(4,6-diphenyl-1,3,5-triazin-2-yl)-1-methyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoxaline（6.3g，15mmol)을 N,N-다이메틸포름아마이드 90.0ml에 녹인 용액을 천천히 첨가 후 0℃를 유지하며 1시간 교반한다. 1시간 후 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacridine（6.6g ，18mmol)을 N,N-다이메틸포름아마이드 130ml에 녹인 용액을 천천히 첨가 후, 완료되면 반응액을 상온으로 올린 후 교반한다. 반응이 종결되면 반응액을 물 1L에 부어 고체를 석출시킨 후 여과한다. 고체를 톨루엔을 이용하여 재결정을 하여 C-1（5.9g， 55.0%)을 얻었다.In a 500 ml round bottom flask, sodium hydride (60% mineral oil) (NaH) (0.8 g, 22 mmol) and 90.0 ml of N,N-dimethylformamide were added in a nitrogen atmosphere, and the reaction solution was cooled to 0°C. 4-(4,6-diphenyl-1,3,5-triazin-2-yl)-1-methyl-4,9-dihydro-1H-pyrrolo[2,3-b]quinoxaline（6.3g， at 0℃ 15mmol) dissolved in 90.0ml of N,N-dimethylformamide was slowly added and stirred at 0℃ for 1 hour. After 1 hour, a solution obtained by dissolving 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacridine (6.6 g, 18 mmol) in 130 ml of N,N-dimethylformamide was slowly added, and when completed, the reaction solution After raising to room temperature, it is stirred. When the reaction is complete, the reaction solution is poured into 1 L of water to precipitate a solid and then filtered. The solid was recrystallized using toluene to obtain C-1 (5.9 g, 55.0%).
MS : [M]= 699MS: [M]= 699
* 실시예 C-2 내지 C-70의 제조* Preparation of Examples C-2 to C-70
상기 실시예 C-1의 제조 방법으로 하기 [표 14]의 화합물을 얻었다:The compound of the following [Table 14] was obtained by the preparation method of Example C-1:
<실험예> <Experimental Example>
ITO가 1500Å의 두께로 박막 코팅된 유리 기판을 피셔사의 세제를 녹인 2차 증류수에 넣고 초음파로 30분간 세척하였다. ITO를 30 분간 세척한 후 증류수로 2 회 반복하여 초음파 세척을 10 분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척하고 건조시킨 후, 플라즈마 세정기로 이송시켜, 산소 플라즈마를 이용하여 상기 기판을 5 분간 세정한 후 진공 증착기로 기판을 이송시켰다.A glass substrate coated with a thin film of ITO with a thickness of 1500 Å was put in secondary distilled water dissolved in Fisher's detergent and washed for 30 minutes with ultrasonic waves. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water was finished, ultrasonically cleaned with a solvent of isopropyl alcohol, acetone, and methanol, dried, transferred to a plasma cleaner, and cleaned for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine)를 500Å 진공증착 후, 정공전달층으로 a-NPD (N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) 300Å 진공 증착한 후, 청색 물질의 경우 청색 호스트로 AND (9,10-Di(2-naphthyl)anthracene)에 도판트 DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine) 5%를 도핑하였으며, 적색의 경우 RH-01 (9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-bicarbazole)에 RD-01 (5,6,11,12-tetraphenyltetracene) 5%를 도핑하여 300Å의 두께로 진공 증착하였다. 그리고 정공저지층 및 정공전달층으로 TPBi (1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene) 물질을 400Å의 두께로 진공 증착 하였으며, 순차적으로 LiF 5Å과 Al(알루미늄) 2000Å 증착하여 음극을 형성하였다. After 500Å vacuum deposition of 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) as a hole injection layer on the prepared ITO transparent electrode, a-NPD (N, N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) 300Å vacuum deposition, and in the case of a blue material, the AND (9, Dopant DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine) 5% was doped in 10-Di(2-naphthyl)anthracene), and in the case of red, RH-01 (9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-bicarbazole) doped with 5% of RD-01 (5,6,11,12-tetraphenyltetracene) Then, TPBi (1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene) material was vacuum deposited to a thickness of 400Å as a hole blocking layer and a hole transport layer, and sequentially LiF 5Å and Al (aluminum) 2000Å were deposited to form a cathode.
상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, LiF는 0.2 Å/sec, 알루미늄은 3~7Å의 증착속도를 유지하였다.In the above process, the deposition rate of the organic material was maintained at 1 Å/sec, the deposition rate for LiF was 0.2 Å/sec, and the deposition rate for aluminum was maintained at 3 to 7 Å.
상기 내용에서 실시예를 이용한 비교실험은 하기와 같다.Comparative experiments using the examples in the above are as follows.
1) 청색 발광의 도판트 (DPAP-DPPA) 비교 실험은 표 151) A comparative experiment of blue light-emitting dopant (DPAP-DPPA) is shown in Table 15.
2) 청색 발광에서 HTL (a-NPD)의 비교실험은 표 162) The comparative experiment of HTL (a-NPD) in blue light emission is shown in Table 16.
3) 청색 발광에서 ETL (TPBi)의 비교실험은 표 173) The comparative experiment of ETL (TPBi) in blue light emission is shown in Table 17.
4) 적색 발광의 호스트 (RH-01)의 비교 실험은 표 18Table 18
5) 적색 발광의 도판트 (RD-01)의 비교 실험은 표 195) Comparative experiment of the red light-emitting dopant (RD-01) is shown in Table 19
표 15 내지 표 19에서, 상기 기재된 실시예의 일부 물질의 성능을 비교하였다.In Tables 15-19, the performance of some materials of the examples described above was compared.
상기에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 하기 표 15 내지 표 19에 나타내었다.The electrical emission characteristics of the organic light-emitting device prepared above are shown in Tables 15 to 19 below.
아래 표 15는 청색 발광에서 AND 호스트 상태에서 DPAP-DPPA와 실시예의 성능 비교를 나타낸다. Table 15 below shows the performance comparison between DPAP-DPPA and the Example in the AND host state in blue light emission.
아래 표 16은 청색 발광의 AND/DPAP-DPPA 상태에서 HTL의 a-NPD와 실시예의 성능 비교를 나타낸다. Table 16 below shows the performance comparison between a-NPD of HTL and the Example in the AND/DPAP-DPPA state of blue light emission.
아래 표 17은 청색 발광의 AND/DPAP-DPPA 상태에서 ETL의 TPBi와 실시예의 성능 비교를 나타낸다. Table 17 below shows the performance comparison between TPBi of ETL and Example in the AND/DPAP-DPPA state of blue light emission.
아래 표 18은 적색 발광의 RH-01/RD-01 상태에서 RH-01과 실시예의 성능 비교를 나타낸다. Table 18 below shows a comparison of the performance of RH-01 and Example in the state of RH-01/RD-01 in red light emission.
아래 표 19는 적색 발광의 RH-01/RD-01 상태에서 RD-01과 실시예의 성능 비교를 나타낸다. Table 19 below shows a comparison of the performance of RD-01 and Example in the state of RH-01/RD-01 in red light emission.
상기 표 15 내지 표 19의 결과로부터, 본 발명에 따른 퓨즈드 화합물은 청색과 적색 발광에서 성능 향상 결과를 얻었으며, 정공수송층 및 전자수송층의 역할에서 발광 효율 및 수명 특성이 향상됨을 확인할 수 있었다.From the results of Tables 15 to 19, it was confirmed that the fused compound according to the present invention obtained performance improvement results in blue and red light emission, and improved luminous efficiency and lifetime characteristics in the role of the hole transport layer and the electron transport layer.
Claims (6)
[화학식 1-2]
상기 X1은 N-R1, O, CH 및 CH2로부터 선택된 어느 1종이며, 상기 X2 및 X3은 각각 서로 독립적으로 N-R1, O, S, CH 및 CH2로부터 선택된 어느 1종이며,
상기 Ar1, Ar2 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,
상기 L1은 0 또는 1의 정수이다.A fused compound characterized by represented by the following formula 1-2:
[Formula 1-2]
The X 1 is any one selected from NR 1 , O, CH and CH 2 , and the X 2 and X 3 are each independently any one selected from NR 1 , O, S, CH and CH 2 ,
Ar 1 , Ar 2 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L 1 is an integer of 0 or 1.
상기 퓨즈드 화합물은 하기 화학식 2-10 내지 2-16 및 2-18 중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물:
[화학식 2-10]
[화학식 2-11]
[화학식 2-12]
[화학식 2-13]
[화학식 2-14]
[화학식 2-15]
[화학식 2-16]
[화학식 2-18]
상기 Ar1, Ar2 및 R1은 각각 서로 독립적으로 치환 또는 비치환된 탄소수 1 내지 30개의 알킬기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기 중에서 선택되고,
L1은 0 또는 1의 정수이다.The method of claim 1,
The fused compound is a fused compound, characterized in that represented by any one of the following Formulas 2-10 to 2-16 and 2-18:
[Chemical Formula 2-10]
[Chemical Formula 2-11]
[Formula 2-12]
[Formula 2-13]
[Formula 2-14]
[Formula 2-15]
[Formula 2-16]
[Formula 2-18]
Ar 1 , Ar 2 and R 1 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted aryl cyan group having 6 to 30 carbon atoms; A substituted or unsubstituted arylhalogen group having 6 to 30 carbon atoms; It is selected from a substituted or unsubstituted C4 to C40 heteroaryl group,
L 1 is an integer of 0 or 1.
상기 퓨즈드 화합물은 아래 화합물들 중 어느 하나인 것을 특징으로 하는 퓨즈드 화합물:
The fused compound is a fused compound, characterized in that any one of the following compounds:
상기 유기물층 중 적어도 1층 이상이 제1항 내지 제3항 중 어느 한 항의 퓨즈드 화합물을 포함하는 유기전자소자. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the electrodes,
An organic electronic device in which at least one or more of the organic material layers include the fused compound of any one of claims 1 to 3.
상기 유기물층은 정공 주입층, 정공 수송층, 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층, 전자 저지층, 발광층, 정공 저지층, 전자 수송층, 전자 주입층, 및 전자 수송 기능 및 전자 주입 기능을 동시에 갖는 기능층 중 적어도 하나를 포함하는 유기전자소자.The method of claim 4,
The organic material layer has a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function at the same time. An organic electronic device comprising at least one of the functional layers having.
상기 유기전자소자가 유기발광소자 (OLED), 유기태양전지 (OSC), 전자종이 (e-Paper), 유기감광체(OPC) 또는 유기트랜지스터 (OTFT)인 유기전자소자.
The method of claim 5,
The organic electronic device is an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoconductor (OPC) or an organic transistor (OTFT).
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