WO2023027203A1 - Luminescent material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device - Google Patents
Luminescent material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device Download PDFInfo
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- WO2023027203A1 WO2023027203A1 PCT/KR2021/011229 KR2021011229W WO2023027203A1 WO 2023027203 A1 WO2023027203 A1 WO 2023027203A1 KR 2021011229 W KR2021011229 W KR 2021011229W WO 2023027203 A1 WO2023027203 A1 WO 2023027203A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/16—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
Definitions
- the present invention relates to a fused compound, a manufacturing method thereof, and a technology intended to contribute to the development of an organic electronic device using the same.
- organic light emitting diodes are composed of a cathode, an anode, and an organic material layer interposed between the cathode and the anode.
- the 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 if necessary, one or two organic layers may be omitted.
- a cathode such as LiAl
- an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side.
- the light-emitting layer formation method is a method of doping a phosphorescence (organic metal) into a fluorescence host (pure organic material) and a method of doping a fluorescence dopant (organic material containing nitrogen, etc.) into a fluorescent host. and a method of implementing a long wavelength by using a dopant (DCM, Rubrene, DCJTB, etc.) on a light emitting body.
- ligand materials for forming the light emitting layer and the common layer include a core such as benzene, naphthalene, florene, spiroflorene, anthracene, pyrene, and carbazole, ligands such as phenyl, biphenyl, naphthalene, and heterocycle, and ortho, meta , para, etc., and structures in which amine, cyan, fluorine, methyl, trimethyl, etc. are substituted.
- the present invention is to improve organic light emitting performance of a planar structure having excellent performance by using a fused compound.
- An object of the present invention is to provide an organic electric device with excellent performance through the development of a material having a planar structure using a fused compound.
- the present invention is to develop organic light emitting device materials of fused compounds.
- the present invention is any one selected from compounds represented by the following Chemical Formulas 1-1 to 1-5.
- Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to
- Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl
- a fused compound characterized in that Formulas 1-1 to 1-5 are represented by any one of the following Formulas 2-1 to 2-26:
- Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to
- Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl
- the present invention is to provide a material with excellent performance of an organic electronic device through a cyclic amine compound using a fused compound, and another aspect of the present invention provides an organic electronic device including a fused compound.
- the fused compound according to the present invention provides a symmetric, asymmetric and planar structure, and the symmetric, asymmetric and planar structure of the present invention has excellent performance, and the structure of the present invention uses the fused compound in terms of embodiments.
- An organic light emitting device with excellent structural performance was obtained.
- any one fused compound selected from compounds represented by Chemical Formulas 1-1 to 1-5 is provided.
- Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to
- Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl
- a fused compound characterized in that Formulas 1-1 to 1-5 are represented by any one of the following Formulas 2-1 to 2-26:
- Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to
- Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl
- a compound characterized in that the compound is one of the following compounds
- an organic electronic device including a first electrode, a second electrode, and one or more organic material layers disposed between these electrodes, wherein at least one layer of the organic material layers includes a fused compound.
- the fused compound may be included in the organic layer in the form of a single material or a mixture of different materials.
- the organic material layer is 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 least one of the functional layers may be included.
- At least one of the hole injection layer, the hole transport layer, and the functional layer having the hole injection function and the hole transport function at the same time, in addition to a conventional hole injection material, a hole transport material, and a material having hole injection and transport functions simultaneously, charge- It may further include a product material.
- organic material layer is a term indicating all layers interposed between the first electrode and the second electrode in an organic electronic device.
- the organic layer may include a light emitting layer
- the light emitting layer may include at least one of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant.
- the light emitting layer may be a red, green or blue light emitting layer.
- the fused compound is included in the electron transport layer, and an organic electronic device having high efficiency, high luminance, high color purity, and long lifespan can be provided.
- the fused compound may be included in structural applications of the light emitting layer, the hole transport layer, and device performance improvement.
- the organic electronic device may be manufactured by conventional organic electronic device manufacturing methods and materials, except for using the fused compounds of Chemical Formulas 1-1 to 1-5.
- the organic electronic device may be 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).
- OLED organic light emitting device
- OSC organic solar cell
- e-Paper electronic paper
- OPC organic photoreceptor
- OTFT organic transistor
- the organic light emitting device uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode by depositing a metal or 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, depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
- PVD physical vapor deposition
- the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer.
- the organic layer can be formed by using various polymer materials and using a solvent process other than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. Can be made in layers.
- the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.
- the compound according to the present invention may 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.
- a glass substrate coated with a thin film of ITO to a thickness of 1500 ⁇ was placed in double distilled water in which Fisher's detergent was dissolved and washed with ultrasonic waves for 30 minutes. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, and drying, the substrate was transferred to a plasma cleaner, and the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator.
- solvents such as isopropyl alcohol, acetone, and methanol
- Table 16 is a table comparing performance of DPAP-DPPA and Examples in the AND host state in blue light emission.
- Table 17 below is a table comparing performance of TPBi of ETL and Example in AND/DPAP-DPPA state of blue light emission.
- Table 18 below is a table comparing the performance of RD-01 and Example in the RH-01 host state in red light emission.
- An organic light emitting device using the fused compound of the present invention was able to obtain excellent improvement in light emitting efficiency and lifespan. For this reason, it is industrially useful as an OLED with high practicality.
- the organic light emitting device of the present invention can be suitably used for light sources such as flat panel displays, flat light emitting bodies, surface light emitting OLED light emitting bodies for lighting, flexible light emitting bodies, copiers, printers, LCD backlights or meters, display boards, signs, etc.
- light sources such as flat panel displays, flat light emitting bodies, surface light emitting OLED light emitting bodies for lighting, flexible light emitting bodies, copiers, printers, LCD backlights or meters, display boards, signs, etc.
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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 manufacturing method thereof, and a technology intended 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 overall composition of the device, the 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 if necessary, one or two organic layers may be omitted. When an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. In addition, these electrons recombine with holes in the light emitting layer to generate 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 light-emitting layer formation method is a method of doping a phosphorescence (organic metal) into a fluorescence host (pure organic material) and a method of doping a fluorescence dopant (organic material containing nitrogen, etc.) into a fluorescent host. and a method of implementing a long wavelength by using a dopant (DCM, Rubrene, DCJTB, etc.) on a light emitting body. Through such doping, the emission wavelength, efficiency, driving voltage, and lifetime are being improved. In general, ligand materials for forming the light emitting layer and the common layer include a core such as benzene, naphthalene, florene, spiroflorene, anthracene, pyrene, and carbazole, ligands such as phenyl, biphenyl, naphthalene, and heterocycle, and ortho, meta , para, etc., and 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 progresses in the direction of large-size, in the case of OLED, materials with more delicate and more vivid colors are required. In addition to the color coordinates of the emission wavelength, a high luminous efficiency at a low driving voltage of the device and a high glass transition temperature and chemical structural 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 organic light emitting performance of a planar structure having excellent performance by using a fused compound. An object of the present invention is to provide an organic electric device with 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 organic light emitting device materials of fused compounds.
본 발명은 하기 화학식 1-1 내지 화학식 1-5로 표시되는 화합물로부터 선택된 어느 하나이다.The present invention is any one selected from compounds represented by the following Chemical 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 Ar1 내지 Ar8은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬티옥시기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬아민기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; 치환 또는 비치환된 탄소수 4 내지 40개의 아미노헤테로기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 보란아릴기 중에서 선택되고,Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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; A substituted or unsubstituted aminoaryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aminohetero group having 4 to 40 carbon atoms; A substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms; It is selected from substituted or unsubstituted borane aryl groups having 6 to 30 carbon atoms,
Ar9와 Ar10은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 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 선택된다.Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl groups having 4 to 40 carbon atoms.
상기 화학식 1-1 내지 화학식 1-5는 하기 화학식 2-1 내지 2-26중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물:A fused compound characterized in that Formulas 1-1 to 1-5 are represented by any one of the following Formulas 2-1 to 2-26:
[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][Formula 2-10]
[화학식 2-11][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][Formula 2-24]
[화학식 2-25][Formula 2-25]
[화학식 2-26][Formula 2-26]
화학식 2-1 내지 화학식 2-26에서In Formula 2-1 to Formula 2-26
상기 Ar1 내지 Ar8은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬티옥시기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬아민기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; 치환 또는 비치환된 탄소수 4 내지 40개의 아미노헤테로기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 보란아릴기 중에서 선택되고,Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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; A substituted or unsubstituted aminoaryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aminohetero group having 4 to 40 carbon atoms; A substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms; It is selected from substituted or unsubstituted borane aryl groups having 6 to 30 carbon atoms,
Ar9와 Ar10은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 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 선택된다.Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl groups having 4 to 40 carbon atoms.
본 발명은 퓨즈드 화합물을 이용한 고리형 아민 화합물 등을 통해, 유기전자소자의 성능이 우수한 물질 제공에 있으며, 또한 본 발명의 또 다른 일 측면에는 퓨즈드 화합물을 포함하는 유기 전자 소자에 제공된다.The present invention is to provide a material with excellent performance of an organic electronic device through a cyclic amine compound using a fused compound, and another aspect of the present invention provides an organic electronic device including a fused compound.
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 symmetric, asymmetric and planar structure, and the symmetric, asymmetric and planar structure of the present invention has excellent performance, and the structure of the present invention uses the fused compound in terms of embodiments. An organic light emitting device with excellent structural performance was obtained.
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 explaining an example of the present invention, so the present invention is not limited thereto.
본 발명의 일 측면에 따라, 하기 화학식 1-1 내지 화학식 1-5로 표시되는 화합물로부터 선택된 어느 하나의 퓨즈드 화합물이 제공된다.According to one aspect of the present invention, any one fused compound selected from compounds represented by Chemical Formulas 1-1 to 1-5 is provided.
[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 Ar1 내지 Ar8은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬티옥시기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬아민기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; 치환 또는 비치환된 탄소수 4 내지 40개의 아미노헤테로기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 보란아릴기 중에서 선택되고,Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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; A substituted or unsubstituted aminoaryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aminohetero group having 4 to 40 carbon atoms; A substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms; It is selected from substituted or unsubstituted borane aryl groups having 6 to 30 carbon atoms,
Ar9와 Ar10은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 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 선택된다.Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl groups having 4 to 40 carbon atoms.
상기 화학식 1-1 내지 화학식 1-5는 하기 화학식 2-1 내지 2-26중 어느 하나로 표시되는 것을 특징으로 하는 퓨즈드 화합물:A fused compound characterized in that Formulas 1-1 to 1-5 are represented by any one of the following Formulas 2-1 to 2-26:
[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][Formula 2-10]
[화학식 2-11][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][Formula 2-24]
[화학식 2-25][Formula 2-25]
[화학식 2-26][Formula 2-26]
화학식 2-1 내지 화학식 2-26에서In Formula 2-1 to Formula 2-26
상기 Ar1 내지 Ar8은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬티옥시기; 치환 또는 비치환된 탄소수 1 내지 20개의 알킬아민기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴할로겐기; 치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; 치환 또는 비치환된 탄소수 4 내지 40개의 아미노헤테로기; 치환 또는 비치환된 탄소수 4 내지 40개의 헤테로아릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 보란아릴기 중에서 선택되고,Ar 1 to Ar 8 are each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; A substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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; A substituted or unsubstituted aminoaryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aminohetero group having 4 to 40 carbon atoms; A substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms; It is selected from substituted or unsubstituted borane aryl groups having 6 to 30 carbon atoms,
Ar9와 Ar10은 각각 서로 독립적으로 수소; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴티옥시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴술폭시기; 치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30개의 아릴포스핀옥사이드기; 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 선택된다.Ar 9 and Ar 10 are each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylthioxy group having 6 to 40 carbon atoms; a substituted or unsubstituted arylsulfoxy group having 6 to 40 carbon atoms; A substituted or unsubstituted arylamine group having 6 to 40 carbon atoms; A substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylphosphine oxide group having 6 to 30 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 substituted or unsubstituted heteroaryl groups having 4 to 40 carbon atoms.
상기 화합물은 아래 화합물들 중 하나인 것을 특징으로 하는 화합물A compound, characterized in that the compound is 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 퓨즈드 화합물을 포함하는 유기전자소자가 제공된다.According to one aspect of the present invention, an organic electronic device including a first electrode, a second electrode, and one or more organic material layers disposed between these electrodes, wherein at least one layer of the organic material layers includes a fused compound. An electronic device 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 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 is 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 least one of the functional layers may be included. At least one of the hole injection layer, the hole transport layer, and the functional layer having the hole injection function and the hole transport function at the same time, in addition to a conventional hole injection material, a hole transport material, and a material having hole injection and transport functions simultaneously, charge- 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, "organic material layer" is a term indicating all layers interposed between the first electrode and the second electrode in an organic electronic device.
*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 layer may include a light emitting layer, and the light emitting 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 light emitting layer may be a red, green or blue light emitting 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 luminance, high color purity, and long lifespan 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 structural applications of the light emitting layer, the hole transport layer, and device performance improvement.
상기 유기전자소자는 화학식 1-1 내지 1-5의 퓨즈드 화합물을 이용하는 것을 제외하고는, 통상의 유기전자소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electronic device may be manufactured by conventional organic electronic device manufacturing methods and materials, except for using the fused compounds of Chemical Formulas 1-1 to 1-5.
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 one aspect of the present invention, the organic electronic device may be 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). 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 physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode by depositing a metal or 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, depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be fabricated 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, a light emitting layer, a hole blocking layer, and an electron transport layer. In addition, the organic layer can be formed by using various polymer materials and using a solvent process other than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. 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 a top emission type, a bottom emission type, or a double side emission type depending on the material used. The compound according to the present invention may 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, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is 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 compounds for which preparation methods are not specifically disclosed in each embodiment of the present invention are prepared by conventional methods in the art or with reference to preparation methods described in other embodiments.
<중간체의 제조><Preparation of intermediates>
* 중간체 7-iodo-1H-indole의 제조* Preparation of intermediate 7-iodo-1H-indole
3-브로모-1H-인돌-7-아민(6.97 g ,20.0 mmol)은 90 mL의98 % 황산에 현탁시키고, 현탁액을 0 ℃로 냉각시켰다. 얼음처럼 차가운 NaNO2(2.5M 20mL) 용액을 적가하여 온도가 58 ℃이상으로 상승하지 않도록 하였다. 노란 현탁액은 KI (30 mL, 40.0 mmol) 용액을 첨가 및 30분 동안 교반 한 후, 혼합물이 형성될 때까지 50 ℃로 가열되었다. 냉각 후, 혼합물을 추출 클로로포름으로 4회 (각각 50 mL). 형성된 유기상을 염수로 세척하고, 무수 황산마그네슘으로 건조시켰다. 회전 증발에 의해 용매를 제거하였다. 잔류물의 용리제로 시클로헥산을 사용하여 실리카겔 컬럼 크로마토그래피로 정제하였다. 헥산으로부터 재결정화한 후, a-1 (4.4g, 68 %)얻었다.3-Bromo-1H-indol-7-amine (6.97 g, 20.0 mmol) was suspended in 90 mL of 98% sulfuric acid and the suspension was cooled to 0 °C. An ice-cold solution of NaNO 2 (2.5M 20mL) was added dropwise so that the temperature did not rise above 58 °C. The yellow suspension was heated to 50° C. after addition of a solution of KI (30 mL, 40.0 mmol) and stirring for 30 min until a mixture formed. After cooling, the mixture was extracted 4 times with chloroform (50 mL each). The organic phase formed was washed with brine and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation. The residue was purified by silica gel column chromatography using cyclohexane as an eluent. After recrystallization from hexane, a-1 (4.4 g, 68%) was obtained.
질량 스펙트럼 m/z: 320.87 (계산치 321.94)Mass spectrum m/z: 320.87 (calculated 321.94)
* 중간체 a-2 내지 a-7의 제조* Preparation of intermediates a-2 to a-7
상기 중간체 a-1의 제조 방법으로 하기 [표 1]의 화합물을 얻었다:The compound of [Table 1] was obtained by the preparation method of the intermediate a-1:
* 중간체 (1H-indol-7-yl)boronic acid의 제조* Preparation of intermediate (1H-indol-7-yl)boronic acid
반응기에 7-요도-1H-인돌(10.35g,42.6mmol)과 테트라하이드로푸란 200mL를 넣어 녹이고 -76℃로 냉각한 후 2.5M n-부틸리튬 21mL를 천천히 적가하고 30분 동안 교반하였다. 트리이소프로필보레이트 14g을 적가하고 실온에서 18시간 교반한 후, 1N 염산 수용액 300mL을 첨가하고 1시간 교반한 다음 반응을 종료하였다. 에틸아세테이트 500mL와 소금물 500mL로 추출 후 유기층은 무수 황산마그네슘 20g으로 탈수하고 감압 농축하였다. 고체는 여과하고 톨루엔과 헥산 혼합용매로 씻어주어 b-1 (5.49g, 수율 80%)을 얻었다. After dissolving 7-iodo-1H-indole (10.35g, 42.6mmol) and 200mL of tetrahydrofuran in a reactor, cooling to -76°C, 21mL of 2.5M n-butyllithium was slowly added dropwise and stirred for 30 minutes. After adding 14 g of triisopropyl borate dropwise and stirring at room temperature for 18 hours, 300 mL of 1N hydrochloric acid aqueous solution was added, followed by stirring for 1 hour, and the reaction was terminated. After extraction with 500 mL of ethyl acetate and 500 mL of brine, the organic layer was dehydrated with 20 g of anhydrous magnesium sulfate and concentrated under reduced pressure. The solid was filtered and washed with a mixed solvent of toluene and hexane to obtain b-1 (5.49 g, yield 80%).
질량 스펙트럼 m/z: 161.06 (계산치 160.97)Mass spectrum m/z: 161.06 (calculated 160.97)
* 중간체 b-2 내지 b-10의 제조* Preparation of intermediates b-2 to b-10
상기 중간체 b-1의 제조 방법으로 하기 [표 2]의 화합물을 얻었다:The compound of [Table 2] was obtained by the method for preparing the intermediate b-1:
* 중간체 7-bromo-1'H-1,7'-biindole의 제조* Preparation of intermediate 7-bromo-1'H-1,7'-biindole
7-브로모-1H-인돌(36.66g, 187 mmol), 7-요오도-1H-인돌/7-iodo-1H-indole (44.48g,183 mmol), Pd(C2H3O2)2(0.4g,1.83 mmol), Pt-Bu3 (0.37g,1.83 mmol) 그리고 NaOt-Bu (22.8g ,238 mmol) 톨루엔 1000 mL에 녹인 후 80 ℃에서 4 시간 동안 교반하였다. 반응액을 상온으로 식힌 후, 물 300 mL 와 디에틸에테르 300 mL로 3번 추출하였다. 모아진 유기층을 무수 황산마그네슘으로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 중간체 1-1(48.97g, 수율 86%)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다. 7-Bromo-1H-indole (36.66g, 187 mmol), 7-iodo-1H-indole/7-iodo-1H-indole (44.48g, 183 mmol), Pd(C 2 H3O 2 ) 2 (0.4 g, 1.83 mmol), Pt-Bu 3 (0.37g, 1.83 mmol) and NaOt-Bu (22.8g, 238 mmol) were dissolved in 1000 mL of toluene and stirred at 80 °C for 4 hours. After cooling the reaction solution to room temperature, it was extracted three times with 300 mL of water and 300 mL of diethyl ether. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue obtained was separated and purified by silica gel and chromatography to obtain intermediate 1-1 (48.97 g, yield 86%). The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 310.01(계산치 311.18)Mass spectrum m/z: 310.01 (calculated 311.18)
* 중간체 1-2 내지 1-15의 제조* Preparation of intermediates 1-2 to 1-15
상기 중간체 1-1의 제조 방법으로 하기 [표 3]의 화합물을 얻었다:By the method for preparing Intermediate 1-1, the following [Table 3] compounds were obtained:
* 중간체 3-bromo-1H,1'H-4,7'-biindole의 제조* Preparation of intermediate 3-bromo-1H,1'H-4,7'-biindole
(3-브로모-1H-인돌-4-닐)브로모에시드(43.89g,183mmol), 7-요오도-1H-인돌 (44.48g ,183mmol), Pd(PPh3)4 (2.1 g ,1.83 mmol) 그리고 K2CO3 75.7 g (549 mmol) 을 THF/H2O (2/1) 혼합용액 60mL 에 녹인 후, 70 ℃에서 5시간 동안 교반하였다. 반응액을 실온으로 식힌 후 물 40 mL를 가하고 에틸에테르 50 mL로 3번 추출하였다. 모아진 유기층을 마그네슘설페이트로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 1-16(39.86g ,수율 70 %)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다.(3-Bromo-1H-indol-4-yl)bromo acid (43.89 g, 183 mmol), 7-iodo-1H-indole (44.48 g, 183 mmol), Pd (PPh 3 ) 4 (2.1 g, 1.83 mmol) and 75.7 g (549 mmol) of K2CO3 were dissolved in 60mL of a mixed solution of THF/H2O (2/1), followed by stirring at 70 °C for 5 hours. After cooling the reaction solution to room temperature, 40 mL of water was added thereto, followed by extraction with 50 mL of ethyl ether three times. The collected organic layer was dried over magnesium sulfate, and the solvent was evaporated. The residue was separated and purified by silica gel and chromatography to obtain 1-16 (39.86 g, yield 70%). The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 310.01 (계산치 311.18) Mass spectrum m/z: 310.01 (calculated 311.18)
* 중간체 1-17 내지 1-27의 제조* Preparation of intermediates 1-17 to 1-27
상기 중간체 1-16의 제조 방법으로 하기 [표 4]의 화합물을 얻었다:By the method for preparing Intermediate 1-16, the following [Table 4] compounds were obtained:
* 중간체 3-bromo-1'H-[1,7'-biindol]-7-amine의 제조* Preparation of intermediate 3-bromo-1'H-[1,7'-biindol]-7-amine
300mL 고압 반응기에 1-1 (30.68 g)을 첨가하고, 에탄올 200mL을 첨가한 후, 5% 팔라듐-탄소 촉매 1g을 첨가하고, 고압 수소를 5MPa로 채우고, 오일 욕에서 4 시간 동안 50℃에서 반응시킨다. 반응액을 냉각, 흡인 여과, 촉매 제거 후, 여과액을 진공 건조하여 고체 2-1 (24.19g, 수율 86%) 얻었다. 1-1 (30.68 g) was added to a 300 mL high-pressure reactor, 200 mL of ethanol was added, 1 g of 5% palladium-carbon catalyst was added, high-pressure hydrogen was charged to 5 MPa, and reaction was performed at 50 ° C. for 4 hours in an oil bath. let it After the reaction liquid was cooled, suction filtered, and the catalyst removed, the filtrate was vacuum-dried to obtain solid 2-1 (24.19 g, yield 86%).
질량 스펙트럼 m/z: 325.02 (계산치 326.19)Mass spectrum m/z: 325.02 (calculated 326.19)
* 중간체 2-2 내지 2-17의 제조* Preparation of intermediates 2-2 to 2-17
상기 중간체 2-1의 제조 방법으로 하기 [표 5]의 화합물을 얻었다:By the method for preparing Intermediate 2-1, the following compounds of [Table 5] were obtained:
* 중간체 3-bromo-7-iodo-1'H-1,7'-biindole의 제조* Preparation of intermediate 3-bromo-7-iodo-1'H-1,7'-biindole
2-1(6.5 g ,20.0 mmol)은 90 mL의98% 황산에 현탁시키고, 현탁액을 0 ℃로 냉각시켰다. 얼음처럼 차가운 NaNO2(2.5M 20mL) 용액을 적가하여 온도가 58 ℃이상으로 상승하지 않도록 하였다. 노란 현탁액은 KI (30mL, 40.0 mmol)의 용액에 첨가하며, 30분 동안 교반 한 후, 혼합물이 형성될 때까지 50 ℃로 가열하였다. 냉각 후, 혼합물을 추출 클로로포름으로 4 회 (각각 50 mL). 형성된 결합 유기상을 염수로 세척하고 무수 황산마그네슘으로 건조시켰다. 회전 증발에 의해 용매를 제거하였다. 잔류물의 용리제로 시클로 헥산을 사용하여 실리카겔 컬럼 크로마토그래피로 정제 하였다. 헥산으로부터 재결정화한 후, 3-1 (5.2g, 60%)얻었다. 2-1 (6.5 g, 20.0 mmol) was suspended in 90 mL of 98% sulfuric acid, and the suspension was cooled to 0 °C. An ice-cold solution of NaNO 2 (2.5M 20mL) was added dropwise so that the temperature did not rise above 58 °C. The yellow suspension was added to a solution of KI (30 mL, 40.0 mmol), stirred for 30 min and then heated to 50 °C until a mixture formed. After cooling, the mixture was extracted with chloroform 4 times (50 mL each). The combined organic phase formed was washed with brine and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation. The residue was purified by silica gel column chromatography using cyclohexane as an eluent. After recrystallization from hexane, 3-1 (5.2 g, 60%) was obtained.
질량 스펙트럼 m/z: 435.91 (계산치 437.07)Mass spectrum m/z: 435.91 (calculated 437.07)
* 중간체 3-2 내지 3-16의 제조* Preparation of intermediates 3-2 to 3-16
상기 중간체 3-1의 제조 방법으로 하기 [표 6]의 화합물을 얻었다:By the method for preparing Intermediate 3-1, the following compounds of [Table 6] were obtained:
* 중간체 퓨즈드 화합물을 이용한의 제조* Preparation of Intermediate Fused Compounds
1-1 (58.19g,187 mmol), Pd(C2H3O2)2(0.4g(1.83 mmol), Pt-Bu3 (0.37g,1.83 mmol) 그리고 NaOt-Bu (22.8 g ,238 mmol) 톨루엔 1000 mL에 녹인 후 80℃에서 4 시간 동안 교반하였다. 반응액을 상온으로 식힌 후, 물 300 mL 와 디에틸에테르 300mL로 3번 추출하였다. 모아진 유기층을 무수 황산마그네슘으로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 중간체 4-1 (34.45g, 수율 80%)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다. 1-1 (58.19g, 187 mmol), Pd (C 2 H 3 O 2 ) 2 (0.4g (1.83 mmol), Pt-Bu 3 (0.37g, 1.83 mmol) and NaOt-Bu (22.8 g, 238 mmol) ) After dissolving in 1000 mL of toluene, the mixture was stirred for 4 hours at 80 ° C. After cooling the reaction solution to room temperature, it was extracted three times with 300 mL of water and 300 mL of diethyl ether. The collected organic layers were dried over anhydrous magnesium sulfate, and the solvent was evaporated. The resulting residue was separated and purified by silica gel and chromatography to obtain intermediate 4-1 (34.45 g, yield 80%), which was confirmed by LC-MS.
질량 스펙트럼 m/z: 230.08(계산치 230.26)Mass spectrum m/z: 230.08 (calculated 230.26)
* 중간체 4-2 내지 4-25의 제조* Preparation of intermediates 4-2 to 4-25
상기 중간체 4-1의 제조 방법으로 하기 [표 7]의 화합물을 얻었다:By the method for preparing Intermediate 4-1, the following compounds of [Table 7] were obtained:
* 중간체 b-11 내지 b-26의 제조* Preparation of intermediates b-11 to b-26
상기 중간체 b-1의 제조 방법으로 하기 [표 8]의 화합물을 얻었다:The compound of [Table 8] was obtained by the preparation method of the intermediate b-1:
* 중간체 3-17 내지 3-18의 제조* Preparation of intermediates 3-17 to 3-18
상기 중간체 1-16의 제조 방법으로 하기 [표 9]의 화합물을 얻었다:By the method for preparing Intermediate 1-16, the following compounds of [Table 9] were obtained:
* 중간체 11-chloro-2-(4,6-diphenyl-1,3,5-triazin-2-yl)퓨즈드 화합물을 이용한의 제조* Preparation of Intermediate 11-chloro-2-(4,6-diphenyl-1,3,5-triazin-2-yl)using a fused compound
(4,6-디페닐-1,3,5-트리벤진-2-닐)브로모에씨드 (50.71g,183mmol), 4-5 (62.88g, 183mmol), Pd(PPh3)4 (2.1g, 1.83 mmol) 그리고 K2CO3 75.7 g (549 mmol)을 THF/H2O (2/1) 혼합용액 60mL에 녹인 후, 70 ℃에서 5시간 동안 교반하였다. 반응액을 실온으로 식힌 후 물 40 mL를 가하고 에틸에테르 50 mL로 3번 추출하였다. 모아진 유기층을 무수 황산마그네슘으로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 C-1 (63.53g, 수율 70 %)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다.(4,6-diphenyl-1,3,5-tribenzin-2-yl) bromo acid (50.71 g, 183 mmol), 4-5 (62.88 g, 183 mmol), Pd (PPh 3 ) 4 (2.1 g , 1.83 mmol) and 75.7 g (549 mmol) of K 2 CO 3 were dissolved in 60 mL of a mixed solution of THF/H 2 O (2/1), followed by stirring at 70 °C for 5 hours. After cooling the reaction solution to room temperature, 40 mL of water was added thereto, followed by extraction with 50 mL of ethyl ether three times. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was separated and purified by silica gel and chromatography to obtain C-1 (63.53g, yield 70%). The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 495.13 (계산치 495.96)Mass spectrum m/z: 495.13 (calculated 495.96)
* 중간체 c-2 내지 c-57의 제조* Preparation of intermediates c-2 to c-57
상기 중간체 c-1의 제조 방법으로 하기 [표 10]의 화합물을 얻었다:The compound of [Table 10] was obtained by the preparation method of the intermediate c-1:
* 중간체 11-chloro-N,N-bis(4-isopropylphenyl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazin-2-amine의 제조* Preparation of intermediate 11-chloro-N,N-bis(4-isopropylphenyl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazin-2-amine
디(4-이소프로필페닐)아민 (bis(4-isopropylphenyl)amine)(47.38g,187 mmol),2-브로모-11-클로로디피롤로[3,2,1-de:3',2',1'-킬]페나진 (62.88g ,183 mmol), Pd(C2H3O2)2( 0.4g,1.83 mmol), Pt-Bu3 (0.37g,1.83 mmol) 그리고 NaOt-Bu (22.8 g,238 mmol) 톨루엔 1000 mL 에 녹인 후 80 ℃ 에서 4 시간 동안 교반하였다. 반응액을 상온으로 식힌 후, 물 300 mL 와 디에틸에테르 300 mL로 3번 추출하였다. 모아진 유기층을 마그네슘설페이트로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 중간체 d-1 (75.55g,수율 80%)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다. Di(4-isopropylphenyl)amine (bis(4-isopropylphenyl)amine) (47.38g, 187 mmol), 2-bromo-11-chlorodipyrrolo[3,2,1-de:3',2' ,1′-kyl]phenazine (62.88g,183 mmol), Pd(C 2 H 3 O 2 ) 2 (0.4g, 1.83 mmol), Pt-Bu 3 (0.37g, 1.83 mmol) and NaOt-Bu ( 22.8 g, 238 mmol) was dissolved in 1000 mL of toluene and stirred at 80 °C for 4 hours. After cooling the reaction solution to room temperature, it was extracted three times with 300 mL of water and 300 mL of diethyl ether. The collected organic layer was dried over magnesium sulfate, and the solvent was evaporated. The residue was separated and purified by silica gel and chromatography to obtain intermediate d-1 (75.55 g, yield 80%). The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 516.21(계산치 516.08)Mass spectrum m/z: 516.21 (calculated 516.08)
* 중간체 d-2 내지 d-37의 제조* Preparation of intermediates d-2 to d-37
상기 중간체 d-1의 제조 방법으로 하기 [표 11]의 화합물을 얻었다:The compound of [Table 11] was obtained by the preparation method of the intermediate d-1:
<실시예의 제조><Preparation of Examples>
* 실시예 2-(10-phenylanthracen-9-yl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazine 제조 (A-1)* Preparation of Example 2-(10-phenylanthracen-9-yl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazine (A-1)
(10-페닐안트라센-9-닐)브로므에시드(((10-phenylanthracen-9-yl)boronic acid) (54.56g, 183mmol), 4-1 (56.58g, 183mmol), Pd(PPh3)4 (2.1g, 1.83 mmol) 그리고 K2CO3 (75.7g ,549 mmol)을 THF/H2O (2/1) 혼합용액 60mL에 녹인 후, 70℃에서 5시간 동안 교반하였다. 반응액을 실온으로 식힌 후 물 40 mL를 가하고 에틸에테르 50 mL로 3번 추출하였다. 모아진 유기층을 무수 황산마그네슘으로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리정제하여 A-1 (61.82g, 수율 70 %)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다.(10-phenylanthracen-9-yl) brome acid (((10-phenylanthracen-9-yl) boronic acid) (54.56 g, 183 mmol), 4-1 (56.58 g, 183 mmol), Pd (PPh 3 ) 4 (2.1g, 1.83 mmol) and K 2 CO 3 (75.7g, 549 mmol) were dissolved in 60mL of a mixed solution of THF/H 2 O (2/1), followed by stirring at 70° C. for 5 hours. After cooling, 40 mL of water was added, and extraction was performed with 50 mL of ethyl ether three times.The collected organic layers were dried over anhydrous magnesium sulfate, and the solvent was evaporated. , Yield 70%) The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 482.18(계산치 482.57)Mass spectrum m/z: 482.18 (calculated 482.57)
* 실시예 A-2 내지 A-79의 제조* Preparation of Examples A-2 to A-79
*상기 실시예 A-1의 제조 방법으로 하기 [표 12]의 화합물을 얻었다:* The following [Table 12] compounds were obtained by the preparation method of Example A-1:
* 실시예 2-(dimesitylboryl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazine의 제조 (A-80)* Example 2 - Preparation of (dimesitylboryl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazine (A-80)
2- 브로모디피롤로[3,2,1-de : 3 ', 2', 1'-kl]페나진 (0.70g, 2.77mmol)을 에테르 (5mL)에 용해한 다음, 0 ℃에서 n-BuLi(1.6M, 1.86mL, 2.97mmol)를 적가하였다. 혼합물을 0 ℃에서 1 시간 동안 교반하였다. 이 혼합물에 에테르중디메틸화 붕소플루오라이드 (891 mg, 3.32 mmol)를 0 ℃에서 첨가하였다. 16 시간 동안 교반한 후, 생성된 침전물을 여과하고, CH2Cl2/헥산으로부터 재결정화하여 황색 고체 A-80(1.17 g ,2.44 mmol,88 %)얻었다.2-Bromodipyrrolo[3,2,1-de: 3', 2', 1'-kl]phenazine (0.70g, 2.77mmol) was dissolved in ether (5mL) and then n-BuLi at 0 °C. (1.6M, 1.86mL, 2.97mmol) was added dropwise. The mixture was stirred at 0 °C for 1 hour. To this mixture was added dimethylated boronfluoride in ether (891 mg, 3.32 mmol) at 0 °C. After stirring for 16 hours, the resulting precipitate was filtered and recrystallized from CH 2 Cl 2 /hexane to give A-80 as a yellow solid (1.17 g, 2.44 mmol, 88 %).
질량 스펙트럼 m/z: 478.26(계산치 478.43)Mass spectrum m/z: 478.26 (calculated 478.43)
* 실시예 A-81와 A-82의 제조* Preparation of Examples A-81 and A-82
상기 실시예 A-80의 제조 방법으로 하기 [표 13]의 화합물을 얻었다:The following [Table 13] compounds were obtained by the preparation method of Example A-80:
* 실시예 N,N-bis(4-isopropylphenyl)dipyrrolo[3,2,1-de:3',2',1'-kl]phenazin-2-amine의 제조* Example Preparation of N, N-bis (4-isopropylphenyl) dipyrrolo [3,2,1-de: 3 ', 2', 1'-kl] phenazin-2-amine
디(4-이소프로필페닐)아민 (bis(4-isopropylphenyl)amine) (47.38g, 187 mmol), 4-브로모-2-클로로-1-나이트로벤젠(4-bromo-2-chloro-1-nitrobenzene) (56.58g, 183 mmol), Pd(C2H3O2)2 (0.4g, 1.83 mmol), Pt-Bu3 (0.37g, 1.83 mmol) 그리고 NaOt-Bu (22.8g, 238 mmol) 톨루엔 1000 mL에 녹인 후 80℃ 에서 4 시간 동안 교반하였다. 반응액을 상온으로 식힌 후, 물 300 mL 와 디에틸에테르 300 mL로 3번 추출하였다. 모아진 유기층을 무수 황산마그네슘으로 건조하고 용매를 증발하여 얻어진 잔류물을 실리카젤과 크로마토그래피로 분리 정제하여 중간체 A-1 (70.51g, 수율 80%)을 얻었다. 생성된 화합물은 LC-MS를 통해 확인하였다. Di(4-isopropylphenyl)amine (bis(4-isopropylphenyl)amine) (47.38g, 187 mmol), 4-bromo-2-chloro-1-nitrobenzene -nitrobenzene) (56.58g, 183 mmol), Pd(C 2 H 3 O 2 ) 2 (0.4g, 1.83 mmol), Pt-Bu 3 (0.37g, 1.83 mmol) and NaOt-Bu (22.8g, 238 mmol) ) After dissolving in 1000 mL of toluene, the mixture was stirred at 80° C. for 4 hours. After cooling the reaction solution to room temperature, it was extracted three times with 300 mL of water and 300 mL of diethyl ether. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was separated and purified by silica gel and chromatography to obtain Intermediate A-1 (70.51 g, yield 80%). The resulting compound was confirmed through LC-MS.
질량 스펙트럼 m/z: 492.26(계산치 492.44)Mass spectrum m/z: 492.26 (calculated 492.44)
* 실시예 B-2 내지 B-54의 제조* Preparation of Examples B-2 to B-54
상기 실시예 B-1의 제조 방법으로 하기 [표 14]의 화합물을 얻었다: The compounds of [Table 14] were obtained by the preparation method of Example B-1:
* 실시예 C-1 내지 C-13의 제조* Preparation of Examples C-1 to C-13
상기 실시예 A-80의 제조 방법으로 하기 [표 15]의 화합물을 얻었다:The following compounds of [Table 15] were obtained by the preparation method of Example A-80:
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 to a thickness of 1500 Å was placed in double distilled water in which Fisher's detergent was dissolved and washed with ultrasonic waves for 30 minutes. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, and drying, the substrate was transferred to a plasma cleaner, and the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was 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 vacuum deposition of 500Å 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, After vacuum depositing N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) 300Å, AND (9, 10-Di(2-naphthyl)anthracene) was doped with 5% of the dopant DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine), and in the case of red, RH-01 (9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-bicarbazole) is doped with 5% of RD-01 (5,6,11,12-tetraphenyltetracene) TPBi (1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene) material was vacuum-deposited to a thickness of 400 Å as a hole blocking layer and a hole transport layer. A cathode was formed by depositing 5 Å of LiF and 2000 Å of Al (aluminum).
상기에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 하기 표 16 내지 표18에 나타내었다.Electrical emission characteristics of the organic light emitting devices prepared above are shown in Tables 16 to 18 below.
아래 표 16은, 청색 발광에서 AND 호스트 상태에서 DPAP-DPPA와 실시예의 성능 비교한 표이다.Table 16 below is a table comparing performance of DPAP-DPPA and Examples in the AND host state in blue light emission.
아래 표 17은, 청색 발광의 AND/DPAP-DPPA 상태에서 ETL의 TPBi와 실시예의 성능 비교한 표이다.Table 17 below is a table comparing performance of TPBi of ETL and Example in AND/DPAP-DPPA state of blue light emission.
아래 표 18은, 적색 발광에서 RH-01 호스트 상태에서 RD-01과 실시예의 성능 비교한 표이다.Table 18 below is a table comparing the performance of RD-01 and Example in the RH-01 host state in red light emission.
상기 표 16 내지 표 18의 결과로부터, 본 발명에 따른 퓨즈드 화합물은 적색 발광에서 성능 향상 결과를 얻었으며, 청색 발광의 응용성이 가능하다는 것을 알 수 있다. 또한 전자수송층의 역할에서 발광 효율 및 수명 특성이 향상됨을 확인할 수 있었다.From the results of Tables 16 to 18, it can be seen that the fused compound according to the present invention has improved performance in red light emission and is applicable to blue light emission. In addition, it was confirmed that the luminous efficiency and lifetime characteristics were improved in the role of the electron transport layer.
본 발명의 퓨즈드 화합물을 이용한 유기발광소자는 발광 효율과 수명이 우수한 향상을 얻을 수 있었다. 이 때문에, 실용성이 높은 OLED로서 산업적으로 유용하다. An organic light emitting device using the fused compound of the present invention was able to obtain excellent improvement in light emitting efficiency and lifespan. For this reason, it is industrially useful as an OLED with high practicality.
본 발명의 유기발광소자는 평면 패널 디스플레이, 평면 발광체, 조명용 면발광 OLED의 발광체, flexible 발광체, 복사기, 프린터, LCD 백라이트 또는 계량기류 등의 광원, 디스플레이판, 표식등 등에 적합하게 이용할 수 있다.The organic light emitting device of the present invention can be suitably used for light sources such as flat panel displays, flat light emitting bodies, surface light emitting OLED light emitting bodies for lighting, flexible light emitting bodies, copiers, printers, LCD backlights or meters, display boards, signs, etc.
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| KR20140079594A (en) * | 2012-12-17 | 2014-06-27 | 주식회사 두산 | Novel organic compounds and organic electro luminescence device comprising the same |
| KR20140083898A (en) * | 2012-12-26 | 2014-07-04 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
| US20150295186A1 (en) * | 2012-07-10 | 2015-10-15 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20190012127A (en) * | 2017-07-26 | 2019-02-08 | 유니버셜 디스플레이 코포레이션 | Organic electroluminescent materials and devices |
| WO2019081416A1 (en) * | 2017-10-23 | 2019-05-02 | Sony Corporation | P active materials for organic photoelectric conversion layers in organic photodiodes |
| KR102175379B1 (en) * | 2020-08-26 | 2020-11-09 | 최돈수 | Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150295186A1 (en) * | 2012-07-10 | 2015-10-15 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20140079594A (en) * | 2012-12-17 | 2014-06-27 | 주식회사 두산 | Novel organic compounds and organic electro luminescence device comprising the same |
| KR20140083898A (en) * | 2012-12-26 | 2014-07-04 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
| KR20190012127A (en) * | 2017-07-26 | 2019-02-08 | 유니버셜 디스플레이 코포레이션 | Organic electroluminescent materials and devices |
| WO2019081416A1 (en) * | 2017-10-23 | 2019-05-02 | Sony Corporation | P active materials for organic photoelectric conversion layers in organic photodiodes |
| KR102175379B1 (en) * | 2020-08-26 | 2020-11-09 | 최돈수 | Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device |
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