KR20220078915A - Hole transporting material and Organic electroluminescent display device using the same - Google Patents
Hole transporting material and Organic electroluminescent display device using the same Download PDFInfo
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- KR20220078915A KR20220078915A KR1020200168195A KR20200168195A KR20220078915A KR 20220078915 A KR20220078915 A KR 20220078915A KR 1020200168195 A KR1020200168195 A KR 1020200168195A KR 20200168195 A KR20200168195 A KR 20200168195A KR 20220078915 A KR20220078915 A KR 20220078915A
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- South Korea
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- organic
- hole transport
- organic electroluminescent
- electrode
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 230000005525 hole transport Effects 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
본 발명은 플루오렌 코어 및 트리페닐아민 또는 카바졸 모이어티를 가지는 신규한 구조의 화합물, 정공 수송 물질로서의 이의 용도, 이를 포함하는 유기전기발광소자 및 전자 기기를 제공한다. The present invention provides a compound having a novel structure having a fluorene core and a triphenylamine or carbazole moiety, its use as a hole transport material, and an organic electroluminescent device and an electronic device comprising the same.
Description
본 발명은 정공 수송 물질 및 이를 사용하는 유기전기발광소자에 관한 것이다. The present invention relates to a hole transport material and an organic electroluminescent device using the same.
유기발광다이오드(OLED)는 연구와 상업 시장에서 흥미로운 요소가 되었다. OLED는 높은 콘트라스트, 높은 밝기, 넓은 시야각, 백라이트 요구 사항이 없다는 점, 가벼운 무게, 얇은 필름 등 기존 디스플레이에 비해 두드러진 장점을 보여준다. 유기발광다이오드(OLED)는 휴대전화, TV, 기타 조명자원에 차세대 디스플레이로 에너지 소비량 감소에 도움이 된다.Organic light emitting diodes (OLEDs) have become an interesting element in research and commercial markets. OLED shows significant advantages over conventional displays such as high contrast, high brightness, wide viewing angle, no backlight requirements, light weight, and thin film. Organic light emitting diodes (OLEDs) are next-generation displays for mobile phones, TVs, and other lighting sources, helping to reduce energy consumption.
1세대 유기발광다이오드는 내부 양자 효율의 25%에 그쳤으며 75%는 비방사성(non-radiative) 방식으로 손실됐다. 이후 금속과 리간드 콤플렉스를 가진 형광 OLED는 OLED에서 2세대 발광체로 확인됐다. 이 때 이리듐과 백금 기반의 중금속 단지를 이용하여 삼중항과 단일항 에너지를 얻었고, 100%의 달성 가능한 내부 양자 효율을 보였다. 그러한 최대 내부 양자 효율은 시스템 간 교차 메커니즘(Intersystem crossing mechanism, ISC)을 통해 도달할 수 있었다. 이 과정은 적절한 도핑 농도의 적합한 호스트 물질로 중금속 기반의 형광 방출기를 도핑해야 한다. 이는 집적으로 인해 발생한 ?칭(Aggregation caused quenching, ACQ) 및 삼중항-삼중항 전멸(triplet-triplet annihilation, TTA)과 같은 ?칭 프로세스를 줄이는 데 도움이 된다. First-generation organic light-emitting diodes only accounted for 25% of their internal quantum efficiency, and 75% was lost non-radiatively. Since then, fluorescent OLEDs with metal and ligand complexes have been identified as second-generation light emitters in OLEDs. In this case, triplet and singlet energies were obtained using an iridium- and platinum-based heavy metal complex, and an achievable internal quantum efficiency of 100% was obtained. Such maximum internal quantum efficiency could be reached through an intersystem crossing mechanism (ISC). This process requires doping the heavy metal-based fluorescence emitter with a suitable host material at an appropriate doping concentration. This helps to reduce quenching processes such as aggregation caused quenching (ACQ) and triplet-triplet annihilation (TTA).
3세대 유기발광다이오드(OLED)는 적절한 도너와 수용체 분자를 빌딩 블록으로 사용하는 금속 없는 형광 방출기다. 이러한 유형의 방출기는 열로 작동되는 지연 형광체(Thermally activated delayed fluorescence, TADF) 방출기로 알려져 있으며 역방향 시스템 교차 (Reverse intersystem crossing, RISC) 메커니즘에 기초하여 작동하는 것으로 알려져 있다. 형광 및 TADF OLED는 모두 소자 효율을 높이기 위해 효율적인 호스트 물질이 필요하다.Third-generation organic light-emitting diodes (OLEDs) are metal-free fluorescence emitters that use appropriate donor and acceptor molecules as building blocks. This type of emitter is known as thermally activated delayed fluorescence (TADF) emitter and is known to operate based on a reverse intersystem crossing (RISC) mechanism. Both fluorescent and TADF OLEDs require efficient host materials to increase device efficiency.
보고된 호스트 물질은 정공 수송 타입(Hole transport type, HT), 전자 수송 타입(Electron transport type, ET) 및 양극성 호스트 물질 등 3종류가 있다. There are three types of reported host materials: a hole transport type (HT), an electron transport type (ET), and a bipolar host material.
정공 수송 물질은 정공 주입에서 중요한 역할을 한다. 적절한 전하 균형을 유지하기 위해 양극에서 방출층으로 더 나은 정공수송을 촉진한다 정공 수송 재료는 높은 정공 이동성, 적절한 HOMO 레벨, 열안정성 및 높은 이온화 잠재력을 가져야 한다. 정공 수송 호스트 물질은 전자를 공여하는 디페닐아민, 트리페닐아민, 카바졸 및 아크리딘 유도체로 만들어진다. 4,4`-(N-카바졸릴)-1,1`-바이페닐, 1,3-비스(N-카바졸릴)-벤젠 및 4,4`-시클로헥실리덴비스[N,N-비스(4-메틸페닐)벤젠아민]은 잘 알려진 정공 물질이나, 이들은 열적 안정성이 불안정하다. 트리스(8-히드록시퀴놀린)알루미늄과 비스[2-(디페닐포스피노)페닐]에테르옥사이드는 형광 및 TADF OLED에 사용되는 전자 수송형 호스트 물질이다. 상기 호스트 물질은 에너지 흐름을 도판트로부터 되돌리는 것을 방지하는 동시에 도판트 물질에 필수적인 에너지 공급원이다. 호스트 물질은 도판트 물질보다 삼중항 에너지를 더 많이 가져야 한다. 동시에, 호스트 물질은 인접 층으로부터의 효율적인 캐리어 수송을 보장하기 위해 적절한 프론티어 분자 궤도 에너지(Frontier molecular orbital energies, FMO)를 가져야 한다. 양극성 물질은 양극성 때문에 연구 공동체로부터 많은 관심을 받아왔다. 양극성 호스트 물질은 단일 분자에 전자 공여 및 전자 수여 단위를 포함한다. 또한 양극성 호스트 물질은 방출 층에서 효과적인 캐리어 재조합을 지원하면서 적절한 캐리어 균형을 제공할 수 있다. 대부분 형광 방출기는 물론 호스트 물질에도 양극성 물질을 활용할 수 있다. Hole transport materials play an important role in hole injection. It promotes better hole transport from the anode to the emissive layer to maintain proper charge balance. The hole transport material should have high hole mobility, adequate HOMO level, thermal stability and high ionization potential. The hole transport host material is made of electron donating diphenylamine, triphenylamine, carbazole and acridine derivatives. 4,4′-(N-carbazolyl)-1,1′-biphenyl, 1,3-bis(N-carbazolyl)-benzene and 4,4′-cyclohexylidenebis[N,N-bis (4-methylphenyl)benzeneamine] is a well-known hole material, but they have unstable thermal stability. Tris(8-hydroxyquinoline)aluminum and bis[2-(diphenylphosphino)phenyl]etheroxide are electron-transporting host materials used in fluorescent and TADF OLEDs. The host material is an essential energy source for the dopant material while preventing the return of energy flow from the dopant. The host material should have more triplet energy than the dopant material. At the same time, the host material must have adequate frontier molecular orbital energies (FMO) to ensure efficient carrier transport from adjacent layers. Bipolar materials have received a lot of attention from the research community because of their polarity. A bipolar host material contains electron donating and electron donating units in a single molecule. The bipolar host material can also provide proper carrier balance while supporting effective carrier recombination in the emissive layer. In most cases, a bipolar material can be used for both the fluorescent emitter and the host material.
본 연구에서는 두 가지 유형의 양극성 물질, 즉 N1-(9,9-디페닐-9H-플루오렌-2-일)-N1-(4,6-디페닐피리미딘-2-일)-N4,N4-디페닐벤젠-1,4-디아민(FLU-TPA/PYR) 및 N1-(4-(4,6-디페닐-1,3,5-트리아진-2-일)페닐)-N1-(9,9-디페닐-9H-플루오렌-2-일)-N4,N4-디페닐벤젠-1,4-디아민 (FLU-TPA/TRZ)을 설계하고 합성하였으며, 이들에는 N1-(9,9-디페닐-9H-플루오렌-2-일)-N4,N4-디페닐벤젠-1,4-디아민 공여자 및 트리아진 또는 피리미딘 수여자가 혼입되었다. 이 두 개의 양극성 물질은 황색 물질과 도핑되지 않은 형광체 방출기로 처리되었다. 이리듐(III) 비스(4-(4-터트-부틸페닐)티에노[3,2-c]피리디나토-N,C2`)아세틸아세토네이트는 황색 인광 도판트로 채용하였다.In this study, there are two types of bipolar materials, N 1 -(9,9-diphenyl-9H-fluoren-2-yl)-N 1 -(4,6-diphenylpyrimidin-2-yl)- N 4 ,N 4 -diphenylbenzene-1,4-diamine (FLU-TPA/PYR) and N 1 -(4-(4,6-diphenyl-1,3,5-triazin-2-yl) Design and synthesis of phenyl)-N 1 -(9,9-diphenyl-9H-fluoren-2-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine (FLU-TPA/TRZ) These include N 1 -(9,9-diphenyl-9H-fluoren-2-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine donor and triazine or pyrimidine acceptor got mixed up These two bipolar materials were treated with a yellow material and an undoped phosphor emitter. Iridium(III)bis(4-(4-tert-butylphenyl)thieno[3,2-c]pyridinato-N,C2`)acetylacetonate was employed as a yellow phosphorescent dopant.
본 발명의 목적은 양자 효율이 뛰어난 신규한 정공 수송 물질을 제공하는 것이다.It is an object of the present invention to provide a novel hole transport material having excellent quantum efficiency.
또한 본 발명의 목적은 상기 정공 수송 물질을 포함하는 유기전기발광소자를 제공하는 것이다. Another object of the present invention is to provide an organic electroluminescent device including the hole transport material.
또한 본 발명의 목적은 상기 유기전기발광소자를 포함하는 전자기기를 제공하는 것이다.It is also an object of the present invention to provide an electronic device including the organic electroluminescent device.
본 발명의 하나의 구현예는 하기 화학식 1로 표시되는 화합물을 제공한다. One embodiment of the present invention provides a compound represented by the following formula (1).
[화학식 1][Formula 1]
식 중에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 
본 발명의 다른 구현예는 상기 화학식 1로 표시되는 정공 수송 물질을 제공한다. Another embodiment of the present invention provides a hole transport material represented by Formula 1 above.
본 발명의 또 다른 구현예는 Another embodiment of the present invention is
제1 전극과;a first electrode;
상기 제1 전극과 마주보는 제2 전극과;a second electrode facing the first electrode;
상기 제1 및 제2 전극 사이에 위치하는 발광물질층과;a light emitting material layer positioned between the first and second electrodes;
상기 제1 전극과 상기 발광물질층 사이에 위치하는 정공수송층을 포함하고, and a hole transport layer positioned between the first electrode and the light emitting material layer,
상기 정공수송층은 제2항에 따른 정공 수송 물질을 포함하여 이루어지는 것인 유기전기발광소자를 제공한다. The hole transport layer provides an organic electroluminescent device comprising the hole transport material according to
본 발명의 또 다른 구현예는 상기 유기전기발광소자를 포함하는 전자 기기를 제공한다.Another embodiment of the present invention provides an electronic device including the organic electroluminescent device.
상기 정공 수송 물질은 외부 양자 효율이 뛰어나면서도 롤오프가 낮아 장기적으로 안정한 유기전기발광소자를 생산하는데 용이하게 이용될 수 있다. 또한, 상기 정공 수송 물질을 사용하여 제조되는 유기전기발광소자는 발광효율이 뛰어나 산업상 유리하다. 새롭게 합성된 화합물은 특히, 황색 인광 OLED의 정공 수송물질로 적용되어 진한 청색 형광 도펀트로 유용하게 활용된다. The hole transport material has excellent external quantum efficiency and low roll-off, so that it can be easily used to produce an organic electroluminescent device that is stable in the long term. In addition, the organic electroluminescent device manufactured using the hole transport material has excellent luminous efficiency, which is advantageous in industry. The newly synthesized compound is particularly useful as a deep blue fluorescent dopant as it is applied as a hole transport material for a yellow phosphorescent OLED.
도 1은 본 발명에 따른 FLU-DTPA 및 FLU-DCAR의 시차 주사 열량 측정 및 열 중량 분석 결과를 나타낸 것이다.
도 2는 본 발명에 따른 FLU-DTPA 및 FLU-DCAR의 UV-Vis 흡수 스펙트럼 및 광발광 스펙트럼 결과를 나타낸 것이다.
도 3은 본 발명에 따른 FLU-DTPA 및 FLU-DCAR의 론티어 분자 궤도 분포를 나타낸 것이다.
도 4는 본 발명에 따라 제조된 황색 인광 유기발광 다이오드(OLED) 소자의 구조를 나타낸 것이다.
도 5는 본 발명에 따라 제조된 황색 인광 유기발광 다이오드(OLED) 소자의 전류 밀도-전압 및 발광 전압-전류 밀도 효율 결과이다.
도 6은 본 발명에 따라 제조된 황색 인광 유기발광 다이오드(OLED) 소자의 최대 외부 양자 효율 결과이다.
도 7은 본 발명에 따라 제조된 황색 인광 유기발광 다이오드(OLED) 소자의 전계발광(Electroluminescent, EL) 스펙트럼 결과이다.
도 8은 본 발명에 따라 제조된 비도핑 형광 소자의 전류 밀도-전압 및 발광 전압-전류 밀도 및 최대 외부 양자 효율 결과이다.
도 9는 본 발명에 따라 제조된 비도핑 형광 소자의 전계발광 스펙트럼 결과이다.1 shows the results of differential scanning calorimetry and thermogravimetric analysis of FLU-DTPA and FLU-DCAR according to the present invention.
Figure 2 shows the UV-Vis absorption spectrum and photoluminescence spectrum results of FLU-DTPA and FLU-DCAR according to the present invention.
3 shows the long-tier molecular orbital distributions of FLU-DTPA and FLU-DCAR according to the present invention.
4 shows the structure of a yellow phosphorescent organic light emitting diode (OLED) device manufactured according to the present invention.
5 is a current density-voltage and light-emitting voltage-current density efficiency results of a yellow phosphorescent organic light emitting diode (OLED) device manufactured according to the present invention.
6 is a result of maximum external quantum efficiency of a yellow phosphorescent organic light emitting diode (OLED) device manufactured according to the present invention.
7 is an electroluminescent (EL) spectrum result of a yellow phosphorescent organic light emitting diode (OLED) device manufactured according to the present invention.
8 is a graph showing current density-voltage and emission voltage-current density and maximum external quantum efficiency of an undoped fluorescent device manufactured according to the present invention.
9 is an electroluminescence spectrum result of an undoped fluorescent device manufactured according to the present invention.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다. The present invention provides a compound represented by the following formula (1).
[화학식 1][Formula 1]
식 중에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 정공 수송 물질로서 제공한다.In addition, the present invention provides a compound represented by Formula 1 as a hole transport material.
본 발명의 일 구현예에 의하면, 상기 화학식 1로 표시되는 정공 수송 물질은 R1이 
본 발명의 다른 일 구현예에 의하면, 상기 화학식 1로 표시되는 정공 수송 물질은 R1이 
본 발명의 바람직한 일 구현예에서, 상기 화학식 1로 표시되는 정공 수송물질은 하기 화학식 2 또는 화학식 3으로 표시되는 화합물일 수 있다. In a preferred embodiment of the present invention, the hole transport material represented by Formula 1 may be a compound represented by Formula 2 or Formula 3 below.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
또한, 본 발명은 Also, the present invention
제1 전극과;a first electrode;
상기 제1 전극과 마주보는 제2 전극과;a second electrode facing the first electrode;
상기 제1 및 제2 전극 사이에 위치하는 발광물질층과;a light emitting material layer positioned between the first and second electrodes;
상기 제1 전극과 상기 발광물질층 사이에 위치하는 정공수송층을 포함하고, and a hole transport layer positioned between the first electrode and the light emitting material layer,
상기 정공수송층은 제2항에 따른 정공 수송 물질을 포함하여 이루어지는 것인 유기전기발광소자를 제공한다.The hole transport layer provides an organic electroluminescent device comprising the hole transport material according to
본 발명의 일 구현예에서, 상기 정공수송층은 스핀코팅 공정, 노즐프린팅 공정, 잉크젯프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정 중 어느 하나에 의해 형성될 수 있으나, 반드시 이에 제한되는 것은 아니며 적절한 유기발광소자를 제조할 수 있는 임의의 공정이 사용될 수 있다.In one embodiment of the present invention, the hole transport layer may be formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, but is not necessarily limited thereto Any process capable of manufacturing an appropriate organic light emitting device may be used.
본 발명의 일 구현예에서, In one embodiment of the present invention,
상기 제1 전극과 상기 정공수송층 사이에 위치하는 정공주입층과;a hole injection layer positioned between the first electrode and the hole transport layer;
상기 발광물질층과 상기 제2 전극 사이에 위치하는 전자수송층과;an electron transport layer positioned between the light emitting material layer and the second electrode;
상기 전자수송층과 상기 제2 전극 사이에 위치하는 전자주입층;을 포함하는 것인 유기전기발광소자를 제공한다. It provides an organic electroluminescent device comprising; an electron injection layer positioned between the electron transport layer and the second electrode.
또한, 본 발명은 상기 유기전기발광소자를 포함하는 전자기기를 제공한다.In addition, the present invention provides an electronic device including the organic electroluminescent device.
또한 본 발명은 상기 전자 기기가 유기 집적 회로 (O-IC), 유기 전기-효과 트랜지스터 (O-FET), 유기 박막 트랜지스터 (O-TFT), 유기전기발광 트랜지스터 (O-LET), 유기 태양 전지 (O-SC), 유기 광학 검출기, 유기 광수용체, 유기 전기-켄치 소자 (O-FQD), 발광 전기화학 전지 (LEC), 유기 레이저 다이오드 (O-레이저) 또는 유기전기발광소자 (OLED)인 전자 기기를 제공한다.In addition, the present invention provides that the electronic device is an organic integrated circuit (O-IC), an organic electric-effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic electroluminescent transistor (O-LET), and an organic solar cell. (O-SC), organic optical detector, organic photoreceptor, organic electro-quenching device (O-FQD), light emitting electrochemical cell (LEC), organic laser diode (O-laser) or organic electroluminescent device (OLED) Electronic devices are provided.
이하에서, 상기 유기전기발광소자에 대하여 예를 들어 설명한다. 그러나, 하기에 예시된 내용이 본 발명의 유기전기발광소자를 한정하는 것은 아니다.Hereinafter, the organic electroluminescent device will be described as an example. However, the contents exemplified below are not limited to the organic electroluminescent device of the present invention.
상기 유기전기발광소자는 양극(정공주입전극), 정공주입층(HIL) 및/또는 정공수송층(HTL), 발광층(EML) 및 음극(전자주입전극)이 순차적으로 적층된 구조를 가질 수 있으며, 바람직하게는, 양극과 발광층 사이에 전자차단층(EBL)을, 그리고 음극과 발광층 사이에 전자수송층(ETL), 전자주입층(EIL) 또는 정공차단층(HBL)을 추가로 포함할 수 있다.The organic electroluminescent device may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL) and/or a hole transport layer (HTL), a light emitting layer (EML) and a cathode (electron injection electrode) are sequentially stacked, Preferably, it may further include an electron blocking layer (EBL) between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) between the cathode and the light emitting layer.
상기 유기전기발광소자의 제조방법으로는, 먼저 기판 표면에 양극용 물질을 통상적인 방법으로 코팅하여 양극을 형성한다. 이때, 사용되는 기판은 투명성, 표면 평활성, 취급 용이성 및 방수성이 우수한 유리기판 또는 투명 플라스틱 기판이 바람직하다. 또한, 양극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등이 사용될 수 있다.In the method for manufacturing the organic electroluminescent device, first, a material for an anode is coated on the surface of a substrate in a conventional manner to form an anode. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), etc. which are transparent and have excellent conductivity may be used.
다음으로, 상기 양극 표면에 정공주입층(HIL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 정공주입층을 형성한다. 이러한 정공주입층 물질로는 상기 유기전기발광 화합물이 사용될 수 있으며, 이 밖에 구리프탈로시아닌(CuPc), 4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민(m-MTDATA), 4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠(m-MTDAPB), 스타버스트(starburst)형 아민류인 4,4',4"-트리(N-카바졸릴)트리페닐아민(TCTA), 4,4',4"-트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민(2-TNATA) 또는 이데미츠사(Idemitsu)에서 구입가능한 IDE406을 예로 들 수 있다.Next, a hole injection layer (HIL) material is vacuum-deposited or spin-coated on the surface of the anode by a conventional method to form a hole injection layer. The organic electroluminescent compound may be used as the hole injection layer material, in addition to copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4 ,4',4"-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB),
상기 정공주입층 표면에 정공수송층(HTL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 정공수송층을 형성한다. 이때, 정공수송층 물질로는 상기 유기전기발광 화합물이 사용될 수 있으며, 이 밖에 비스(N-(1-나프틸-n-페닐))벤지딘(α-NPD), N,N'-다이(나프탈렌-1-일)-N,N'-바이페닐-벤지딘(NPB) 또는 N,N'-바이페닐-N,N'-비스(3-메틸페닐)-1,1'-바이페닐-4,4'-다이아민(TPD)을 예로 들 수 있다.A hole transport layer is formed by vacuum thermal evaporation or spin coating of a hole transport layer (HTL) material on the surface of the hole injection layer by a conventional method. In this case, the organic electroluminescent compound may be used as the hole transport layer material, and in addition, bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N′-di(naphthalene- 1-yl)-N,N'-biphenyl-benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4' -Diamine (TPD) is an example.
상기 정공수송층 표면에 발광층(EML) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 발광층을 형성한다. 이때, 사용되는 발광층 물질 중 단독 발광물질 또는 발광 호스트 물질은 녹색의 경우 상기 유기전기발광 화합물이 인광 녹색 호스트 물질로 사용될 수 있으며, 황색의 경우 상기 유기전기발광 화합물이 인광 황색 호스트 물질로 사용될 수 있다.The light emitting layer is formed by vacuum thermal evaporation or spin coating of the light emitting layer (EML) material on the surface of the hole transport layer in a conventional manner. In this case, the organic electroluminescent compound may be used as a phosphorescent green host material in the case of green as a single light emitting material or a light emitting host material among the light emitting layer materials used, and in the case of yellow, the organic electroluminescent compound may be used as a phosphorescent yellow host material. .
발광층 물질 중 발광 호스트와 함께 사용될 수 있는 도판트(dopant)의 경우 형광 도판트로서 이데미츠사(Idemitsu)에서 구입 가능한 IDE102, IDE105, 인광 도판트로는 트리스(2-페닐피리딘)이리듐(III)(Ir(ppy)3), 이리듐(III)비스[(4,6-다이플루오로페닐)피리디나토-N,C-2']피콜린산염(FIrpic) (참조문헌[Chihaya Adachi et al., Appl. Phys. Lett., 2001, 79, 3082-3084]), 플라티늄(II)옥타에틸포르피린(PtOEP), TBE002(코비온사) 등을 사용할 수 있다.Among the light emitting layer materials, in the case of a dopant that can be used together with a light emitting host, IDE102 and IDE105 available from Idemitsu as fluorescent dopants, and tris (2-phenylpyridine) iridium (III) (Ir) as phosphorescent dopants. (ppy) 3 ), iridium(III)bis[(4,6-difluorophenyl)pyridinato-N,C-2′]picolinic acid salt (FIrpic) (Chihaya Adachi et al., Appl Phys. Lett., 2001, 79, 3082-3084]), platinum (II) octaethyl porphyrin (PtOEP), TBE002 (Cobion), and the like can be used.
상기 발광층 표면에 전자수송층(ETL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 전자수송층을 형성한다. 이때, 사용되는 전자수송층 물질로는 상기 유기전기발광 화합물을 사용할 수 있으며, 이 밖에 트리스(8-하이드록시퀴놀리놀라토)알루미늄(Alq3) 등을 사용할 수 있다.An electron transport layer (ETL) is formed on the surface of the light emitting layer by vacuum thermal evaporation or spin coating of an electron transport layer (ETL) material in a conventional manner. In this case, as the material for the electron transport layer used, the organic electroluminescent compound may be used, and in addition, tris(8-hydroxyquinolinolato)aluminum (Alq3) or the like may be used.
선택적으로는, 발광층과 전자수송층 사이에 정공차단층(HBL)을 추가로 형성하고 발광층에 인광 도판트를 함께 사용함으로써, 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지할 수 있다.Optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant together in the light emitting layer, the diffusion of triplet excitons or holes into the electron transport layer can be prevented.
정공차단층의 형성은 정공차단층 물질을 통상적인 방법으로 진공 열증착 및 스핀 코팅하여 실시할 수 있으며, 정공차단층 물질의 경우 특별히 제한되지는 않으나, 바람직하게는 (8-하이드록시퀴놀리놀라토)리튬(Liq), 비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄비페녹사이드(BAlq), 바쏘쿠프로인 (bathocuproine, BCP) 및 LiF 등을 사용할 수 있다.The formation of the hole blocking layer can be carried out by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner, and the hole blocking layer material is not particularly limited, but preferably (8-hydroxyquinolinola Earth) lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF, and the like may be used.
상기 전자수송층 표면에 전자주입층(EIL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 전자주입층을 형성한다. 이때, 사용되는 전자주입층 물질로는 상기 유기전기발광 화합물을 사용할 수 있으며, 이 밖에 LiF, Liq, Li2O, BaO, NaCl 또는 CsF 등의 물질을 사용할 수 있다. An electron injection layer is formed by vacuum thermal evaporation or spin coating of an electron injection layer (EIL) material on the surface of the electron transport layer in a conventional manner. In this case, as the material for the electron injection layer used, the organic electroluminescent compound may be used, and other materials such as LiF, Liq, Li 2 O, BaO, NaCl or CsF may be used.
마지막으로, 상기 전자주입층 표면에 음극용 물질을 통상적인 방법으로 진공 열증착하여 음극을 형성한다.Finally, a cathode is formed by vacuum thermal evaporation of a material for a cathode on the surface of the electron injection layer in a conventional manner.
이때, 사용되는 음극용 물질로는 리튬(Li), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘(Mg), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 사용될 수 있다. 또한, 전면발광 유기전기발광소자의 경우 산화인듐주석(ITO) 또는 산화인듐아연(IZO)를 사용하여 빛이 투과할 수 있는 투명한 음극을 형성할 수도 있다.At this time, as the material for the anode used, lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of a top light emitting organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).
실시예Example
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예 및 실험예를 제시한다. 그러나 하기의 실시예 및 실험예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예 및 실험예에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred examples and experimental examples are presented to help the understanding of the present invention. However, the following Examples and Experimental Examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited by the Examples and Experimental Examples.
재료ingredient
모든 시약 및 용매는 판매되는 것을 구입하였으며 추가 정제없이 사용하였다. 1H- 및 13C-NMR 스펙트럼은 500 MHz에서 작동하는 JNM-ECP FT-NMR 분광기(JEOL, Peabody, MA, USA)를 사용하여 기록하였다. 알루미늄으로 받쳐진 Merck Kiesegel 60으로 코팅된 TLC 플레이트를 사용하여 분석 박막 크로마토그래피(TLC)를 수행하였다. 컬럼 크로마토그래피는 실리카겔(메쉬 크기 200~300)을 사용하여 수행하였다. 1H- 및 13C-NMR 스펙트럼은 500 MHz에서 작동하는 JNM-ECP FT-NMR 분광기(JEOL, Peabody, MA, USA)를 사용하여 기록하였다. UV-Vis 흡광도 특성은 람다 1050 자외선 가시(UV-VIS) 분광도계(Perkin Elmer, Waltham, MA, USA)를 사용하여 분석하였다. 밴드 간격(Eg)의 에너지는 UV-Vis 흡광도 스펙트럼의 개시 파장에서 얻었다. 광발광 스펙트럼은 HR800 스펙트럼 형관분광계(Horiba Jobin Yvon, Paris, France)를 사용해 측정하였다. 질량 분석기 분석은 Xevo TQ-S 분광계(Waters, Milford, MA, USA)를 사용하여 수행하였다. 원소 분석은 ThermoFisher(Flash2000) 원소 분석기(Loughborough, England)로 얻었다. 열중량 분석과 시차주사열량계는 질소 대기하에 10 °C/분의 가열속도로 PerkinElmer DSC 4000 및 TGA 8000 시스템(Melville, NY, USA)을 사용하여 기록하였다. 삼중항 에너지 레벨은 톨루엔 내 77 K에서의 방출 스펙트럼의 개시 파장에서 평가하였다. HOMO(highest occupied molecular orbital) 값은 광전자 분광계(RIKEN, Saitama, Japan)를 이용한 AC-2 방법으로 결정하였다. LUMO 에너지는 얻은 HOMO 에너지에 밴드 갭 에너지를 더하여 계산했다. 유기발광다이오드(OLED) 소자는 5 × 10-7 torr(Sunicel plus, Seoul, Korea)의 압력하에 열적 증발 시스템으로 구성하였다. 유기발광다이오드(OLED) I-V-L 테스트 시스템(Polarmix M6100, Suwon, Korea)에서 현재 밀도-전압-발광량(J-V-L) 성능을 관측하였다. 전기 발광(EL) 스펙트럼은 분광방사계(Konica Minolta CS-2000, Tokyo, Japan)를 이용해 기록하였다.All reagents and solvents were purchased commercially and used without further purification. 1 H- and 13 C-NMR spectra were recorded using a JNM-ECP FT-NMR spectrometer (JEOL, Peabody, MA, USA) operating at 500 MHz. Analytical thin layer chromatography (TLC) was performed using a TLC plate coated with
실시예 1. N1-(4-(디페닐아미노)페닐)-N4,N4-디페닐-N1-(9,9-디페닐-9H-플루 오렌-7-일)벤젠-1,4-디아민 (FLU-DTPA)의 합성Example 1. N 1 -(4-(diphenylamino)phenyl)-N 4 ,N 4 -diphenyl-N 1 -(9,9-diphenyl-9H-fluoren-7-yl)benzene-1 Synthesis of ,4-diamine (FLU-DTPA)
9,9-디페닐-9H-플루오렌-2-아민 (1.0 g, 3 mmol), N-(4-아이오도페닐)-N-페닐벤젠아민 (2.45 g, 6.6 mmol), Pd(OAc)2, (0.01 g, 0.06 mmol), t-Bu3P (톨루엔 내 10%, 0.42 mL, 0.18 mmol), NaOt-Bu (1.15 g, 12 mmol) 및 무수 톨루엔(80ml)을 응축기가 장착된 2구 둥근 바닥 플라스크에 첨가하고, 불활성 조건의 110 ℃에서 12 시간 동안 교반하였다. 박층 크로마토그래피로 모니터링하여 반응을 완료한 후, 조 혼합물을 디클로로메탄 및 탈이온수로 3회 추출하였다. 유기층을 무수 황상마그네슘으로 건조시키고, 여과하고, 회전증발기를 사용하여 농축하였다. 조농축물을 n-헥산-디클로로메탄 용매 시스템을 사용하여 실리카겔 컬럼 크로마토그래피법으로 정제하고, 증발시켜 목적 화합물 FLU-DTPA를 수득하였다. 9,9-diphenyl-9H-fluoren-2-amine (1.0 g, 3 mmol), N-(4-iodophenyl)-N-phenylbenzeneamine (2.45 g, 6.6 mmol), Pd(OAc) 2 , (0.01 g, 0.06 mmol), t-Bu 3 P (10% in toluene, 0.42 mL, 0.18 mmol), NaOt-Bu (1.15 g, 12 mmol) and anhydrous toluene (80 ml) 2 equipped with a condenser It was added to a round-bottomed flask and stirred at 110° C. under inert conditions for 12 hours. After completion of the reaction by monitoring by thin layer chromatography, the crude mixture was extracted three times with dichloromethane and deionized water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated using a rotary evaporator. The crude concentrate was purified by silica gel column chromatography using an n-hexane-dichloromethane solvent system and evaporated to obtain the target compound FLU-DTPA.
수율: 61%; 노란색 고체; FT-IR (KBr 펠렛): υmax 3033, 1587, 1487, 1451, 1307, 1260, 1155, 1110, 1075, 1029, 824, 783, 748; 1H NMR (500 MHz, DMSO-d6) δ 7.72-7.75 (t, J= 8.0 Hz, 2H), 7.34-7.36 (d, J= 7.5 Hz, 1H), 7.29-7.32 (t, J= 7.5 Hz, 1H), 7.22-7.29 (t, J= 8.0 Hz, 9H), 7.12-7.13 (m, 6H), 6.98-7.00 (m, 5H), 6.88-6.96 (m, 17H), 6.83-6.85 (d, J= 9.0 Hz, 4H); 13C NMR (500 MHz, DMSO-d6) δ 152.3, 150.6, 147.7, 145.9, 142.8, 142.6, 140.0, 134.0, 129.9, 128.8, 128.1, 127.1, 125.7, 125.6, 123.7, 123.1, 65.3; MS (APCI) m/z: 819.62 for C61H45N3 [(M+H)+]. Anal. Calcd for C61H45N3 (%): C, 89.34; H, 5.53; N, 5.12. Found: C, 89.11; H, 5.60; N, 5.14.Yield: 61%; yellow solid; FT-IR (KBr pellets): υ max 3033, 1587, 1487, 1451, 1307, 1260, 1155, 1110, 1075, 1029, 824, 783, 748; 1 H NMR (500 MHz, DMSO- d6 ) δ 7.72-7.75 (t, J = 8.0 Hz, 2H), 7.34-7.36 (d, J = 7.5 Hz, 1H), 7.29-7.32 (t, J = 7.5 Hz) , 1H), 7.22-7.29 (t, J = 8.0 Hz, 9H), 7.12-7.13 (m, 6H), 6.98-7.00 (m, 5H), 6.88-6.96 (m, 17H), 6.83-6.85 (d , J = 9.0 Hz, 4H); 13 C NMR (500 MHz, DMSO- d6 ) δ 152.3, 150.6, 147.7, 145.9, 142.8, 142.6, 140.0, 134.0, 129.9, 128.8, 128.1, 127.1, 125.7, 125.6, 123.7, 123.1, 65.3; MS (APCI) m/z: 819.62 for C 61 H 45 N 3 [(M+H) + ]. Anal. Calcd for C 61 H 45 N 3 (%): C, 89.34; H, 5.53; N, 5.12. Found: C, 89.11; H, 5.60; N, 5.14.
실시예 2. N,N-비스(4-(9H-카바졸-9-일)페닐)-9,9-디페닐-9H-플루오렌-2-아민 (FLU-DCAR)의 합성Example 2. Synthesis of N,N-bis(4-(9H-carbazol-9-yl)phenyl)-9,9-diphenyl-9H-fluoren-2-amine (FLU-DCAR)
9,9-디페닐-9H-플루오렌-2-아민 (1.0 g, 3 mmol), 9-(4-브로모페닐)-9H-카바졸 (2.12 g, 6.6 mmol), Pd(OAc)2, (0.01 g, 0.06 mmol), t-Bu3P (톨루엔 내 10%, 0.42 mL, 0.18 mmol), NaOt-Bu (1.15 g, 12 mmol) 및 무수 톨루엔(80ml)을 응축기가 장착된 2구 둥근 바닥 플라스크에 첨가하고, 불활성 조건의 110 ℃에서 12 시간 동안 교반하였다. 박층 크로마토그래피로 모니터링하여 반응을 완료한 후, 조 혼합물을 디클로로메탄 및 탈이온수로 3회 추출하였다. 유기층을 무수 황상마그네슘으로 건조시키고, 여과하고, 회전증발기를 사용하여 농축하였다. 조농축물을 n-헥산-디클로로메탄 용매 시스템을 사용하여 실리카겔 컬럼 크로마토그래피법으로 정제하고, 증발시켜 목적 화합물 FLU-DCAㄲ를 수득하였다. 9,9-diphenyl-9H-fluoren-2-amine (1.0 g, 3 mmol), 9-(4-bromophenyl)-9H-carbazole (2.12 g, 6.6 mmol), Pd(OAc) 2 , (0.01 g, 0.06 mmol), t-Bu 3 P (10% in toluene, 0.42 mL, 0.18 mmol), NaOt-Bu (1.15 g, 12 mmol) and anhydrous toluene (80 ml) were mixed with two necks equipped with a condenser It was added to a round bottom flask and stirred at 110° C. under inert conditions for 12 hours. After completion of the reaction by monitoring by thin layer chromatography, the crude mixture was extracted three times with dichloromethane and deionized water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated using a rotary evaporator. The crude concentrate was purified by silica gel column chromatography using an n-hexane-dichloromethane solvent system and evaporated to obtain the target compound FLU-DCAㄲ.
수율: 73 %; 주황색 고체; FT-IR (KBr 펠릿): υmax 3045, 1888, 1597, 1505, 1479, 1449, 1334, 1307, 1286, 1227, 1181, 1147, 1116, 1079, 1028, 1014, 911, 874, 828, 784, 744, 721 cm-1; 1H NMR (500 MHz, DMSO-d6) δ 8.21-8.22 (d, J= 7.5 Hz, 3H), 7.95-7.96 (d, J= 8.0 Hz, 1H), 7.87-7.88 (d, J= 7.5 Hz, 1H), 7.51-7.53 (d, J= 9.0 Hz, 5H), 7.41-7.44 (m, 6H), 7.34-7.37 (t, J= 9.0 Hz, 10H), 7.11-7.28 (m, 12 H), 7.096-7.11 (d, J= 7.0 Hz, 3H); 13C NMR (500 MHz, DMSO-d6) δ 140.8, 128.9, 128.2, 125.0, 123.1, 121.0, 120.5, 116.7, 110.1; MS (APCI) m/z: 815.97 for C61H41N3 [(M+H)+]. Anal. Calcd for C61H41N3 (%): C, 89.79; H, 5.06; N, 5.15. Found: C, 89.58; H, 5.09; N, 5.17.Yield: 73%; orange solid; FT-IR (KBr pellets): υ max 3045, 1888, 1597, 1505, 1479, 1449, 1334, 1307, 1286, 1227, 1181, 1147, 1116, 1079, 1028, 1014, 911, 874, 828, 784, 744, 721 cm -1 ; 1 H NMR (500 MHz, DMSO- d6 ) δ 8.21-8.22 (d, J = 7.5 Hz, 3H), 7.95-7.96 (d, J = 8.0 Hz, 1H), 7.87-7.88 (d, J = 7.5 Hz) , 1H), 7.51-7.53 (d, J = 9.0 Hz, 5H), 7.41-7.44 (m, 6H), 7.34-7.37 (t, J = 9.0 Hz, 10H), 7.11-7.28 (m, 12 H) , 7.096-7.11 (d, J = 7.0 Hz, 3H); 13 C NMR (500 MHz, DMSO- d6 ) δ 140.8, 128.9, 128.2, 125.0, 123.1, 121.0, 120.5, 116.7, 110.1; MS (APCI) m/z: 815.97 for C 61 H 41 N 3 [(M+H) + ]. Anal. Calcd for C 61 H 41 N 3 (%): C, 89.79; H, 5.06; N, 5.15. Found: C, 89.58; H, 5.09; N, 5.17.
실시예 3. 소자 제작Example 3. Device Fabrication
50 nm의 인듐 주석 산화물 (ITO)로 코팅된 유리 기판을 초음파 배스 내에서 10분 동안 과량의 이소프로필알코올 및 아세톤을 사용하여 세척하였다. 이어서, 잔류물을 탈이온수로 세척하였고, 기판을 N2 가스 하에 건조시켰다. 세척된 기판을 UV-오존 챔버에서 10분 동안 처리하였다. 모든 유기층은 1×10-7 torr 이하의 압력하에 고진공 증발 장치 내에서 ITO 기판 상에 0.1 내지 0.5 Å s-1의 다양한 증착 비로 증착시켰다. LiF 및 알루미늄은 각각 0.15 및 4) Å-s-1의 비로 증착시켰다. 증착 후, 모든 소자를 N2 분위기 글로브 박스 하에 UV-경화성 수지를 갖는 유리 커버로 캡슐화하였다. 각 소자의 활성 면적은 4 mm2이었다.A glass substrate coated with 50 nm of indium tin oxide (ITO) was washed in an ultrasonic bath for 10 minutes using an excess of isopropyl alcohol and acetone. The residue was then washed with deionized water, and the substrate was dried under N2 gas. The cleaned substrates were treated in a UV-ozone chamber for 10 minutes. All organic layers were deposited at various deposition ratios of 0.1 to 0.5 Å s −1 on the ITO substrate in a high vacuum evaporation apparatus under a pressure of 1×10 −7 torr or less. LiF and aluminum were deposited at a ratio of 0.15 and 4) Å-s −1 , respectively. After deposition, all devices were encapsulated with a glass cover with UV-curable resin under an N 2 atmosphere glove box. The active area of each device was 4 mm 2 .
시험예 1. 열중량 분석 및 시차 주사 열량계 분석Test Example 1. Thermogravimetric analysis and differential scanning calorimetry analysis
FLU-DTPA 및 FLU-DCAR의 열적 안정성을 이해하기 위해 질소 분위기 하에서 열중량 분석 (Thermogravimetric analysis, TGA) 및 시차 주사 열량계 분석(Differential scanning calorimetry, DSC)을 수행하여 그 결과를 표 1 및 도 1에 나타내었다.To understand the thermal stability of FLU-DTPA and FLU-DCAR, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed under a nitrogen atmosphere, and the results are shown in Table 1 and FIG. 1 indicated.
도 1 및 표 1에 나타난 바와 같이, FLU-DTPA의 유리전이온도는 315 ℃로 기록되었으며, FLU-DTPA 및 FLU-DCAR의 열분해 온도는 각각 약 426℃ 및 448 ℃에서 10% 중량 감소를 보였다. 이러한 열적 특성은 소자 제조 공정 동안 균일한 필름 형성 및 소자의 형태적 안정성을 도모할 수 있으므로 유리하다. 1 and Table 1, the glass transition temperature of FLU-DTPA was recorded as 315 °C, and the thermal decomposition temperature of FLU-DTPA and FLU-DCAR showed a 10% weight loss at about 426 °C and 448 °C, respectively. Such thermal properties are advantageous because uniform film formation and morphological stability of the device can be promoted during the device manufacturing process.
시험예 2. UV-vis 흡수 및 광발광 방출을 이용한 광물리학적 분석Test Example 2. Photophysical analysis using UV-vis absorption and photoluminescence emission
톨루엔 용매 내에 UV-vis 흡수 및 광발광 (photoluminescence PL) 방출로 광물리학적 연구를 수행하였으며 이를 표 1 및 도 2에 나타내었다. Photophysical studies were performed with UV-vis absorption and photoluminescence PL emission in toluene solvent, and are shown in Table 1 and FIG. 2 .
표 1 및 도 2에 나타난 바와 같이, UV-vis 최대 흡수 피크는 FLU-DTPA는 389 nm, FLU-DCAR는 405 nm에서 관찰되었다. FLU-DCAR는 디페닐아민계 유도체와 대비할 때, 견고하고 연장된 접합 길이로 인해 더 긴 흡수를 나타내었다. FLU-DTPA 및 FLU-DCAR의 밴드 갭 에너지 값은 각각 2.39 eV 및 2.48 eV로 측정되었고, 이는 각각 517 nm 및 500 nm의 시작 흡수 파장(onset absorption wavelength)에 해당하는 값이다. 한편, 톨루엔 용액에서의 FLU-DTPA 및 FLU-DCAR의 실온 PL 최대값은 각각 444 nm 및 411 nm로 관찰되었다. 삼중항 에너지 측정에서 FLU-DTPA 및 FLU-DCAR는 각각 2.99 eV 및 3.18 eV로 측정되어 두 물질 모두 높은 삼중항 에너지를 나타내는 것을 확인하였다.As shown in Table 1 and FIG. 2, the UV-vis maximum absorption peak was observed at 389 nm for FLU-DTPA and 405 nm for FLU-DCAR. FLU-DCAR exhibited longer absorption due to robust and extended junction length when compared to diphenylamine derivatives. The band gap energy values of FLU-DTPA and FLU-DCAR were measured to be 2.39 eV and 2.48 eV, respectively, which correspond to onset absorption wavelengths of 517 nm and 500 nm, respectively. Meanwhile, room temperature PL maxima of FLU-DTPA and FLU-DCAR in toluene solution were observed to be 444 nm and 411 nm, respectively. In the triplet energy measurement, FLU-DTPA and FLU-DCAR were measured at 2.99 eV and 3.18 eV, respectively, confirming that both materials exhibit high triplet energy.
a 녹는점, b 열분해온도, c 톨루엔의 UV 흡수파장, d THF의 광발광 최대 방출, e 에너지 밴드 갭, f 삼중항 에너지, g 가장 높은 점유 분자 궤도 에너지, h 가장 낮은 비점유 분자 궤도 에너지 a melting point, b pyrolysis temperature, c UV absorption wavelength of toluene, d photoluminescence maximum emission of THF, e energy band gap, f triplet energy, g highest occupied molecular orbital energy, h lowest unoccupied molecular orbital energy
시험예test example 3. HOMO, 3. HOMO, LUMOLUMO 에너지 레벨 분석 Energy level analysis
본 발명에 따른 실시예 1, 2의 화합물에 대한 가장 높은 점유 분자 궤도 에너지 (HOMO) 레벨을 계산하였으며, FLU-DTPA 및 FLU-DCAR에 대해 각각 5.27 eV 및 -4.82 eV 였다. 밴드 갭 에너지에 HOMO 에너지를 추가하여 얻은 가장 낮은 비점유 분자 궤도 (LUMO) 에너지 값은 FLU-DTPA 및 FLU-DCAR에 대해 각각 2.34 eV 및 2.88 eV 이었다. 계산 데이터는 B3LYP/6-31G 레벨에서 Schrodinger 2020-2 프로그램을 사용하여 수행하였으며, 프론티어 분자 궤도 에너지(Frontier molecular orbital energies, FMO) 분포를 도 3에 나타내었다. The highest occupied molecular orbital energy (HOMO) level was calculated for the compounds of Examples 1 and 2 according to the present invention, which were 5.27 eV and -4.82 eV for FLU-DTPA and FLU-DCAR, respectively. The lowest unoccupied molecular orbital (LUMO) energy values obtained by adding the HOMO energy to the bandgap energy were 2.34 eV and 2.88 eV for FLU-DTPA and FLU-DCAR, respectively. Calculation data was performed using the Schrodinger 2020-2 program at the B3LYP/6-31G level, and the distribution of frontier molecular orbital energies (FMO) is shown in FIG. 3 .
HOMO 분포는 주로 전자 공여체 타입인 트리페닐아민 및 카바졸 모이어티 상에 위치하였으며, LUMO 분포는 플루오렌 단위에서 나타났고, 전자공여체와 플루오렌 모이어티 사이에 작은 중첩(overlap)이 관찰되었다. 한편, 밀도 함수 이론 계산을 수행하였으며, FLU-DTPA 및 FLU-DCAR의 계산된 HOMO 에너지 레벨은 -5.23 eV 및 -5.59 eV이었고, 계산된 LUMO 값은 각각 -2.15 및 -2.38 eV으로 나타나 측정된 에너지 수준과 동일한 경향을 따르는 것이 확인되었다. The HOMO distribution was mainly located on the electron donor type triphenylamine and carbazole moieties, the LUMO distribution was in the fluorene unit, and a small overlap was observed between the electron donor and the fluorene moiety. Meanwhile, density functional theory calculations were performed, and the calculated HOMO energy levels of FLU-DTPA and FLU-DCAR were -5.23 eV and -5.59 eV, and the calculated LUMO values were -2.15 and -2.38 eV, respectively. It was confirmed that the same trend was followed by the level.
시험예test example 4. 소자 제작 및 특성 분석 4. Device Fabrication and Characterization
소자 성능을 조사하기 위해, FLU-DTPA 및 FLU-DCAR를 정공 수송 물질로 사용하여 황색 인광 OLED를 제작하였으며, 소자 구조와 에너지 다이어그램을 도 4에 나타내었다. 황색 인광 소자의 구조는 다음과 같다: 인듐 주석 산화물(ITO) (150 nm) / 1,4,5,8,9,11-헥사아자트리페닐렌헥사카보니트릴 (HATCN) (7 nm) / 4,4'-시클로헥실리덴비스[N,N-비스(4-메틸페닐)벤즈아민] (TAPC) (43 nm) / FLU-DTPA 또는 FLU-DCAR: 10 중량% 이리듐(III) 비스(4-(4-터트-부틸페닐)티에노[3,2-c]피리디나토-N,C2') 아세틸아세토네이트 (20nm)/ 1,3,5-트리(m-피리딘-3-일페닐)벤젠 (TmPyPB) (35nm) / 8-퀴놀리놀라토 리튬 (Liq) (1.5nm) / 알루미늄 (Al) (100nm). To investigate device performance, a yellow phosphorescent OLED was fabricated using FLU-DTPA and FLU-DCAR as hole transport materials, and the device structure and energy diagram are shown in FIG. 4 . The structure of the yellow phosphorescent device is as follows: indium tin oxide (ITO) (150 nm) / 1,4,5,8,9,11-hexaazatriphenylenehexacapitrile (HATCN) (7 nm) / 4 ,4′-Cyclohexylidenebis[N,N-bis(4-methylphenyl)benzamine] (TAPC) (43 nm) / FLU-DTPA or FLU-DCAR: 10 wt % iridium(III) bis(4- (4-tert-butylphenyl)thieno[3,2-c]pyridinato-N,C2')acetylacetonate (20nm)/1,3,5-tri(m-pyridin-3-ylphenyl) Benzene (TmPyPB) (35 nm) / 8-quinolinolatolithium (Liq) (1.5 nm) / Aluminum (Al) (100 nm).
양극에는 ITO가 사용되고, 음극은 Al이 사용되었고, 정공 주입 층 (hole injecting layer, HIL)에는 HATCN, 호스트 물질로는 4,4'-비스(N-카바졸릴)-1,10-비페닐 (CBP), 황색 인광 도펀트로 PO-O1, 전자 수송 층 (electron transport layer, ETL)에는 TmPyPB, 전자 주입 층 (Electron injection layer, EIL)으로 Liq을 사용하였다.ITO was used for the anode, Al was used for the cathode, HATCN for the hole injecting layer (HIL), and 4,4'-bis(N-carbazolyl)-1,10-biphenyl ( CBP), PO-O1 as a yellow phosphorescent dopant, TmPyPB as an electron transport layer (ETL), and Liq as an electron injection layer (EIL) were used.
제작된 소자의 전자 발광 특성을 분석하기 위해, 전류밀도-전압-발광 성능(JVL)을 측정하여 표 2 및 도 5에 나타내었으며, 외부 양자 효율을 측정하여 도 6에 나타내었다.In order to analyze the electroluminescence characteristics of the fabricated device, the current density-voltage-luminescence performance (JVL) was measured and shown in Tables 2 and 5, and the external quantum efficiency was measured and shown in FIG. 6 .
(황색 소자)FLU-DTPA
(yellow element)
(황색 소자)FLU-DCAR
(yellow element)
(기준 소자)TAPC
(reference element)
TAPC 기반 기준 소자 (5 V)에 비해 FLU-DTPA 및 FLU-DCAR 기반 소자는 각각 5.5 V 및 6 V의 더 높은 문턱전압(turn on voltage)을 보여주었다. FLU-DCAR 기반 소자의 전류 효율은 44.25 cd/A로 TAPC 기반 기준 소자에 비해 높은 전류 효율을 보여주었으며, FLU-DTPA 기반 소자 역시 기준소자에 비해 높은 전류 효율을 보여주었다. 한편, FLU-DCAR 기반 소자의 전력 효율은 21.39 lm/W로 나타났으며, 이는 트리페닐아민 기반 FLU-DTPA 소자보다 우수하였다. 최대 외부 양자 효율(external quantum efficiency: EQE)은 FLU-DCAR 기반 소자의 경우 17.80 %로 다른 소자에 비해 우수하였다. FLU-DCAR 기반 소자는 특히 우수한 장치특성을 나타내었다.Compared to the TAPC-based reference device (5 V), the FLU-DTPA and FLU-DCAR based devices showed higher turn on voltages of 5.5 V and 6 V, respectively. The current efficiency of the FLU-DCAR-based device was 44.25 cd/A, which showed higher current efficiency compared to the TAPC-based reference device, and the FLU-DTPA-based device also showed higher current efficiency than the reference device. Meanwhile, the power efficiency of the FLU-DCAR-based device was 21.39 lm/W, which was superior to that of the triphenylamine-based FLU-DTPA device. The maximum external quantum efficiency (EQE) was 17.80% for the FLU-DCAR-based device, which was superior to other devices. The FLU-DCAR-based device showed particularly good device characteristics.
또한, 황색 인광 장치의 EL (Electroluminescent) 스펙트럼을 확인하였으며, 이를 도 7에 나타내었다. 모든 황색 소자의 최대 방출은 560nm으로 유사했으며, 이로 황색 도판트로부터의 황색 방출을 입증하였다.In addition, the EL (Electroluminescent) spectrum of the yellow phosphorescent device was confirmed, which is shown in FIG. 7 . The maximum emission of all yellow devices was similar at 560 nm, demonstrating yellow emission from the yellow dopant.
시험예test example 4. 4. 비도핑non-doping 형광 소자 제작 및 특성 분석 Fluorescent device fabrication and characterization
방출기로서 분자 성능을 이해하기 위해 도핑되지 않은 형광 소자를 제작하였다. 도핑되지 않은 소자 구조는 다음과 같다 : 인듐 주석 산화물 (ITO) (150 nm) / 1,4,5,8,9,11-헥사아자트리페닐렌헥사카보니트릴 (HATCN) (7 nm) / 4,4'-시클로헥실리덴비스[N,N-비스(4-메틸페닐)벤즈아민] (TAPC) (43 nm) / FLU-DTPA 또는 FLU-DCAR (20 nm) / 1,3,5-트리(m-피리딘-3-일페닐)벤젠 (TmPyPB) (35 nm) / 8-퀴놀리놀라토리튬 (Liq) (1.5 nm) / 알루미늄 (Al) (100 nm). To understand molecular performance as emitters, undoped fluorescent devices were fabricated. The undoped device structure is as follows: indium tin oxide (ITO) (150 nm) / 1,4,5,8,9,11-hexaazatriphenylenehexacapitrile (HATCN) (7 nm) / 4 ,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzamine] (TAPC) (43 nm) / FLU-DTPA or FLU-DCAR (20 nm) / 1,3,5-tri (m-pyridin-3-ylphenyl)benzene (TmPyPB) (35 nm) / 8-quinolinolatolithium (Liq) (1.5 nm) / aluminum (Al) (100 nm).
제작된 비도핑 형광 소자의 성능을 도 8에 나타내었으며, 전계발광 스펙트럼을 도 9에 나타내었다. 본 발명에 따른 상기 두 종의 비도핑 소자의 문턱전압은 4.5 V였고, FLU-DTPA와 FLU-DCAR의 전류 효율은 각각 1.23과 0.52 cd/A로 측정되었다. FLU-DCAR의 EQE는 1.95%로 FLU-DTPA의 1.46%보다 약간 높았고, 두 장치 모두 진한 청색의 방출을 보였다. CIE 색상 좌표(x, y)는 0.16 및 0.12이였다. The performance of the fabricated undoped fluorescent device is shown in FIG. 8 , and the electroluminescence spectrum is shown in FIG. 9 . The threshold voltage of the two types of undoped devices according to the present invention was 4.5 V, and the current efficiencies of FLU-DTPA and FLU-DCAR were measured to be 1.23 and 0.52 cd/A, respectively. EQE of FLU-DCAR was 1.95%, which was slightly higher than 1.46% of FLU-DTPA, and both devices showed dark blue emission. The CIE color coordinates (x, y) were 0.16 and 0.12.
살펴본 바와 같이, 본 발명에 따른 플루오렌 코어와 트리페닐아민 또는 카바졸 모이어티를 가지는 신규한 구조의 물질 FLU-DTPA와 FLU-DCAR는 황색 인광 OLED의 정공 수송 재료로 종래 TAPC 기반 소자와 비교하여 우수한 성능을 나타낸다. As can be seen, FLU-DTPA and FLU-DCAR, which have novel structures having a fluorene core and a triphenylamine or carbazole moiety according to the present invention, are hole transport materials for yellow phosphorescent OLEDs compared to conventional TAPC-based devices. It shows excellent performance.
Claims (8)
[화학식 1]
식 중에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로
[Formula 1]
In the formula, R 1 and R 2 are the same as or different from each other, and each independently
[화학식 1]
식 중에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로
[Formula 1]
In the formula, R 1 and R 2 are the same as or different from each other, and each independently
화학식 1로 표시되는 정공 수송 물질은 하기 화학식 2 또는 화학식 3으로 표시되는 화합물인, 정공 수송 물질:
[화학식 2]
[화학식 3]
The hole transport material represented by Formula 1 is a compound represented by Formula 2 or Formula 3, a hole transport material:
[Formula 2]
[Formula 3]
상기 제1 전극과 마주보는 제2 전극과;
상기 제1 및 제2 전극 사이에 위치하는 발광물질층과;
상기 제1 전극과 상기 발광물질층 사이에 위치하는 정공수송층을 포함하고,
상기 정공수송층은 제2항에 따른 정공 수송 물질을 포함하여 이루어지는 것인 유기전기발광소자.a first electrode;
a second electrode facing the first electrode;
a light emitting material layer positioned between the first and second electrodes;
and a hole transport layer positioned between the first electrode and the light emitting material layer,
The hole transport layer is an organic electroluminescent device comprising the hole transport material according to claim 2 .
상기 정공수송층은 스핀코팅 공정, 노즐프린팅 공정, 잉크젯프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정으로 이루어진 군으로부터 선택되는 어느 하나에 의해 형성되는 것인 유기전기발광소자.5. The method of claim 4,
The hole transport layer is an organic electroluminescent device formed by any one selected from the group consisting of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
상기 제1 전극과 상기 정공수송층 사이에 위치하는 정공주입층과;
상기 발광물질층과 상기 제2 전극 사이에 위치하는 전자수송층과;
상기 전자수송층과 상기 제2 전극 사이에 위치하는 전자주입층;을 포함하는 것인 유기전기발광소자.5. The method of claim 4,
a hole injection layer positioned between the first electrode and the hole transport layer;
an electron transport layer positioned between the light emitting material layer and the second electrode;
An organic electroluminescent device comprising a; an electron injection layer positioned between the electron transport layer and the second electrode.
상기 전자 기기가 유기 집적 회로 (O-IC), 유기 전기-효과 트랜지스터 (O-FET), 유기 박막 트랜지스터 (O-TFT), 유기전기발광 트랜지스터 (O-LET), 유기 태양 전지 (O-SC), 유기 광학 검출기, 유기 광수용체, 유기 전기-켄치 소자 (O-FQD), 발광 전기화학 전지 (LEC), 유기 레이저 다이오드 (O-레이저) 또는 유기전기발광소자 (OLED)인 전자 기기.8. The method of claim 7,
The electronic device is an organic integrated circuit (O-IC), an organic electric-effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic electroluminescent transistor (O-LET), an organic solar cell (O-SC). ), organic optical detectors, organic photoreceptors, organic electro-quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) or organic electroluminescent devices (OLEDs).
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