KR101177172B1 - Novel anthracene derivative and organic electroluminescence device using the same - Google Patents
Novel anthracene derivative and organic electroluminescence device using the same Download PDFInfo
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- KR101177172B1 KR101177172B1 KR1020090089821A KR20090089821A KR101177172B1 KR 101177172 B1 KR101177172 B1 KR 101177172B1 KR 1020090089821 A KR1020090089821 A KR 1020090089821A KR 20090089821 A KR20090089821 A KR 20090089821A KR 101177172 B1 KR101177172 B1 KR 101177172B1
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- South Korea
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- substituted
- organic
- light emitting
- unsubstituted
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- 150000001454 anthracenes Chemical class 0.000 title abstract description 12
- 238000005401 electroluminescence Methods 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000011368 organic material Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 17
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 7
- 125000004076 pyridyl group Chemical group 0.000 abstract description 5
- 125000005577 anthracene group Chemical group 0.000 abstract description 4
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- Electroluminescent Light Sources (AREA)
Abstract
본 발명은 안트라센 유도체 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 N(질소)을 포함하는 헤테로아릴기, 비제한적인 예를 들면 피리디닐(pyridinyl)기, 피라지닐(pyrazinyl)기, 피리미디닐(pyrimidinyl)기, 또는 피리다지닐(pyridazinyl)기 등이 안트라센 모이어티(moiety)에 치환된 신규 안트라센 유도체; 및 상기 안트라센 유도체를 함유하는 유기물층(바람직하게는 본 발명의 안트라센 유도체가 녹색 및/또는 청색 발광 재료로서 함유된 발광층)이 양극과 음극 사이에 개재(介在)되어 발광효율, 휘도, 열적 안정성, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to an anthracene derivative and an organic electroluminescent device using the same, and more particularly, heteroaryl group containing N (nitrogen), non-limiting examples such as pyridinyl group, pyrazinyl group A novel anthracene derivative in which a pyrimidinyl group, a pyridazinyl group, or the like is substituted for an anthracene moiety; And an organic material layer containing the anthracene derivative (preferably a light emitting layer in which the anthracene derivative of the present invention is contained as a green and / or blue light emitting material) is interposed between the anode and the cathode so that luminous efficiency, brightness, thermal stability, driving The present invention relates to an organic EL device having improved characteristics such as voltage and lifetime.
Description
본 발명은 안트라센 유도체 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 N(질소)을 포함하는 헤테로아릴기, 비제한적인 예를 들면 피리디닐기, 피라지닐기, 피리미디닐기, 또는 피리다지닐기 등이 안트라센 모이어티(moiety)에 치환된 신규 안트라센 유도체; 및 상기 안트라센 유도체를 함유하는 유기물층(바람직하게는 본 발명의 안트라센 유도체가 녹색 및/또는 청색 발광 재료로서 함유된 발광층)이 양극과 음극 사이에 개재(介在)되어 발광효율, 휘도, 열적 안정성, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to an anthracene derivative and an organic electroluminescent device using the same, and more particularly, heteroaryl group containing N (nitrogen), non-limiting examples such as pyridinyl group, pyrazinyl group, pyrimidinyl group, or Novel anthracene derivatives in which a pyridazinyl group and the like are substituted with an anthracene moiety; And an organic material layer containing the anthracene derivative (preferably a light emitting layer in which the anthracene derivative of the present invention is contained as a green and / or blue light emitting material) is interposed between the anode and the cathode so that luminous efficiency, brightness, thermal stability, driving The present invention relates to an organic EL device having improved characteristics such as voltage and lifetime.
현재 유기 전계 발광 소자(유기 EL 소자)는 플라즈마 디스플레이 패널(PDP)이나 무기 전계발광소자 디스플레이에 비해 낮은 구동 전압, 넓은 시야 각, 고속 응답성, 고 콘트라스트 (contrast) 등의 뛰어난 특징을 갖게 됨으로써, 그래픽 디스플레이의 픽셀 (pixel), 텔레비전 영상 디스플레이나 표면 광원 (surface light source)의 픽셀로서 사용될 수 있다. 휠 수 있는 투명 기판 위에도 소자를 형성할 수 있고, 매우 얇고 가볍게 만들 수 있으며, 색감이 좋기 때문에 차세대 평면 디스 플레이에 적합한 소자로 부상하고 있다. 1987년 이스트만 코닥에서는 발광층 형성용 재료로서 저 분자인 방향족 디아민과 알루미늄 착물을 이용하고 있는 유기 EL 소자를 처음으로 개발하였다. Currently, organic electroluminescent devices (organic EL devices) have excellent characteristics such as low driving voltage, wide viewing angle, high-speed response, and high contrast compared to plasma display panel (PDP) or inorganic electroluminescent device display. It can be used as a pixel of a graphic display, as a pixel of a television image display or a surface light source. The device can be formed on a bendable transparent substrate, can be made very thin and light, and has good color, which is emerging as a suitable device for the next generation flat panel display. In 1987, Eastman Kodak developed for the first time an organic EL device using a low molecular aromatic diamine and an aluminum complex as a material for forming a light emitting layer.
소자에 순방향의 전압을 가하면 양극과 음극으로부터 각각 정공과 전자가 주입이 되며 이들은 발광 층에서 재결합되어 전자-정공 쌍인 엑시톤(exciton)을 형성한다. 분자의 파이 전자(pi-electron)가 여기된 상태의 구조를 가진 엑시톤은 다시 바닥 상태로 돌아오면서 그에 해당하는 에너지를 빛으로 변환시킨다. When a forward voltage is applied to the device, holes and electrons are injected from the anode and the cathode, respectively, and they are recombined in the emission layer to form an exciton, an electron-hole pair. Excitons, whose structures are excited by the pi-electron excited state, return to the ground and convert their energy into light.
최근에는 발광하는 빛의 색순도와 효율을 높이기 위하여 엑시톤을 형성하는 발광 층에 소량의 형광성 염료 또는 인광성 염료를 도핑 (doping)하는 방법이 알려져 있다. 그 원리는 발광층을 형성하는 분자보다 에너지 대역간극이 작은 형광성 또는 인광성 염료(이하, '도판트'라 약칭함)를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 이송되어 효율이 높은 빛을 내는 원리이다. Recently, a method of doping a small amount of fluorescent dyes or phosphorescent dyes to the light emitting layer forming the exciton in order to increase the color purity and efficiency of the light emitted is known. The principle is that when a small amount of fluorescent or phosphorescent dye (hereinafter, referred to as 'dopant') in the light emitting layer is mixed with a smaller energy band gap than the molecules forming the light emitting layer, excitons generated in the light emitting layer are transferred to the dopant, thereby providing high efficiency light. It is a principle to pay.
이데미쓰-고산의 디페닐비닐비페닐 (4,4'-bis(2,2-diphenylvinyl)biphenyl)과 이스트만 코닥의 디나프틸안트라센 (dinaphthylanthracen), 테트라(티부틸)페릴렌 (tetra(t-butyl)perlyene) 시스템이 청색 재료로서 많이 알려져 있으며, 현재에도 많은 연구 개발이 진행되고 있다. 현재까지 가장 효율이 좋다고 알려진 이데미쓰 고산의 디스트릴 화합물의 시스템은 소자 수명이 30,000 시간 이상으로 좋기는 하나, 구동 시간에 따른 색 순도의 저하로 인하여 풀 컬러 디스플레이에 적용 시 수명은 수천 시간에 불과하다. 따라서, 현재까지도 색순도가 좋고 (순청색) 고효율을 나타내며, 열적 안정성이 뛰어난 재료의 연구 개발이 시급한 부분이라 하겠다.Diphenylvinylbiphenyl of idemis-high acid (4,4'-bis (2,2-diphenylvinyl) biphenyl), dinaphthylanthracen of Eastman Kodak, tetra (tibutyl) perylene (tetra (t- The butyl) perlyene) system is widely known as a blue material, and much research and development is still in progress. Although the system of Idemitsu high acid distrile compound, which is known to be the most efficient to date, has a device life of more than 30,000 hours, its lifetime is only a few thousand hours when applied to a full color display due to the deterioration of color purity according to the driving time. Do. Therefore, it is an urgent part to research and develop a material having good color purity (high blue color), high efficiency, and excellent thermal stability.
본 발명은 기존의 안트라센 아릴 유도체와는 달리 N(질소)을 포함하는 헤테로아릴기(예를 들면 피리디닐기, 피라지닐기, 피리미디닐기, 피리다지닐기 등)가 안트라센에 치환된 신규 안트라센 유도체의 개발을 목적으로 한다. 또한, 본 발명은 상기 안트라센 유도체를 소자 내 유기층, 바람직하게는 발광층의 재료로 적용함으로써 발광효율, 휘도가 향상되고 저 전압 구동이 가능하며, 열 안정성이 뛰어난 유기 전계 발광 소자의 제공을 목적으로 한다.The present invention is a novel anthracene in which a heteroaryl group (for example, pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, etc.) containing N (nitrogen) is substituted with anthracene, unlike the existing anthracene aryl derivatives. It is aimed at the development of derivatives. In addition, an object of the present invention is to provide an organic electroluminescent device having improved luminous efficiency, brightness, low voltage driving, and excellent thermal stability by applying the anthracene derivative as a material of an organic layer, preferably a light emitting layer in the device. .
앞에서 기술한 과제들을 해결 위하여 본 발명은 하기 화학식 1로 표시되는 화합물, 바람직하게는 안트라센 유도체를 제공한다.The present invention provides a compound, preferably an anthracene derivative represented by the following formula (1) to solve the problems described above.
[화학식 1][Formula 1]
상기 화학식 1에서, Z1 내지 Z5는 서로 같거나 다르고, 각각 독립적으로 C 또 는 N이며, Z1 내지 Z5 중 하나 이상은 N이며;In Chemical Formula 1, Z 1 to Z 5 are the same as or different from each other, and each independently C or N, and at least one of Z 1 to Z 5 is N;
Ar1 및 Ar2 은 서로 같거나 다르고, 각각 독립적으로 수소, 중수소, 치환 혹은 비치환된 C6~C60 의 방향족기이며;Ar 1 and Ar 2 are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 6 -C 60 aromatic group;
X1 및 X2는 서로 같거나 다르고, 각각 독립적으로 수소, 중수소, 치환 혹은 비치환된 C6~C60 의 방향족기, 치환 혹은 비치환된 C5~C60의 방향족 복소환기, 치환 혹은 비치환된 C1~C60의 알킬기, 치환 혹은 비치환된 C3~C60의 시클로알킬기, 치환 혹은 비치환된 C1~C60의 알콕시기, 치환 혹은 비치환된 C6~C60의 아릴알킬기, 치환 혹은 비치환된 C1~C60의 알킬옥시기, 치환 혹은 비치환된 C5~C60의 아릴옥시기, 치환 혹은 비치환된 C5~C60의 아릴기, 또는 치환 혹은 비치환된 C5~C60의 헤테로아릴기이며;X 1 and X 2 are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 6 ~ C 60 aromatic group, a substituted or unsubstituted C 5 ~ C 60 aromatic heterocyclic group, substituted or unsubstituted A substituted C 1 to C 60 alkyl group, a substituted or unsubstituted C 3 to C 60 cycloalkyl group, a substituted or unsubstituted C 1 to C 60 alkoxy group, a substituted or unsubstituted C 6 to C 60 aryl Alkyl group, substituted or unsubstituted C 1 to C 60 alkyloxy group, substituted or unsubstituted C 5 to C 60 aryloxy group, substituted or unsubstituted C 5 to C 60 aryl group, or substituted or unsubstituted Ring C 5 ~ C 60 Heteroaryl group;
a 및 b는 각각 독립적으로 0~4의 정수이고, n 은 1~3의 정수이다.a and b are the integers of 0-4 each independently, and n is an integer of 1-3.
상기 화학식 1의 Ar1, Ar2, X1 및 X2에서, 치환 혹은 비치환된 C6~C60 의 방향족기, 치환 혹은 비치환된 C5~C60의 방향족 복소환기, 치환 혹은 비치환된 C1~C60의 알킬기, 치환 혹은 비치환된 C3~C60의 시클로알킬기, 치환 혹은 비치환된 C1~C60의 알콕시기, 치환 혹은 비치환된 C6~C60의 아릴알킬기, 치환 혹은 비치환된 C1~C60의 알킬옥시기, 치환 혹은 비치환된 C5~C60의 아릴옥시기, 치환 혹은 비치환된 C5~C60의 아릴 기, 또는 치환 혹은 비치환된 C5~C60의 헤테로아릴기의 상기 치환은, 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, C1~C60의 알킬기, C2~C60의 알케닐기, C1~C60의 알콕시기, C1~C60의 아미노기, C3~C60의 시클로알킬기, C3~C60의 헤테로시클로알킬기, C6~C60의 아릴기, 또는 C5~C60의 헤테로아릴기로 치환되는 것이나, 이에 한정되지 않는다.In Ar 1 , Ar 2 , X 1 and X 2 of Formula 1, a substituted or unsubstituted C 6 ~ C 60 aromatic group, a substituted or unsubstituted C 5 ~ C 60 aromatic heterocyclic group, substituted or unsubstituted A C 1 to C 60 alkyl group, a substituted or unsubstituted C 3 to C 60 cycloalkyl group, a substituted or unsubstituted C 1 to C 60 alkoxy group, a substituted or unsubstituted C 6 to C 60 arylalkyl group , Substituted or unsubstituted C 1 ~ C 60 alkyloxy group, substituted or unsubstituted C 5 ~ C 60 aryloxy group, substituted or unsubstituted C 5 ~ C 60 aryl group, or substituted or unsubstituted The above substitution of the C 5 to C 60 heteroaryl group is independently deuterium, halogen, nitrile group, nitro group, C 1 to C 60 alkyl group, C 2 to C 60 alkenyl group, C 1 to C 60 An alkoxy group, a C 1 to C 60 amino group, a C 3 to C 60 cycloalkyl group, a C 3 to C 60 heterocycloalkyl group, a C 6 to C 60 aryl group, or a C 5 to C 60 heteroaryl group Substituted Or, and the like.
또한, 본 발명은, 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서,In addition, the present invention, the anode; cathode; And one or more organic material layers interposed between the anode and the cathode.
상기 1층 이상의 유기물층 중 적어도 하나는 본 발명에 따른 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층인 것이 특징인 유기 전계 발광 소자를 제공한다.At least one of the at least one organic material layer provides an organic electroluminescent device, characterized in that the organic material layer containing a compound represented by the formula (1) according to the present invention.
본 발명의 유기 전계 발광 소자에서 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 발광층인 것이 바람직하다.In the organic electroluminescent device of the present invention, the organic material layer including the compound represented by Chemical Formula 1 is preferably a light emitting layer.
본 발명의 화학식 1로 표시되는 화합물을 유기 전계 발광 소자의 발광층 재료로 채택하는 경우, 종래의 발광물질을 사용하는 경우에 비해 전자 수송 능력이 증가됨에 따라 발광효율, 휘도, 전력효율, 구동전압 및 수명 면에서 우수한 특성을 나타내며, 이에 따라 풀 칼라 유기 EL 패널에서 성능 극대화 및 수명 향상에도 큰 효과가 있다.When the compound represented by Chemical Formula 1 of the present invention is adopted as a light emitting layer material of an organic EL device, light emission efficiency, luminance, power efficiency, driving voltage and It exhibits excellent characteristics in terms of lifespan, and therefore has a great effect in maximizing performance and improving lifetime in full color organic EL panels.
본 발명의 화학식 1로 표시되는 화합물은 N(질소)을 포함하는 헤테로아릴기, 비제한적인 예를 들면 피리디닐(pyridinyl)기, 피라지닐(pyrazinyl)기, 피리미디닐(pyrimidinyl)기, 피리다지닐(pyridazinyl)기 등이 안트라센 모이어티(moiety)에 치환된 안트라센 유도체이다. 본 발명의 화학식 1로 표시되는 화합물은 녹색 및/또는 청색 발광 능력을 가진 물질이며, 유기 전계 발광 소자의 유기물층의 재료, 바람직하게는 발광층의 재료, 보다 바람직하게는 발광층의 호스트 재료로 사용될 수 있다.Compound represented by the formula (1) of the present invention is a heteroaryl group containing N (nitrogen), non-limiting examples, such as pyridinyl (pyridinyl), pyrazinyl group, pyrimidinyl group, pyrimidin A pyridazinyl group and the like are anthracene derivatives substituted with an anthracene moiety. The compound represented by Formula 1 of the present invention is a material having green and / or blue light emitting ability, and may be used as a material of an organic material layer of an organic electroluminescent device, preferably a material of a light emitting layer, and more preferably a host material of a light emitting layer. .
아래 화학식 2로 표현된 화합물들은 본 발명의 화학식 1로 표시되는 화합물의 대표적인 예들이나, 본 발명의 화학식 1로 표시되는 화합물이 하기 예시된 것들에 한정되는 것은 아니다.The compounds represented by Formula 2 below are representative examples of the compound represented by Formula 1 of the present invention, but the compound represented by Formula 1 of the present invention is not limited to those illustrated below.
[화학식 2][Formula 2]
이하, 본 발명의 유기 전계 발광 소자의 구성에 대하여 설명한다. Hereinafter, the structure of the organic electroluminescent element of this invention is demonstrated.
본 발명의 유기 전계 발광 소자(이하 '유기 EL 소자'라 함)는, 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 본 발명에 따른 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층인 것이 특징이다.The organic electroluminescent device (hereinafter referred to as 'organic EL device') of the present invention comprises an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer comprising the compound represented by Formula 1 according to the present invention. Is characteristic.
본 발명의 유기 EL 소자의 대표적인 소자 구성으로서는, (1) 양극/발광층/음극; (2) 양극/정공 주입층/발광층/음극; (3) 양극/발광층/전자 주입층/음극; (4) 양극/정공 주입층/발광층/전자 주입층/음극; (5) 양극/유기 반도체층/발광층/음극; (6) 양극/유기 반도체층/전자 장벽층/발광층/음극; (7) 양극/유기 반도체층/발광층/부착 개선층/음극; (8) 양극/정공 주입층/정공 수송층/발광층/전자 주입층/음극; (9) 양극/절연층/발광층/절연층/음극; (10) 양극/무기 반도체층/절연층/발광층/절연층/음극; (11) 양극/유기 반도체층/절연층/발광층/절연층/음극; (12) 양극/절연층/정공 주입층/정공 수송층/발광층/절연층/음극; 또는 (13) 양극/절연층/정공 주입층/정공 수송층/발광층/전자 주입층/음극 등의 구조를 예로 들 수 있으나, 이에 한정되는 것은 아니다. 이들 중 보통 (8)의 구성이 바람직하게 사용되지만, 이에 한정되는 것이 아니다.As a typical element structure of the organic electroluminescent element of this invention, (1) anode / light emitting layer / cathode; (2) anode / hole injection layer / light emitting layer / cathode; (3) anode / light emitting layer / electron injection layer / cathode; (4) anode / hole injection layer / light emitting layer / electron injection layer / cathode; (5) anode / organic semiconductor layer / light emitting layer / cathode; (6) anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode; (7) anode / organic semiconductor layer / light emitting layer / adhesion improving layer / cathode; (8) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode; (9) anode / insulating layer / light emitting layer / insulating layer / cathode; (10) anode / inorganic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode; (11) anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode; (12) anode / insulation layer / hole injection layer / hole transport layer / light emitting layer / insulation layer / cathode; Or (13) an anode / insulating layer / hole injection layer / hole transporting layer / light emitting layer / electron injection layer / cathode. Although the structure of (8) is normally used preferably among these, it is not limited to this.
본 발명의 유기 EL 소자에서, 상기 발광층은 호스트 재료를 함유한다. 상기 호스트 재료가 본 발명의 유기 EL 소자용 재료, 즉 상기 화학식 1로 표시되는 화합물을 함유하는 것이 바람직하며, 상기 호스트 재료가 본 발명의 유기 EL 소자용 재료로 이루어진 것이 보다 더 바람직하다. 이와 같이 발광층이 상기 화학식1로 표시 되는 화합물을 함유할 경우 전자 수송 능력이 증가되어 전공과 전자가 발광층에서 더 좋은 결합을 이루기 때문에 발광효율이 우수할 뿐만 아니라 휘도, 전력효율, 구동전압, 수명 특성 또한 향상된 유기 EL 소자를 제공할 수 있다.In the organic EL device of the present invention, the light emitting layer contains a host material. It is preferable that the said host material contains the organic electroluminescent element material of this invention, ie, the compound represented by the said General formula (1), and it is still more preferable that the said host material consists of the organic electroluminescent element material of this invention. As such, when the light emitting layer contains the compound represented by Chemical Formula 1, the electron transport ability is increased, so that the electron and the electron make a better bond in the light emitting layer, so that the light emitting efficiency is not only excellent, but also the luminance, power efficiency, driving voltage, and lifetime characteristics. It is also possible to provide an improved organic EL device.
본 발명에 있어서 발광층을 형성하는 방법으로서는 증착법, 스핀 코팅법, 또는 LB 법 등과 같은 공지된 방법을 적용할 수 있다.As the method for forming the light emitting layer in the present invention, a known method such as a vapor deposition method, a spin coating method, or an LB method can be applied.
또한, 본 발명의 목적이 손상되지 않는 범위 내에서 본 발명의 유기 EL 소자용 재료 이외의 다른 공지된 발광 재료(예를 들면, PVK, PPV, CBP, Alq, BAlq, 또는 공지된 착체 등)를 발광층에 혼입시킬 수도 있다.In addition, other well-known light emitting materials (for example, PVK, PPV, CBP, Alq, BAlq, a known complex, etc.) other than the material for organic electroluminescent elements of this invention are provided in the range which does not impair the objective of this invention. It can also be mixed in a light emitting layer.
본 발명의 유기 EL 소자는 5 nm 내지 5 ㎛ 의 두께를 갖는 정공 주입층을 구비할 수 있다. 이러한 정공 주입층을 구비하면 발광층 내로의 정공 주입이 양호하게 되어 높은 발광 휘도가 얻어지거나, 또는 저 전압 구동이 가능해 진다. 또한, 이러한 정공 주입층에는, 1 x 104 내지 1 x 106 V/㎝ 범위의 전압을 인가한 경우에 측정되는 정공 이동도가 1 x 10-6 ㎠/V?sec 이상이고 이온화 에너지가 5.5 eV 이하인 화합물을 사용하는 것이 바람직하다.The organic EL device of the present invention may be provided with a hole injection layer having a thickness of 5 nm to 5 mu m. When the hole injection layer is provided, the hole injection into the light emitting layer becomes good, so that high light emission luminance can be obtained or low voltage driving can be performed. In addition, in such a hole injection layer, the hole mobility measured when a voltage in the range of 1 × 10 4 to 1 × 10 6 V / cm is applied is 1 × 10 −6 cm 2 / V · sec or more and the ionization energy is 5.5. Preference is given to using compounds which are below eV.
이러한 정공 주입층용 재료의 예로서는 포르피린 화합물, 방향족 3급 아민 화합물, 스타이릴아민 화합물, 방향족 다이메틸리딘계 화합물 및 축합 방향족 고리 화합물을 들 수 있으며, 보다 구체적인 예로는 4,4'-비스[N-(1-나프틸)-N-페닐아미노]바이페닐 (보통 'NPD' 라 칭한다) 및 4,4',4"-트리스[N-(3-메틸페닐)-N-페닐아미노]트라이페닐아민 (보통 'MTDATA' 라 칭한다) 등과 같은 유기 화합물을 들 수 있다. 또한, 경우에 따라서는 2층 이상의 정공 주입층을 적층하는 것이 더 바람직하다. 이러한 경우, 양극/정공 주입층 1 (정공 주입 재료 1)/정공 주입층 2 (정공 주입 재료 2)/???/발광층의 순서로 적층할 경우, 정공 주입 재료의 이온화 에너지 (Ip) 는 Ip (정공 주입 재료 1)〈 Ip (정공 주입 재료 2) ???의 관계를 만족시키는 것이 소자의 구동 전압을 감소시키는 데에 있어서 바람직하다.Examples of such a hole injection layer material include a porphyrin compound, an aromatic tertiary amine compound, a styrylamine compound, an aromatic dimethylidine compound, and a condensed aromatic ring compound, and more specific examples thereof include 4,4'-bis [N-. (1-naphthyl) -N-phenylamino] biphenyl (commonly referred to as' NPD ') and 4,4', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine ( Organic compounds such as commonly referred to as 'MTDATA', etc. Also, in some cases, it is more preferable to stack two or more hole injection layers, in which case the anode / hole injection layer 1 (hole injection material 1). ) / Hole injection layer 2 (hole injection material 2) / ??? / light emitting layer, the ionization energy Ip of the hole injection material is Ip (hole injection material 1) <Ip (hole injection material 2) Satisfying the relation of ??? to reduce the driving voltage of the device desirable.
또한, 정공 주입층의 구성 성분으로서 p-형 Si 또는 p-형 SiC 와 같은 무기 화합물을 사용하는 것이 바람직하다. 상기 정공 주입층과 양극 사이, 또는 상기 정공 주입층과 발광층 사이에 1 x 10-10 s/㎝ 이상의 전도도를 갖는 유기 반도체층을 설치하는 것도 또한 바람직하다. 이러한 유기 반도체 층을 설치함으로써 발광층 내로의 정공 주입이 더 양호해 진다.It is also preferable to use an inorganic compound such as p-type Si or p-type SiC as a constituent of the hole injection layer. It is also preferable to provide an organic semiconductor layer having a conductivity of 1 × 10 −10 s / cm or more between the hole injection layer and the anode, or between the hole injection layer and the light emitting layer. By providing such an organic semiconductor layer, hole injection into the light emitting layer becomes better.
본 발명의 유기 EL 소자는 5 nm 내지 5 ㎛ 의 두께를 갖는 전자 주입층을 구비할 수 있다. 이러한 전자 주입층을 구비하면 발광층 내로의 전자 주입이 양호하게 되어 높은 발광 휘도가 얻어지거나, 또는 저 전압 구동이 가능해 진다. 또한, 이러한 전자 주입층에는, 1 x 104 내지 1 x 106 V/㎝ 범위의 전압을 인가한 경우에 측정되는 전자 이동도가 1 x 10-6 ㎠/V?sec 이상이고 이온화 에너지가 5.5 eV 초과하는 화합물을 사용하는 것이 바람직하다. 이러한 전자 주입층용 재료의 예로서는 8-하이드록시퀴놀린의 금속 착체(Al 킬레이트: Alq) 또는 그의 유도체, 및 옥사다이아졸 유도체 등을 들 수 있다. 또한, 전자 주입층 내에 알칼리 금속을 혼입시키면 전압을 현저하게 감소시키는 동시에 수명을 연장시킬 수 있다.The organic EL device of the present invention may be provided with an electron injection layer having a thickness of 5 nm to 5 mu m. When such an electron injection layer is provided, electron injection into the light emitting layer becomes good, so that high light emission luminance can be obtained or low voltage driving can be performed. In addition, in such an electron injection layer, the electron mobility measured when a voltage in the range of 1 × 10 4 to 1 × 10 6 V / cm is applied is 1 × 10 −6 cm 2 / V · sec or more and the ionization energy is 5.5. Preference is given to using compounds exceeding eV. As an example of such an electron injection layer material, the metal complex of 8-hydroxyquinoline (Al chelate: Alq) or its derivative (s), an oxadiazole derivative, etc. are mentioned. In addition, incorporation of an alkali metal into the electron injection layer can significantly reduce the voltage and extend the life.
본 발명의 유기 EL 소자는 발광층과 음극과의 사이에 5 nm 내지 5 ㎛ 의 두께를 갖는 정공 장벽층을 설치할 수 있다. 이러한 정공 장벽층을 설치함으로써 유기 발광층 내에 정공을 가두어 두는 성능이 향상되어 높은 발광 휘도가 얻어지거나, 또는 저 전압 구동이 가능해진다.In the organic EL device of the present invention, a hole barrier layer having a thickness of 5 nm to 5 m can be provided between the light emitting layer and the cathode. By providing such a hole barrier layer, the performance of confining holes in the organic light emitting layer is improved, so that high emission luminance is obtained or low voltage driving is possible.
이러한 정공 장벽층의 예로는 2,9-다이메틸-4,7-다이페닐-1,10-페난트롤린 및 2,9-다이에틸-4,7-다이페닐-1,10-페난트롤린 등을 들 수 있지만, 알칼리 금속, 예를 들면 Li 또는 Cs 를 더 함유하는 것이 바람직하다. 상술된 바와 같이, 정공 장벽층용 재료에 알칼리 금속을 조합시키면 유기 EL 소자를 구동시키는 전압을 현저하게 감소시키는 동시에 소자의 수명을 연장시킬 수 있다. 한편, 알칼리 금속을 함유시키는 경우, 그 함유량은 정공 장벽층의 총량을 100 중량%라 정의하였을 때 바람직하게는 0.01 내지 30 중량%, 보다 바람직하게는 0.05 내지 20 중량%, 보다 더 바람직하게는 0.1 내지 15 중량%이다. 그 이유는, 알칼리 금속의 함유량이 0.01 중량% 이상인 경우에는 알칼리 금속의 첨가 효과가 발휘되는 반면, 함유량이 30 중량% 이하인 경우에는 알칼리 금속의 분산성이 균일하게 되어 발광 휘도가 변하지 않기 때문이다.Examples of such hole barrier layers are 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 2,9-diethyl-4,7-diphenyl-1,10-phenanthroline Although an alkali metal, for example, Li or Cs is contained further, it is preferable. As described above, incorporation of an alkali metal into the material for the hole barrier layer can significantly reduce the voltage for driving the organic EL element and at the same time extend the life of the element. On the other hand, when the alkali metal is contained, the content thereof is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, even more preferably 0.1 when the total amount of the hole barrier layer is defined as 100% by weight. To 15% by weight. The reason is that when the content of the alkali metal is 0.01% by weight or more, the effect of adding the alkali metal is exerted, whereas when the content is 30% by weight or less, the dispersibility of the alkali metal is uniform and the luminescence brightness does not change.
본 발명에 있어서, 상기 정공 주입층, 전자 주입층 또는 정공 장벽층을 형성하는 방법으로서는, 예를 들면 증착법, 스핀 코팅법 또는 LB 법 등과 같은 공지된 방법을 적용할 수 있다.In the present invention, as the method for forming the hole injection layer, the electron injection layer or the hole barrier layer, a known method such as a vapor deposition method, spin coating method or LB method can be applied.
본 발명의 유기 EL 소자에는 음극과 유기 박막층 사이의 계면 영역에 환원성 도펀트가 첨가되는 것이 바람직하다. 환원성 도펀트의 예로서는 알칼리 금속, 알칼 리 금속 착체, 알칼리 금속 화합물, 알칼리 토금속, 알칼리 토금속 착체, 알칼리 토금속 화합물, 희토류 금속, 희토류 금속 착체, 희토류 금속 화합물, 및 이들의 할로겐 화합물 및 산화물 중에서 선택된 적어도 1 종류를 들 수 있다.In the organic EL device of the present invention, it is preferable that a reducing dopant is added to the interface region between the cathode and the organic thin film layer. Examples of the reducing dopant include at least one selected from alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earth metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and halogen compounds and oxides thereof. Can be mentioned.
상기 알칼리 금속의 예로서는 Li (일함수 : 2.93 eV), Na (일함수 : 2.36 eV), K (일함수 : 2.28 eV), Rb (일함수 : 2.16 eV), Cs (일함수 : 1.95 eV) 등을 들 수 있으며, 일함수가 3.0 eV 이하의 알칼리 금속이 특히 바람직하다. 물론, Li, K, Rb 및 Cs 가 바람직하다.Examples of the alkali metal include Li (work function: 2.93 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like. And alkali metals having a work function of 3.0 eV or less are particularly preferable. Of course, Li, K, Rb and Cs are preferred.
상기 알칼리 토금속의 예로서는 Ca (일함수 : 2.9 eV), Sr (일함수 : 2.0 내지 2.5 eV) 및 Ba (일함수 : 2.52 eV) 등을 들 수 있으며, 일함수가 3.0 eV 이하의 알칼리 토금속이 특히 바람직하다.Examples of the alkaline earth metal include Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), Ba (work function: 2.52 eV), and the like. desirable.
상기 희토류 금속의 예로서는 Sc, Y, Ce, Tb 및 Yb 등을 들 수 있으며, 일함수가 3.0 eV 이하의 희토류 금속이 특히 바람직하다.Examples of the rare earth metal include Sc, Y, Ce, Tb and Yb, and a rare earth metal having a work function of 3.0 eV or less is particularly preferable.
이상의 금속 중에서 바람직한 금속은 특히 높은 환원 능력을 가지므로, 전자 주입역에 비교적 소량의 금속을 첨가함으로써 유기 EL 소자의 발광 강도를 향상시키고 수명을 연장 시킬 수 있다.Preferred metals among the above metals have particularly high reducing ability, and therefore, by adding a relatively small amount of metal to the electron injection region, the light emission intensity of the organic EL device can be improved and the life can be extended.
상기 알칼리 금속 화합물의 예로서는 Li2O, Cs2O 또는 K2O 등과 같은 알칼리 산화물, 및 LiF, NaF, CsF 또는 KF 등과 같은 알칼리 할로겐화물 등을 들 수 있으며, LiF, Li2O 또는 NaF 와 같은 알칼리 산화물 또는 알칼리 불화물이 바람직하다.Examples of the alkali metal compound include alkali oxides such as Li 2 O, Cs 2 O or K 2 O, and alkali halides such as LiF, NaF, CsF or KF, and the like, and examples thereof include LiF, Li 2 O or NaF. Alkali oxides or alkali fluorides are preferred.
상기 알칼리 토금속 화합물의 예로서는 BaO, SrO, CaO, 및 이들의 혼합물, 예를 들면 BaxSr1-xO (0〈x〈1) 및 BaxCa1-xO (0〈x〈1) 등을 들 수 있으며, 이들 중 BaO, SrO 및 CaO 가 바람직하다.Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixtures thereof, such as Ba x Sr 1-x O (0 <x <1) and Ba x Ca 1-x O (0 <x <1) and the like. These include BaO, SrO and CaO.
상기 희토류 금속 화합물의 예로서는 YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3 및 TbF3 등이 있으며, 이들 중 YbF3, ScF3 및 TbF3 이 바람직하다.Examples of the rare earth metal compound include YbF 3 , ScF 3 , ScO 3 , Y 2 O 3 , Ce 2 O 3 , GdF 3 and TbF 3 , and among these, YbF 3 , ScF 3 and TbF 3 are preferable.
상기 알칼리 금속 착체, 알칼리 토금속 착체, 희토류 금속 착체는 그들이 각각 금속 이온으로서 하나 이상의 알칼리 금속 이온, 알칼리 토금속 이온, 희토류 금속 이온을 함유하는 한은 특별한 한정은 없다. 또한, 리간드의 바람직한 예로는 퀴놀린올, 벤조퀴놀린올, 아키리딘올, 페난트리딘올, 하이드록시페닐옥사졸, 하이드록시페닐싸이아졸, 하이드록시다이아릴옥사다이아졸, 하이드록시다이아릴싸이아다이아졸, 하이드록시페닐피리딘, 하이드록시페닐벤조이미다졸, 하이드록시벤조트라이아졸, 하이드록시플루보레인, 바이피리딜, 페난트롤린, 프탈로시아닌, 포르피린, 사이클로펜타다이엔, β-다이케톤류, 아조메타인류, 및 그들의 유도체 등을 들 수 있지만, 그들로 국한되는 것은 아니다.The alkali metal complex, alkaline earth metal complex and rare earth metal complex are not particularly limited as long as they each contain one or more alkali metal ions, alkaline earth metal ions and rare earth metal ions as metal ions. In addition, preferred examples of the ligand include quinolinol, benzoquinolinol, akyridinol, phenantridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxy diaryl oxadiazole, and hydroxy diaryl thiazole. , Hydroxyphenylpyridine, hydroxyphenylbenzoimidazole, hydroxybenzotriazole, hydroxyflubolane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines , And derivatives thereof, and the like, but are not limited thereto.
환원성 도펀트의 첨가 형태로서는, 환원성 도펀트가 상기 계면 영역 내에 층상 또는 섬(island) 형상으로 형성되는 것이 바람직하다. 바람직한 형성 방법으로서는 저항 가열 증착법에 의해 환원성 도펀트를 증착하는 동시에 계면 영역을 형성하는 발광 재료나 전자 주입 재료인 유기 물질을 동시에 증착시킴으로써 유기 물질 중에 환원성 도펀트를 분산시키는 방법이 있다. 유기 화합물 : 환원성 도펀트의 몰 비로서의 분산 농도는 100 : 1 내지 1 : 100, 바람직하게는 5 : 1 내지 1 : 5 이 다.As a form of addition of the reducing dopant, it is preferable that the reducing dopant is formed in a layered or island shape in the interface region. As a preferable formation method, there is a method of dispersing a reducing dopant in an organic material by depositing a reducing dopant by a resistive heating deposition method and simultaneously depositing an organic material which is a light emitting material or an electron injection material that forms an interface region. The dispersion concentration as the molar ratio of organic compound: reducing dopant is 100: 1 to 1: 100, preferably 5: 1 to 1: 5.
환원성 도펀트를 층 형상으로 형성하는 경우, 계면 내에 유기층으로서 제공하는 발광 재료 또는 전자 주입 재료를 층 형상으로 형성 시킨 후에, 환원성 도펀트를 저항 가열 증착법에 의해 단독으로 증착시켜 바람직하게는 0.05 내지 1㎚의 두께를 갖는 섬을 형성시킨다.In the case of forming the reducing dopant in the form of a layer, after forming the light emitting material or the electron injecting material serving as the organic layer in the interface in the form of a layer, the reducing dopant is deposited by resistive heating evaporation alone, preferably 0.05 to 1 nm. Form an island with a thickness.
본 발명의 유기 EL 소자에 있어서의 양극은 유기 EL 표시 장치의 구성에 따라 하부 전극 또는 대향 전극에 해당하지만, 큰 (예를 들면, 4.0 eV 이상) 일함수를 갖는 금속, 합금, 또는 전기 전도성 화합물 또는 이들의 혼합물을 상기 양극에 사용하는 것이 바람직하다. 구체적으로는, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO), 요오드화 구리(CuI), 산화주석(SnO2), 산화아연(ZnO), 금, 백금, 팔라듐 등과 같은 전극 재료를 단독으로 사용하거나, 또는 이들 전극 재료를 2종 이상 조합하여 사용하는 것이 바람직하다. 이러한 전극 재료를 사용함으로써 진공 증착법, 스퍼터링법, 이온 도금법, 전자빔 증착법, CVD(Chemical Vapor Deposition) 방법, MOCVD(Metal Oxide Chemical Vapor Deposition) 방법, 또는 플라즈마 CVD 방법과 같은 건조 상태에서 성막이 가능한 방법을 이용하여 균일한 두께를 갖는 양극을 형성할 수 있다. The anode in the organic EL device of the present invention corresponds to the lower electrode or the counter electrode depending on the structure of the organic EL display device, but is a metal, alloy, or electrically conductive compound having a large (for example, 4.0 eV or more) work function. Or a mixture thereof is preferably used for the positive electrode. Specifically, electrode materials such as indium tin oxide (ITO), indium zinc oxide (IZO), copper iodide (CuI), tin oxide (SnO 2 ), zinc oxide (ZnO), gold, platinum, palladium and the like are used alone. Or it is preferable to use these electrode materials in combination of 2 or more type. By using such an electrode material, a method capable of forming a film in a dry state such as vacuum deposition, sputtering, ion plating, electron beam deposition, chemical vapor deposition (CVD), metal oxide chemical vapor deposition (MOCVD), or plasma CVD It can be used to form a positive electrode having a uniform thickness.
한편, 양극에서 EL 발광을 추출하는 경우, 상기 양극을 투명 전극으로 할 필요가 있다. 그러한 경우에는, ITO, IZO, CuI, SnO2 또는 ZnO 와 같은 도전성 투명 재료를 사용하여 EL 발광의 투과율 값이 70% 이상이 되도록 하는 것이 바람직하다. On the other hand, when extracting EL light emission from an anode, it is necessary to make the anode into a transparent electrode. In such a case, it is preferable to use a conductive transparent material such as ITO, IZO, CuI, SnO 2 or ZnO so that the transmittance value of EL light emission is 70% or more.
또한, 양극의 막 두께도 특별히 제한되는 것이 아니지만, 이들 두께 값은 바람직하게는 10 내지 1,000㎚ 범위, 보다 바람직하게는 10 내지 200㎚ 범위 내의 값으로 하는 것이 좋다. 그 이유는, 양극의 막 두께가 이러한 범위 내의 값을 갖는 경우에 균일한 막 두께 분포 및 70 % 이상의 EL 발광의 투과율이 얻어지는 한편, 시이트 저항값을 바람직하게는 1,000 Ω/A 이하, 보다 바람직하게는 100 Ω/A 이하로 유지할 수 있기 때문이다. Further, the thickness of the anode is not particularly limited either, but these thickness values are preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 200 nm. The reason is that when the thickness of the anode has a value within this range, a uniform film thickness distribution and transmittance of EL light emission of 70% or more are obtained, while the sheet resistance value is preferably 1,000 Ω / A or less, more preferably. This is because it can be kept below 100 Ω / A.
한편, 양극(하부 전극), 유기 발광매체, 및 음극(대향 전극)을 순차적으로 설치하고, 상기 하부 전극 및 대향 전극을 XY 매트릭스 형상으로 구성함으로써 발광면 내의 임의의 화소를 발광시키는 것도 바람직하다. 즉, 상술한 바와 같이 양극 등을 구성함으로써 유기 EL 소자에 있어서 다양한 정보를 용이하게 표시할 수 있다.On the other hand, the anode (lower electrode), the organic light emitting medium, and the cathode (counter electrode) are sequentially provided, and the lower electrode and the counter electrode are configured in an XY matrix shape to emit any pixel in the light emitting surface. That is, by forming an anode or the like as described above, various information can be easily displayed in the organic EL element.
또한, 본 발명의 유기 EL 소자에 있어서의 음극도 유기 EL 소자의 구성에 따라 하부 전극 또는 대향 전극에 해당하지만, 작은(예를 들면, 4.0 eV 미만) 일함수를 갖는 금속, 합금, 또는 전기 전도성 화합물 또는 이들의 혼합물 또는 이들을 함유하는 함유물을 사용하는 것이 바람직하다. 구체적으로는 나트륨, 나트륨-칼륨 합금, 세슘, 마그네슘, 리튬, 마그네슘-은 합금, 알루미늄, 산화 알루미늄, 알루미늄-리튬 합금, 인듐, 및 희토류 금속; 이들 금속과 유기 박막층용 재료와의 혼합물; 및 이들 금속과 전자 주입층용 재료와의 혼합물로 이루어진 전극 재료를 단독으로 사용하거나 또는 이들의 전극 재료를 2종 이상 조합하여 사용하는 것이 바람직하다. In addition, the cathode in the organic EL device of the present invention also corresponds to the lower electrode or the counter electrode depending on the structure of the organic EL device, but has a small (for example, less than 4.0 eV) metal, alloy, or electrical conductivity. Preference is given to using the compounds or mixtures thereof or inclusions containing them. Specifically, sodium, sodium-potassium alloys, cesium, magnesium, lithium, magnesium-silver alloys, aluminum, aluminum oxide, aluminum-lithium alloys, indium, and rare earth metals; Mixtures of these metals and materials for organic thin film layers; And it is preferable to use the electrode material which consists of a mixture of these metals and the material for an electron injection layer alone, or to use these electrode materials in combination of 2 or more types.
또한, 음극의 막 두꼐도 양극의 경우와 같이 특별히 제한되는 것이 아니지만, 음극의 막 두께는 바람직하게는 10 내지 1,000㎚의 범위, 보다 바람직하게는 10 내지 200㎚의 범위이다. 또한, 음극으로부터 EL 발광을 끌어내는 경우에는 상기 음극은 투명 전극이 되어야 하며, 그러한 경우, EL 발광의 투과율 값을 70 % 이상으로 하는 것이 바람직하다. 한편 음극의 경우에도 양극의 경우에서와 같이, 진공 증착법이나 스퍼터링법과 같은 건조 상태에서 성막이 가능한 방법을 이용하여 음극을 형성하는 것이 바람직하다.Further, the film thickness of the cathode is not particularly limited as in the case of the anode, but the film thickness of the cathode is preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 200 nm. In addition, in the case of drawing the EL light emission from the cathode, the cathode should be a transparent electrode, and in such a case, it is preferable that the transmittance value of the EL light emission is 70% or more. In the case of the cathode, on the other hand, as in the case of the anode, it is preferable to form the cathode by using a method capable of film formation in a dry state such as vacuum deposition or sputtering.
본 발명의 유기 EL 소자에 있어서의 지지 기판은 기계적 강도가 우수하여 수분이나 산소의 투과성이 적은 것이 바람직하다. 이러한 지지 기판의 구체적인 예로는 유리 시이트, 금속 시이트, 세라믹 시이트 및 플라스틱 시이트 (예를 들면, 폴리카보네이트 수지, 아크릴 수지, 바이닐 클로라이드 수지, 폴리에틸렌 테레프탈레이트 수지, 폴리이미드 수지, 폴리에스터 수지, 에폭시 수지, 페놀 수지, 실리콘 수지 또는 불소 수지등으로 제조한 시이트) 등을 들 수 있다. 또한, 이들 재료로 이루어진 지지 기판은 유기 EL 소자 내로 수분이 침입하는 것을 방지하기 위하여 지지 기판상에 무기막을 더 형성시키거나 또는 불소 수지를 도포하여 방습 처리하거나 소수성 처리를 하는 것이 바람직하다. 또한 특히 유기 박막층 내로 수분이 침입하는 것을 방지하기 위하여 지지 기판에 있어서의 함수율 및 가스 투과 계수를 작게 하는 것이 바람직하다. 구체적으로는 지지 기판의 함수율 및 가스 투과 계수를 각각 0.0001 중량% 이하 및 1 × 10-1 ㏄?㎝/㎠?sec?㎝Hg 이하로 하는 것이 바람직하다.It is preferable that the support substrate in the organic electroluminescent element of this invention is excellent in mechanical strength, and has little water and oxygen permeability. Specific examples of such support substrates include glass sheets, metal sheets, ceramic sheets and plastic sheets (eg, polycarbonate resins, acrylic resins, vinyl chloride resins, polyethylene terephthalate resins, polyimide resins, polyester resins, epoxy resins, A sheet made of a phenol resin, a silicone resin, a fluororesin, or the like). In addition, it is preferable that the supporting substrate made of these materials is further formed with an inorganic film on the supporting substrate or coated with a fluorine resin to provide moisture proof or hydrophobic treatment in order to prevent moisture from entering the organic EL element. In addition, in order to prevent the ingress of moisture into the organic thin film layer, it is particularly desirable to reduce the moisture content and the gas permeability coefficient in the support substrate. Specifically, the water content and the gas permeability coefficient of the support substrate are preferably 0.0001 wt% or less and 1 × 10 −1 Pa · cm / cm 2 · sec · cmHg or less, respectively.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[합성예 1] 5-bromo-2-(naphthalen-1-yl)pyridine의 제조Synthesis Example 1 Preparation of 5-bromo-2- (naphthalen-1-yl) pyridine
2,5-dibromopyridine (82.6 g, 348.7 mmol), naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol)을 toluene 800 mL에 녹인 후 Pd(PPh3)4 (10.1 g, 8.7 mmol)을 질소 하에서 넣었다. 그리고 Na2CO3 (92.4 g, 871.7 mmol)을 증류수 240 mL에 녹여서 투입하였다. 그리고 EtOH (240 mL)를 추가로 넣었다. 반응 용액을 5시간 동안 환류 교반하였다. 반응이 종결된 후 dichloromethane와 distilledwater을 사용하여 추출하고, 얇은 실리카겔 패드에 고온 여과를 하여 팔라듐을 제거하였다. 이 유기 용매층을 감압 증류하여 용매를 거의 날린 후 여과하여 1차로 갈색의 고체 생성물을 얻었다. 여액을 소량의 dichloromethane로 녹인 다음 온도를 내려 재결정화하고 이것을 여과하여 흰색 고체 (74.5 g, 수율 91 %)를 얻었다.2,5-dibromopyridine (82.6 g, 348.7 mmol) and naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol) were dissolved in 800 mL of toluene and Pd (PPh 3 ) 4 (10.1 g, 8.7 mmol) was added under nitrogen. . And Na 2 CO 3 (92.4 g, 871.7 mmol) was dissolved in 240 mL of distilled water was added. And additional EtOH (240 mL) was added. The reaction solution was stirred at reflux for 5 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then cooled to recrystallization and filtered to give a white solid (74.5 g, 91% yield).
1H NMR : 7.35 (m, 3H), 7.71 (t, 2H), 7.83 (d, 2H), 8.10 (d, 1H), 8.49 (t, 1H), 8.81 (s, 1H). 1 H NMR: 7.35 (m, 3H), 7.71 (t, 2H), 7.83 (d, 2H), 8.10 (d, 1H), 8.49 (t, 1H), 8.81 (s, 1H).
[합성예 2] 2-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine의 제조Synthesis Example 2 Preparation of 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine
5-bromo-2-(naphthalen-1-yl)pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH3COOK (67.1 g, 683.5 mmol)을 1,4-dioxane 1000 mL에 녹인 후 Pd(dppf)Cl2 (5.0 g, 0.8 mmol)을 질소 하에서 넣었다. 반응 용액을 12시간 동안 환류 교반하였다. 반응이 종결된 후 dichloromethane와 distilledwater을 사용하여 추출하고, 얇은 실리카겔 패드에 여과를 하여 팔라듐을 제거하였다. 이 유기 용매층을 감압 증류하여 용매를 거의 날린 후 여과하여 1차로 갈색의 고체 생성물을 얻었다. 여액을 소량의 dichloromethane로 녹인 다음 silicacolumn하여 연갈색 고체 (67.9 g, 수율 90 %)를 얻었다.5-bromo-2- (naphthalen-1-yl) pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH 3 COOK (67.1 g, 683.5 mmol) After dissolving in 1000 mL of dioxane, Pd (dppf) Cl 2 (5.0 g, 0.8 mmol) was added under nitrogen. The reaction solution was stirred at reflux for 12 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and filtered through a thin pad of silica gel to remove palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then silicacolumn to give a light brown solid (67.9 g, yield 90%).
1H NMR : 1.31 (s, 12H), 7.36 (m, 3H), 7.46 (t, 2H), 7.78 (d, 2H), 8.06 (d, 1H), 8.47 (t, 1H), 8.55 (s, 1H). 1 H NMR: 1.31 (s, 12H), 7.36 (m, 3H), 7.46 (t, 2H), 7.78 (d, 2H), 8.06 (d, 1H), 8.47 (t, 1H), 8.55 (s, 1H).
[합성예 3] 2-bromo-6-(naphthalen-1-yl)pyridine의 제조Synthesis Example 3 Preparation of 2-bromo-6- (naphthalen-1-yl) pyridine
2,6-dibromopyridine (82.6 g, 348.7 mmol), naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol)을 toluene 800 mL에 녹인 후 Pd(PPh3)4 (10.1 g, 8.7 mmol)을 질소 하에서 넣었다. 그리고 Na2CO3 (92.4 g, 871.7 mmol)을 증류수 240 mL에 녹여서 투입하였다. 그리고 EtOH (240 mL)를 추가로 넣었다. 반응 용액을 5시간 동안 환류 교반하였다. 반응이 종결된 후 dichloromethane와 distilledwater을 사용하여 추출하고, 얇은 실리카겔 패드에 고온 여과를 하여 팔라듐을 제거하였다. 이 유기 용매층을 감압 증류하여 용매를 거의 날린 후 여과하여 1차로 갈색의 고체 생성물을 얻었다. 여액을 소량의 dichloromethane로 녹인 다음 온도를 내려 재결정화하고 이것을 여과하여 흰색 고체 (71.5 g, 수율 87 %)를 얻었다.2,6-dibromopyridine (82.6 g, 348.7 mmol) and naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol) were dissolved in 800 mL of toluene and Pd (PPh 3 ) 4 (10.1 g, 8.7 mmol) was added under nitrogen. . And Na 2 CO 3 (92.4 g, 871.7 mmol) was dissolved in 240 mL of distilled water was added. And additional EtOH (240 mL) was added. The reaction solution was stirred at reflux for 5 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then cooled down to recrystallize and filtered to give a white solid (71.5 g, 87% yield).
1H NMR : 7.33 (m, 4H), 7.58 (m, 4H), 8.01 (d, 1H), 8.47 (d, 1H). 1 H NMR: 7.33 (m, 4H), 7.58 (m, 4H), 8.01 (d, 1H), 8.47 (d, 1H).
[합성예 4] 2-(naphthalen-1-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine의 제조Synthesis Example 4 Preparation of 2- (naphthalen-1-yl) -6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine
2-bromo-6-(naphthalen-1-yl)pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH3COOK (67.1 g, 683.5 mmol)을 1,4-dioxane 1000 mL에 녹인 후 Pd(dppf)Cl2 (5.0 g, 0.8 mmol)을 질소 하에서 넣었다. 반응 용액을 12시간 동안 환류 교반하였다. 반응이 종결된 후 dichloromethane와 distilledwater을 사용하여 추출하고, 얇은 실리카겔 패드에 여과를 하여 팔라듐을 제거하였다. 이 유기 용매층을 감압 증류하여 용매를 거의 날린 후 여과하여 1차로 갈색의 고체 생성물을 얻었다. 여액을 소량의 dichloromethane로 녹인 다음 silicacolumn하여 연갈색 고체 (60.4 g, 수율 80 %)를 얻었다.2-bromo-6- (naphthalen-1-yl) pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH 3 COOK (67.1 g, 683.5 mmol) After dissolving in 1000 mL of dioxane, Pd (dppf) Cl 2 (5.0 g, 0.8 mmol) was added under nitrogen. The reaction solution was stirred at reflux for 12 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and filtered through a thin pad of silica gel to remove palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and silicacolumn to give a light brown solid (60.4 g, yield 80%).
1H NMR : 1.34 (s, 12H), 7.12 (t, 1H), 7.31 (m, 2H), 7.51 (m, 5H), 8.05 (d, 1H), 8.45 (d, 1H). 1 H NMR: 1.34 (s, 12H), 7.12 (t, 1H), 7.31 (m, 2H), 7.51 (m, 5H), 8.05 (d, 1H), 8.45 (d, 1H).
[실시예 1] Inv-1 의 제조Example 1 Preparation of Inv-1
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (10.4 g, 31.4 mmol)을 toluene 200 mL에 녹인 후 Pd(PPh3)4 (0.6 g, 0.5 mmol)을 질소 하에서 넣었다. 그리고 Na2CO3 (8.3 g, 78.5 mmol)을 증류수 100 mL에 녹여서 투입하였다. 반응 용액을 6시간 동안 환류 교반하였다. 반응이 종결된 후 dichloromethane와 distilledwater을 사용하여 추출하고, 얇은 실리카겔 패드에 고온 여과를 하여 팔라듐을 제거하였다. 이 유기 용매층을 감압 증류하여 용매를 거의 날린 후 여과하여 1차로 갈색의 고체 생성물을 얻었다. 여액을 소량의 dichloromethane로 녹인 다음 silicacolumn 하여 연노란색 고체 (10.9 g, 수율 82 %)를 얻었다.9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene and Pd (PPh 3 ) 4 (0.6 g, 0.5 mmol) was added under nitrogen. And Na 2 CO 3 (8.3 g, 78.5 mmol) was dissolved in 100 mL of distilled water was added. The reaction solution was stirred at reflux for 6 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and silicacolumn to give a pale yellow solid (10.9 g, yield 82%).
1H NMR : 7.37 (t, 2H), 7.38 (t, 2H), 7.48 (dd, 2H), 7.52 (t, 2H), 7.58 (d, 1H), 7.62 (m, 4H), 7.71 (d, 2H), 7.81 (m, 4H), 7.98 (m, 4H), 8.53 (t, 1H), 8.85 (d, 1H) ; FD-MS: m/z 508 (M+). 1 H NMR: 7.37 (t, 2H), 7.38 (t, 2H), 7.48 (dd, 2H), 7.52 (t, 2H), 7.58 (d, 1H), 7.62 (m, 4H), 7.71 (d, 2H), 7.81 (m, 4H), 7.98 (m, 4H), 8.53 (t, 1H), 8.85 (d, 1H); FD-MS: m / z 508 (M + ).
[실시예 2] Inv-3 의 제조Example 2 Preparation of Inv-3
9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (10.8 g, 32.5 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-3 (10.2 g, 수 율 82 %)를 얻었다. FD-MS: m/z 408 (M+).9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Pyridine (10.8 g, 32.5 mmol) was dissolved in 200 mL of toluene. Inv-3 (10.2 g, yield 82%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 408 (M + ).
[실시예 3] Inv-4 의 제조Example 3 Preparation of Inv-4
9-(biphenyl-4-yl)-10-bromoanthracene (10.0 g, 24.5 mmol), 2-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (9.7 g, 29.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-4 (11.2 g, 수율 86 %) 를 얻었다. FD-MS: m/z 534 (M+).9- (biphenyl-4-yl) -10-bromoanthracene (10.0 g, 24.5 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl) pyridine (9.7 g, 29.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-4 (11.2 g, yield 86%). FD-MS: m / z 534 (M + ).
[실시예 4] Inv-11 의 제조Example 4 Preparation of Inv-11
9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2-(naphthalen-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (10.8 g, 32.5 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-11 (9.9 g, 수율 80 %) 를 얻었다. FD-MS: m/z 458 (M+).9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2- (naphthalen-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Pyridine (10.8 g, 32.5 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-11 (9.9 g, 80% yield). FD-MS: m / z 458 (M + ).
[실시예 5] Inv-17 의 제조Example 5 Preparation of Inv-17
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (8.8 g, 31.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-17 (11.0 g, 수 율 92 %) 를 얻었다. FD-MS: m/z 458 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl pyridine (8.8 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-17 (11.0 g, yield 92%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 458 (M + ).
[실시예 6] Inv-20 의 제조Example 6 Preparation of Inv-20
9-(biphenyl-4-yl)-10-bromoanthracene (10.0 g, 24.5 mmol), 2-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (8.3 g, 29.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-20 (10.4 g, 수율 88 %) 를 얻었다. FD-MS: m/z 484 (M+).9- (biphenyl-4-yl) -10-bromoanthracene (10.0 g, 24.5 mmol), 2-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (8.3 g, 29.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-20 (10.4 g, yield 88%). FD-MS: m / z 484 (M + ).
[실시예 7] Inv-25 의 제조Example 7 Preparation of Inv-25
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(naphthalen-1-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (10.4 g, 31.4 mmol)을 toluene 200 mL 에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-25 (12.1 g, 수율 91 %)를 얻었다. FD-MS: m/z 508 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-1-yl) -6- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-25 (12.1 g, 91% yield). FD-MS: m / z 508 (M + ).
[실시예 8] Inv-33 의 제조Example 8 Preparation of Inv-33
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(naphthalen-2-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (10.4 g, 31.4 mmol)을 toluene 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합 성하여 Inv-33 (11.8 g, 수율 89 %)를 얻었다. FD-MS: m/z 508 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-2-yl) -6- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-33 (11.8 g, 89% yield). FD-MS: m / z 508 (M + ).
[실시예 9] Inv-41 의 제조Example 9 Preparation of Inv-41
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (8.8 g, 31.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-41 (10.7 g, 수율 84 %)를 얻었다. FD-MS: m/z 458 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl pyridine (8.8 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-41 (10.7 g, yield 84%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 458 (M + ).
[실시예 10] Inv-50 의 제조Example 10 Preparation of Inv-50
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazine (6.5 g, 31.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-50 (7.5 g, 수율 75 %)를 얻었다. FD-MS: m/z 383 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrazine (6.5 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-50 (7.5 g, yield 75%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 383 (M + ).
[실시예 11] Inv-62 의 제조Example 11 Preparation of Inv-62
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine (6.5 g, 31.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-62 (7.0 g, 수율 70 %) 를 얻었다. FD-MS: m/z 383 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrimidine (6.5 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-62 (7.0 g, yield 70%). FD-MS: m / z 383 (M + ).
[실시예 12] Inv-65 의 제조Example 12 Preparation of Inv-65
9-bromo-10-(naphthalen-2-yl)anthracene (10.0 g, 26.2 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(thiophen-2-yl)pyridine (9.0 g, 31.4 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-65 (9.0 g, 수율 74 %)를 얻었다. FD-MS: m/z 464 (M+).9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (thiophen-2-yl) pyridine (9.0 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-65 (9.0 g, yield 74%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 464 (M + ).
[실시예 13] Inv-69 의 제조Example 13 Preparation of Inv-69
9-bromo-10-(naphthalen-2-yl)-2-phenylanthracene (10.0 g, 21.8 mmol), 2-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (8.7 g, 26.2 mmol)을 톨루엔 200 mL에 녹였다. 실시예 1과 동일한 방법으로 합성하여 Inv-69 (10.2 g, 수율 80 %)를 얻었다. FD-MS: m/z 584 (M+).9-bromo-10- (naphthalen-2-yl) -2-phenylanthracene (10.0 g, 21.8 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) pyridine (8.7 g, 26.2 mmol) was dissolved in 200 mL of toluene. Inv-69 (10.2 g, yield 80%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 584 (M + ).
[실시예 14 ~ 27] 유기 EL 소자의 제조 및 평가Examples 14 to 27 Fabrication and Evaluation of Organic EL Device
실시예 1 내지 실시예 13을 통해 합성된 각각의 생성물(Inv-x)을 녹색 또는 청색 호스트 재료로 이용하여 표 1 및 표 2 와 같은 소자를 구성한 후 표 3에 평가 결과를 나타내었다.Each product (Inv-x) synthesized through Examples 1 to 13 was used as a green or blue host material to configure devices as shown in Tables 1 and 2, and the evaluation results are shown in Table 3 below.
녹색 발광 도판트 재료는 당사에서 기출원한 재료인 DS-501(두산社) 및 청색 발광 도판트 재료는 당사에서 기출원한 재료인 DS-405(두산 社)를 사용하였다.Green-emitting dopant material is DS-501 (Doosan Corporation), which is a material that we have previously applied, and DS-405 (Doosan Corporation), which is a material we have previously used, is used.
[비교예 1] 유기 EL 소자의 제조 및 평가Comparative Example 1 Fabrication and Evaluation of Organic EL Device
실시예 1 내지 13에서 합성된 생성물(Inv-x) 대신 종래 C545T를 녹색 호스트 재료로 이용한 것을 제외하고는 표 2와 동일한 형태의 소자를 구성한 후 표 3에 평가 결과를 나타내었다.The evaluation results are shown in Table 3 after configuring the same type of device as in Table 2 except for using the conventional C545T as a green host material instead of the product (Inv-x) synthesized in Examples 1 to 13.
[비교예 2] 유기 EL 소자의 제조 및 평가Comparative Example 2 Fabrication and Evaluation of Organic EL Device
실시예 1 내지 13에서 합성된 생성물(Inv-x) 대신 종래 ADN을 청색 호스트 재료로 이용한 것을 제외하고는 표 1과 동일한 형태의 소자를 구성한 후 표 3에 평가 결과를 나타내었다. The evaluation results are shown in Table 3 after configuring the same type of device as in Table 1 except for using ADN as a blue host material instead of the product (Inv-x) synthesized in Examples 1 to 13.
[표 1] 청색 소자 구조[Table 1] Blue Device Structure
[표 2] 녹색 및 소자 구조Table 2 Green and Device Structure
이때, NPB, ADN 및 C545T의 구조는 하기와 같다.At this time, the structure of NPB, ADN and C545T is as follows.
NPBNPB
C545TC545T
ADNADN
[표 3] 소자 특성[Table 3] Device Characteristics
Density
(mA/㎠)Current
Density
(mA / ㎠)
(V)Voltage
(V)
(cd/㎡)Luminance
(cd / ㎡)
(cd/A)Efficiency
(cd / A)
구조
device
rescue
이상에서 살펴본 바와 같이, 본 발명에 따른 화합물을 사용한 유기 EL 소자 (실시예 13 내지 27)는 호스트 재료별로 종래 C545T 및 ADN을 사용한 유기 EL 소자(비교예 1 및 2)와 비교했을 때 전압 및 효율 면에서 월등한 성능을 나타내는 것을 확인할 수 있었다.As described above, the organic EL device (Examples 13 to 27) using the compound according to the present invention has a voltage and efficiency when compared with the organic EL device (Comparative Examples 1 and 2) using conventional C545T and ADN for each host material. It was confirmed that the performance was excellent in terms of.
이상을 통해 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various changes and modifications may be made without departing from the scope of the invention. It is natural to belong.
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