WO2015076601A1 - Novel light emission compound and organic light emitting device comprising same - Google Patents

Novel light emission compound and organic light emitting device comprising same Download PDF

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WO2015076601A1
WO2015076601A1 PCT/KR2014/011227 KR2014011227W WO2015076601A1 WO 2015076601 A1 WO2015076601 A1 WO 2015076601A1 KR 2014011227 W KR2014011227 W KR 2014011227W WO 2015076601 A1 WO2015076601 A1 WO 2015076601A1
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deuterium
halogen
nitrile
amino
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Korean (ko)
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함호완
김봉기
안현철
김동준
한정우
김근태
이형진
임동환
김성훈
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주식회사 동진쎄미켐
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Priority to CN201480063380.1A priority Critical patent/CN105745301B/en
Priority claimed from KR1020140162289A external-priority patent/KR20150058083A/en
Publication of WO2015076601A1 publication Critical patent/WO2015076601A1/en

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Definitions

  • the present invention relates to a novel light emitting compound and an organic light emitting device comprising the same.
  • an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices.
  • LCD liquid crystal display
  • the material used as the organic material layer in the organic light emitting device can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function.
  • the light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. According to the emission color can be divided into blue, green, red light emitting material and yellow and orange light emitting material required to implement a better natural color.
  • a host / dopant system may be used as a light emitting material.
  • the principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light.
  • the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host used.
  • the present invention has excellent charge transfer characteristics, and at the same time have a high triplet energy and high Tg, when applied to an organic light emitting device can have a low driving voltage, high efficiency, low power consumption, long life. It is an object to provide a novel light emitting compound.
  • the present invention provides a light emitting compound represented by the following formula (1):
  • Each X is independently CR 0 or N, and R 0 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a
  • Y is C or Si
  • R 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 al
  • R 2 , R 3, R 4 and R 5 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30
  • the present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer as a light emitting material.
  • the light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has a high triplet energy and a high Tg, and can have a low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.
  • FIG. 1 schematically illustrates a cross section of an OLED according to an embodiment of the invention.
  • the compound of the present invention is characterized by represented by the following formula (1).
  • Each X is independently CR 0 or N, and R 0 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a
  • Y is C or Si
  • R 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 al
  • R 2 , R 3, R 4 and R 5 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30
  • the compound represented by Formula 1 may be one of the following structures.
  • Z is CR 8 or N, and R 8 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroary
  • A is O, S, Se, TE, N-Ar 1 where Ar 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group;
  • Ar is each independently deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6 A C 6-38 aryl group which is optionally substituted with an aryloxy group of -30 , an C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl oxy group, a heteroaryl group, a C 6-30 aryl group, or an C 2-30 aryl group optionally substituted heteroaryl of C 2-38,
  • R 6 and R 7 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is
  • n is an integer of 2-6.
  • Compound of Formula 1 according to the present invention has excellent charge transfer characteristics, and at the same time have a high triplet energy and high Tg, when applied to the organic light emitting device can have a low drive voltage, high efficiency, low power consumption, long life.
  • the present invention provides a method of formula (I) comprising the steps of Scheme 1:
  • Scheme 1 may be the following Scheme 1-1.
  • X, Y, Ar, R 1 , R 2 , R 3 , R 4 and R 5 in the schemes are as defined above, respectively.
  • the present invention provides an organic light emitting device comprising a compound represented by the formula (1) in the organic material layer as a light emitting material.
  • the compound of the present invention may be used alone or in combination with a known organic light emitting compound.
  • the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
  • the organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) between an anode and a cathode. It may contain one or more.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML emission layer
  • ETL electron transport layer
  • EIL electron injection layer
  • an anode is formed by depositing a material for an anode electrode having a high work function on the substrate.
  • the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof.
  • the anode electrode material transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used.
  • the anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
  • the hole injection layer material may be formed on the anode by vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), etc., but it is easy to obtain a uniform film quality and also pinholes. It is preferable to form by the vacuum evaporation method in that it is hard to generate
  • the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It is preferable to select appropriately from a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 mu m.
  • the hole injection layer material is not particularly limited and described in US Patent No. 4,356,429.
  • TCTA 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine
  • TCTA 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine
  • TCTA phthalocyanine compounds or starburst amine derivatives such as the disclosed copper phthalocyanine, m-MTDATA (4,4', 4" -tris (3-methylphenylamino) triphenylamine), m-MTDAPB (4,4 ', 4 "-tris (3-methylphenylamino) phenoxybenzene), HI-406 (N 1 , N 1 '-(biphenyl- 4,4'-diyl) bis (N 1-(naphthalen- 1 -yl) -N 4 , N 4 -diphenylbenzene-1,4-diamine) and the like may be used as the hole injection layer material.
  • the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, etc., but it is easy to obtain a uniform film quality and is difficult to generate pin holes. It is preferable to form by a vapor deposition method.
  • the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
  • the hole transport layer material is not particularly limited, and may be arbitrarily selected and used from conventionally known materials used in the hole transport layer.
  • the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine ( ⁇ -NPD) Derivatives and the like can be used.
  • carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4
  • the light emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but the vacuum deposition method is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by.
  • the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer.
  • the light emitting layer material may use the compound represented by Formula 1 of the present invention as a host or dopant.
  • a light emitting layer may be formed by using a phosphorescent or fluorescent dopant together.
  • the fluorescent dopant may be IDE102 or IDE105, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyrylcrisne- which can be purchased from Idemitsu Co., Ltd.).
  • 6,12-diamine can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).
  • the doping concentration of the dopant is not particularly limited, but the dopant is preferably doped at 0.01 to 15 parts by weight based on 100 parts by weight of the host.
  • the content of the dopant is less than 0.01 parts by weight, there is a problem in that the color development is not performed properly because the amount of the dopant is not sufficient, and if it exceeds 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon.
  • the hole suppression material HBL
  • HBL hole suppression material
  • the hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used.
  • an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited.
  • Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound e.g., BCP (vasocuproin) from UDC
  • BCP vasocuproin
  • An electron transport layer is formed on the light emitting layer formed as above, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.
  • the electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited, and examples thereof include quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3). ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine).
  • an electron injection layer (EIL) which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
  • the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.
  • an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is preferable to form by.
  • a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode.
  • the cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this.
  • a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
  • the organic light emitting device of the present invention is not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device of the cathode structure, but also the structure of an organic light emitting device of various structures, 1 It is also possible to form a layer or two intermediate layers.
  • each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.
  • the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
  • the organic light emitting device of the present invention may implement low driving voltage, high efficiency, low power consumption, and long life, including the compound represented by Formula 1 having excellent charge transfer characteristics and at the same time having a high triplet energy and a high Tg.
  • Compound 2 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyridine.
  • Compound 3 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4-bromo-2,6-diphenylpyrimidine.
  • Compound 4 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyrimidine.
  • Compound 6 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4- (3-bromophenyl) -2,6-diphenylpyrimidine.
  • Compound 7 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine.
  • Compound 8 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyridine as intermediate B instead of intermediate A.
  • Compound 12 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 9- (3-bromophenyl) -9H-carbazole.
  • Compound 13 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 3-bromo-9-phenyl-9H-carbazole.
  • An organic light emitting device was manufactured according to the structure of FIG. 1.
  • the organic light emitting element is formed from the bottom of the anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transfer layer 15 / cathode (electron injection electrode 16) It was laminated in order.
  • the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples used the following materials.
  • a glass substrate coated with an indium tin oxide (ITO) 1500 ⁇ thick thin film was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes by using an oxygen plasma.
  • NPB 250 ⁇ was formed into a hole injection layer HT01 600 ⁇ and a hole transport layer.
  • the light emitting layer was doped with 10% of Compound 1: Ir (ppy) 3 to form 250 ⁇ .
  • ET01: Liq (1: 1) 300 ⁇ was formed into an electron transport layer, followed by LiF 10 ⁇ and aluminum (Al) 1000 ⁇ , which were encapsulated in a glove box to produce a green organic light emitting device. .
  • a green organic light emitting diode was manufactured according to the same method as a light emitting layer host of Example 1, except that Compound 1 was used as CBP.
  • a green organic light emitting diode was manufactured according to the same method as Comparative Example 1, except that Compound 1 was used as the emission layer host of Example 1.
  • the embodiment of the present invention can be confirmed that the physical properties in all the organic light emitting device as compared to Comparative Examples 1 to 2.
  • the light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has a high triplet energy and a high Tg, and can have a low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.

Abstract

An organic light emission compound of the present invention has excellent charge transport characteristics while having high triplet energy and Tg, thereby allowing an organic light emitting device to have a low driving voltage, high efficiency, low-consumption power, and a long lifespan when the organic light emission compound is applied to the organic light emitting device.

Description

신규한 발광 화합물 및 이를 포함하는 유기발광소자Novel light emitting compound and organic light emitting device comprising the same
본 발명은 신규한 발광 화합물 및 이를 포함하는 유기발광소자에 관한 것이다.The present invention relates to a novel light emitting compound and an organic light emitting device comprising the same.
최근, 자체 발광형으로 저전압 구동이 가능한 유기발광소자는, 평판 표시소자의 주류인 액정디스플레이(LCD, liquid crystal display)에 비해, 시야각, 대조비 등이 우수하고 백라이트가 불필요하여 경량 및 박형이 가능하며 소비전력 측면에서도 유리하고 색 재현 범위가 넓어, 차세대 표시소자로서 주목을 받고 있다.Recently, an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices. In terms of power consumption and wide color reproduction range, it is attracting attention as a next-generation display device.
유기발광소자에서 유기물 층으로 사용되는 재료는 크게 기능에 따라, 발광 재료, 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. 상기 발광 재료는 분자량에 따라 고분자과 저분자로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있으며, 발광 재료는 발광 색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도판트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도판트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트와 호스트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다. The material used as the organic material layer in the organic light emitting device can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function. The light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. According to the emission color can be divided into blue, green, red light emitting material and yellow and orange light emitting material required to implement a better natural color. In addition, in order to increase luminous efficiency through an increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host used.
현재까지 이러한 유기발광소자에 사용되는 물질로서 다양한 화합물들이 알려져 있으나, 이제까지 알려진 물질을 이용한 유기발광소자의 경우 높은 구동전압, 낮은 효율 및 짧은 수명으로 인해 실용화하는 데에 많은 어려움이 있었다. 따라서, 우수한 특성을 갖는 물질을 이용하여 저전압 구동, 고휘도 및 장수명을 갖는 유기발광소자를 개발하려는 노력이 지속되어 왔다. To date, various compounds are known as materials used in such organic light emitting diodes, but in the case of organic light emitting diodes using materials known to date, there are many difficulties in practical use due to high driving voltage, low efficiency, and short lifespan. Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent properties.
상기와 같은 문제점을 해결하기 위해, 본 발명은 전하전달 특성이 우수하고, 동시에 높은 삼중항 에너지 및 높은 Tg를 가져, 유기발광소자에 적용시 낮은 구동전압, 고효율, 저소비전력, 장수명을 가지게 할 수 있는 신규한 발광 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention has excellent charge transfer characteristics, and at the same time have a high triplet energy and high Tg, when applied to an organic light emitting device can have a low driving voltage, high efficiency, low power consumption, long life. It is an object to provide a novel light emitting compound.
본 발명은 또한 상기 화합물을 포함하여 낮은 구동전압, 고효율, 저소비전력, 장수명 구현이 가능한 유기발광소자를 제공하는 것을 목적으로 한다.It is another object of the present invention to provide an organic light emitting device capable of realizing low driving voltage, high efficiency, low power consumption, and long life including the compound.
상기 목적을 달성하기 위해 본 발명은 하기 화학식 1로 표시되는 발광 화합물을 제공한다:In order to achieve the above object, the present invention provides a light emitting compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2014011227-appb-I000001
Figure PCTKR2014011227-appb-I000001
상기 식에서,Where
X는 각각 독립적으로 CR0 또는 N이며, R0는 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,Each X is independently CR 0 or N, and R 0 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
Y는 C 또는 Si이며,Y is C or Si,
R1은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,R 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade C 6-50 aryl group which is unsubstituted or substituted with a C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group,
R2, R3, R4 및 R5는 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며, 선택적으로 R4 및 R5는 고리를 형성할 수 있다.R 2 , R 3, R 4 and R 5 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade C 6-50 aryl group which is unsubstituted or substituted with a C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group, optionally R 4 and R 5 may form a ring.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 발광물질로서 유기물층에 포함하는 유기발광소자를 제공한다.The present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer as a light emitting material.
본 발명의 발광 화합물은 전하전달 특성이 우수하고, 동시에 높은 삼중항 에너지 및 높은 Tg를 가져, 유기발광소자에 적용시 낮은 구동전압, 고효율, 저소비전력, 장수명을 가지게 할 수 있다.The light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has a high triplet energy and a high Tg, and can have a low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.
도 1은 본 발명의 일 실시예에 따른 OLED의 단면을 개략적으로 도시한 것이다. 1 schematically illustrates a cross section of an OLED according to an embodiment of the invention.
도면의 부호Sign of drawing
10 : 기판10: substrate
11 : 양극11: anode
12 : 정공주입층12: hole injection layer
13 : 정공전달층13: hole transport layer
14 : 발광층14: light emitting layer
15 : 전자전달층15: electron transport layer
16: 음극16: cathode
본 발명의 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.The compound of the present invention is characterized by represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2014011227-appb-I000002
Figure PCTKR2014011227-appb-I000002
상기 식에서,Where
X는 각각 독립적으로 CR0 또는 N이며, R0는 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,Each X is independently CR 0 or N, and R 0 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
Y는 C 또는 Si이며,Y is C or Si,
R1은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,R 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade C 6-50 aryl group which is unsubstituted or substituted with a C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group,
R2, R3, R4 및 R5는 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며, 선택적으로 R4 및 R5는 고리를 형성할 수 있다.R 2 , R 3, R 4 and R 5 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade C 6-50 aryl group which is unsubstituted or substituted with a C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group, optionally R 4 and R 5 may form a ring.
본 발명에 있어서 상기 화학식 1로 표시되는 화합물은 하기 구조들 중 하나인 것이 좋다.In the present invention, the compound represented by Formula 1 may be one of the following structures.
Figure PCTKR2014011227-appb-I000003
Figure PCTKR2014011227-appb-I000003
상기 구조들에서 X, R4 및 R5는 화학식 1에서 정의한 바와 같으며, X, R 4 and R 5 in the above structures are as defined in Formula 1,
Z는 CR8 또는 N이며, R8은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,Z is CR 8 or N, and R 8 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
A는 O, S, Se, TE, N-Ar1이며 여기서 Ar1은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,A is O, S, Se, TE, N-Ar 1 where Ar 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-38의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-38의 헤테로아릴기이며,Ar is each independently deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6 A C 6-38 aryl group which is optionally substituted with an aryloxy group of -30 , an C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl oxy group, a heteroaryl group, a C 6-30 aryl group, or an C 2-30 aryl group optionally substituted heteroaryl of C 2-38,
R6 및 R7은 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,R 6 and R 7 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
n은 2 내지 6의 정수이다.n is an integer of 2-6.
본 발명에 있어서, 상기 화학식 1로 표시되는 화합물의 바람직한 예는 다음과 같다:In the present invention, preferred examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2014011227-appb-I000004
Figure PCTKR2014011227-appb-I000004
Figure PCTKR2014011227-appb-I000005
Figure PCTKR2014011227-appb-I000005
Figure PCTKR2014011227-appb-I000006
Figure PCTKR2014011227-appb-I000006
Figure PCTKR2014011227-appb-I000007
Figure PCTKR2014011227-appb-I000007
Figure PCTKR2014011227-appb-I000008
Figure PCTKR2014011227-appb-I000008
Figure PCTKR2014011227-appb-I000009
Figure PCTKR2014011227-appb-I000009
Figure PCTKR2014011227-appb-I000010
Figure PCTKR2014011227-appb-I000010
Figure PCTKR2014011227-appb-I000011
Figure PCTKR2014011227-appb-I000011
Figure PCTKR2014011227-appb-I000012
Figure PCTKR2014011227-appb-I000012
Figure PCTKR2014011227-appb-I000013
Figure PCTKR2014011227-appb-I000013
Figure PCTKR2014011227-appb-I000014
Figure PCTKR2014011227-appb-I000014
Figure PCTKR2014011227-appb-I000015
Figure PCTKR2014011227-appb-I000015
Figure PCTKR2014011227-appb-I000016
Figure PCTKR2014011227-appb-I000016
Figure PCTKR2014011227-appb-I000017
Figure PCTKR2014011227-appb-I000017
Figure PCTKR2014011227-appb-I000018
Figure PCTKR2014011227-appb-I000018
Figure PCTKR2014011227-appb-I000019
Figure PCTKR2014011227-appb-I000019
Figure PCTKR2014011227-appb-I000020
Figure PCTKR2014011227-appb-I000020
Figure PCTKR2014011227-appb-I000021
Figure PCTKR2014011227-appb-I000021
Figure PCTKR2014011227-appb-I000022
Figure PCTKR2014011227-appb-I000022
Figure PCTKR2014011227-appb-I000023
Figure PCTKR2014011227-appb-I000023
Figure PCTKR2014011227-appb-I000024
Figure PCTKR2014011227-appb-I000024
Figure PCTKR2014011227-appb-I000025
Figure PCTKR2014011227-appb-I000025
본 발명에 따른 화학식 1의 화합물은 전하전달 특성이 우수하고, 동시에 높은 삼중항 에너지 및 높은 Tg를 가져, 유기발광소자에 적용시 낮은 구동전압, 고효율, 저소비전력, 장수명을 가지게 할 수 있다.Compound of Formula 1 according to the present invention has excellent charge transfer characteristics, and at the same time have a high triplet energy and high Tg, when applied to the organic light emitting device can have a low drive voltage, high efficiency, low power consumption, long life.
또한 본 발명은 하기 반응식 1의 단계를 포함하는 것을 특징으로 하는 화학식 1의 제조방법을 제공한다:In another aspect, the present invention provides a method of formula (I) comprising the steps of Scheme 1:
[반응식 1]Scheme 1
Figure PCTKR2014011227-appb-I000026
Figure PCTKR2014011227-appb-I000026
상기 반응식 1의 구체적인 일예는 하기 반응식 1-1일 수 있다.Specific examples of Scheme 1 may be the following Scheme 1-1.
[반응식 1-1]Scheme 1-1
Figure PCTKR2014011227-appb-I000027
Figure PCTKR2014011227-appb-I000027
상기 반응식들에서 X, Y, Ar, R1, R2, R3, R4 및 R5는 각각 상기에서 정의한 바와 같다.X, Y, Ar, R 1 , R 2 , R 3 , R 4 and R 5 in the schemes are as defined above, respectively.
또한, 본 발명은 발광물질로서 상기 화학식 1로 표시되는 화합물을 유기물층에 포함하는 유기발광소자를 제공한다. 이때, 본 발명의 화합물은 단독으로 사용되거나 공지의 유기발광 화합물과 함께 사용될 수 있다.In addition, the present invention provides an organic light emitting device comprising a compound represented by the formula (1) in the organic material layer as a light emitting material. In this case, the compound of the present invention may be used alone or in combination with a known organic light emitting compound.
또한 본 발명의 유기발광소자는 상기 화학식 1로 표시되는 화합물을 포함하는 1층 이상의 유기물층을 포함하는 바, 상기 유기발광소자의 제조방법을 설명하면 다음과 같다.In addition, the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
상기 유기발광소자는 애노드(anode)와 캐소드(cathod) 사이에 정공주입층(HIL), 정공수송층(HTL), 발광층(EML), 전자수송층(ETL), 전자주입층(EIL) 등의 유기물층을 1 개 이상 포함할 수 있다.The organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) between an anode and a cathode. It may contain one or more.
먼저, 기판 상부에 높은 일함수를 갖는 애노드 전극용 물질을 증착시켜 애노드를 형성한다. 이때, 상기 기판은 통상의 유기발광소자에서 사용되는 기판을 사용할 수 있으며, 특히 기계적 강도, 열적 안정성, 투명성, 표면평활성, 취급용이성, 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판을 사용하는 것이 좋다. 또한, 애노드 전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용할 수 있다. 상기 애노드 전극용 물질은 통상의 애노드 형성방법에 의해 증착할 수 있으며, 구체적으로 증착법 또는 스퍼터링법에 의해 증착할 수 있다.First, an anode is formed by depositing a material for an anode electrode having a high work function on the substrate. In this case, the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof. In addition, as the anode electrode material, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used. The anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
그 다음, 상기 애노드 전극 상부에 정공주입층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB(Langmuir-Blodgett)법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 또한 핀정공이 발생하기 어렵다는 등의 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 정공주입층을 형성하는 경우 그 증착조건은 정공주입층의 재료로서 사용하는 화합물, 목적하는 정공주입층의 구조 및 열적특성 등에 따라 다르지만, 일반적으로 50-500 ℃의 증착온도, 10-8 내지 10-3 torr의 진공도, 0.01 내지 100 Å/sec의 증착속도, 10 Å 내지 5 ㎛의 층 두께 범위에서 적절히 선택하는 것이 바람직하다.Subsequently, the hole injection layer material may be formed on the anode by vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), etc., but it is easy to obtain a uniform film quality and also pinholes. It is preferable to form by the vacuum evaporation method in that it is hard to generate | occur | produce. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It is preferable to select appropriately from a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 mu m.
상기 정공주입층 물질은 특별히 제한되지 않으며, 미국특허 제4,356,429호에 The hole injection layer material is not particularly limited and described in US Patent No. 4,356,429.
개시된 구리 프탈로시아닌 등의 프탈로시아닌 화합물 또는 스타버스트형 아민 유도체류인 TCTA(4,4',4"-트리(N-카바졸릴)트리페닐아민), m-MTDATA(4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민), m-MTDAPB(4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠), HI-406(N1,N1'-(비페닐-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민) 등을 정공주입층 물질로 사용할 수 있다.TCTA (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), which are phthalocyanine compounds or starburst amine derivatives such as the disclosed copper phthalocyanine, m-MTDATA (4,4', 4" -tris (3-methylphenylamino) triphenylamine), m-MTDAPB (4,4 ', 4 "-tris (3-methylphenylamino) phenoxybenzene), HI-406 (N 1 , N 1 '-(biphenyl- 4,4'-diyl) bis (N 1-(naphthalen- 1 -yl) -N 4 , N 4 -diphenylbenzene-1,4-diamine) and the like may be used as the hole injection layer material.
다음으로 상기 정공주입층 상부에 정공수송층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 핀정공이 발생하기 어렵다는 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 정공수송층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다.Next, the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, etc., but it is easy to obtain a uniform film quality and is difficult to generate pin holes. It is preferable to form by a vapor deposition method. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
또한, 상기 정공수송층 물질은 특별히 제한되지는 않으며, 정공수송층에 사용되고 있는 통상의 공지 물질 중에서 임의로 선택하여 사용할 수 있다. 구체적으로, 상기 정공수송층 물질은 N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N.N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상의 아민 유도체 등이 사용될 수 있다.In addition, the hole transport layer material is not particularly limited, and may be arbitrarily selected and used from conventionally known materials used in the hole transport layer. Specifically, the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) Derivatives and the like can be used.
그 후, 상기 정공수송층 상부에 발광층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 핀정공이 발생하기 어렵다는 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 발광층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다. 또한, 상기 발광층 재료는 본 발명의 화학식 1로 표시되는 화합물을 호스트 또는 도펀트로 사용할 수 있다.Thereafter, the light emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but the vacuum deposition method is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use the compound represented by Formula 1 of the present invention as a host or dopant.
상기 화학식 1로 표시되는 화합물을 발광 호스트로 사용하는 경우, 인광 또는 형광 도펀트를 함께 사용하여 발광층을 형성할 수 있다. 이때, 형광 도펀트로는 이데미츠사(Idemitsu사)에서 구입 가능한 IDE102 또는 IDE105, 또는 BD142(N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸크리센-6,12-디아민)를 사용할 수 있으며, 인광 도펀트로는 녹색 인광 도펀트 Ir(ppy)3(트리스(2-페닐피리딘) 이리듐), 청색 인광 도펀트인 F2Irpic(이리듐(Ⅲ) 비스[4,6-다이플루오로페닐)-피리디나토-N,C2'] 피콜린산염), UDC사의 적색 인광 도펀트 RD61 등이 공동 진공증착(도핑)될 수 있다. 도펀트의 도핑농도는 특별히 제한되지 않으나, 호스트 100 중량부 대비 도펀트가 0.01 내지 15 중량부로 도핑되는 것이 바람직하다. 만약 도펀트의 함량이 0.01 중량부 미만일 경우에는 도펀트량이 충분치 못하여 발색이 제대로 이루어지지 않는다는 문제점이 있으며, 15 중량부를 초과할 경우에는 농도 소광 현상으로 인해 효율이 급격히 감소된다는 문제점이 있다.When the compound represented by Chemical Formula 1 is used as a light emitting host, a light emitting layer may be formed by using a phosphorescent or fluorescent dopant together. In this case, the fluorescent dopant may be IDE102 or IDE105, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyrylcrisne- which can be purchased from Idemitsu Co., Ltd.). 6,12-diamine) can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped). The doping concentration of the dopant is not particularly limited, but the dopant is preferably doped at 0.01 to 15 parts by weight based on 100 parts by weight of the host. If the content of the dopant is less than 0.01 parts by weight, there is a problem in that the color development is not performed properly because the amount of the dopant is not sufficient, and if it exceeds 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon.
또한, 발광층에 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지하기 위하여 정공억제재료(HBL)를 추가로 진공증착법 또는 스핀코팅법에 의해 적층시키는 것이 바람직하다. 이때 사용할 수 있는 정공억제물질은 특별히 제한되지는 않으나, 정공억제재료로 사용되고 있는 공지의 것에서 임의의 것을 선택해서 이용할 수 있다. 예를 들면, 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, 또는 일본특개평 11-329734(A1)에 기재되어 있는 정공억제재료 등을 들 수 있으며, 대표적으로 Balq(비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄 비페녹사이드), 페난트롤린(phenanthrolines)계 화합물(예: UDC사 BCP(바쏘쿠프로인)) 등을 사용할 수 있다.In addition, when using the phosphorescent dopant in the light emitting layer, it is preferable to further laminate the hole suppression material (HBL) by vacuum deposition or spin coating to prevent the triplet excitons or holes from diffusing into the electron transport layer. The hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BCP (vasocuproin) from UDC) can be used.
상기와 같이 형성된 발광층 상부에는 전자수송층이 형성되는데, 이때 상기 전자수송층은 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다.An electron transport layer is formed on the light emitting layer formed as above, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.
상기 전자수송층 재료는 전자주입전극으로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서 그 종류가 특별히 제한되지는 않으며, 예를 들어 퀴놀린 유도체, 특히 트리스(8-퀴놀리놀라토)알루미늄(Alq3), 또는 ET4(6,6'-(3,4-디메시틸-1,1-디메틸-1H-실올-2,5-디일)디-2,2'-비피리딘)을 사용할 수 있다. 또한, 전자수송층 상부에 캐소드로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자주입층(EIL)이 적층될 수 있으며, 전자주입층 물질로는 LiF, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다.The electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited, and examples thereof include quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3). ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine). In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
또한, 상기 전자수송층의 증착조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다.In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.
그 뒤, 상기 전자수송층 상부에 전자주입층 물질을 형성할 수 있으며, 이때 상기 전자수송층은 통상의 전자주입층 물질을 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다.Subsequently, an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is preferable to form by.
마지막으로 전자주입층 상부에 캐소드 형성용 금속을 진공증착법이나 스퍼터링법 등의 방법에 의해 형성하고 캐소드로 사용한다. 여기서 캐소드 형성용 금속으로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물, 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 있다. 또한, 전면 발광소자를 얻기 위하여 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다.Finally, a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode. The cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this. In addition, a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
본 발명의 유기발광소자는 애노드, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 캐소드 구조의 유기발광소자 뿐만 아니라, 다양한 구조의 유기발광소자의 구조가 가능하며, 필요에 따라 1층 또는 2층의 중간층을 더 형성하는 것도 가능하다.The organic light emitting device of the present invention is not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device of the cathode structure, but also the structure of an organic light emitting device of various structures, 1 It is also possible to form a layer or two intermediate layers.
상기와 같이 본 발명에 따라 형성되는 각 유기물층의 두께는 요구되는 정도에 따라 조절할 수 있으며, 바람직하게는 10 내지 1,000 ㎚이며, 더욱 바람직하게는 20 내지 150 ㎚인 것이 좋다.As described above, the thickness of each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 유기물층의 두께를 분자 단위로 조절할 수 있기 때문에 표면이 균일하며, 형태안정성이 뛰어난 장점이 있다.In addition, the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
본 발명의 유기발광소자는 전하전달 특성이 우수하고, 동시에 높은 삼중항 에너지 및 높은 Tg를 가지는 화학식 1로 표시되는 화합물을 포함하여 낮은 구동전압, 고효율, 저소비전력, 장수명을 구현할 수 있다.The organic light emitting device of the present invention may implement low driving voltage, high efficiency, low power consumption, and long life, including the compound represented by Formula 1 having excellent charge transfer characteristics and at the same time having a high triplet energy and a high Tg.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
중간체 A의 합성Synthesis of Intermediate A
Figure PCTKR2014011227-appb-I000028
Figure PCTKR2014011227-appb-I000028
[A-1의 합성][Synthesis of A-1]
둥근바닥플라스크에 (1H-indol-3-yl)boronic acid 41.17 g, methyl 2-bromobenzoate 50 g을 톨루엔 600 ml에 녹이고 K2CO3(2M) 350 ml와 Pd(PPh3)4 8.1 g을 넣은 후 환류 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결시켰다. 유기층을 EA로 추출하고 감압여과한 후 컬럼정제하여 중간체 A-1 42.1 g (수율 72%)를 얻었다.In a round bottom flask, 41.17 g of (1H-indol-3-yl) boronic acid and 50 g of methyl 2-bromobenzoate were dissolved in 600 ml of toluene, followed by 350 ml of K 2 CO 3 (2M) and 8.1 g of Pd (PPh 3 ) 4. After stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 42.1 g of Intermediate A-1 (72% yield).
[A-2의 합성][Synthesis of A-2]
상기 A-1 42 g을 THF 1000 ml에 녹인 후, 0 ℃까지 온도를 내렸다. CH3MgBr 167 ml를 천천히 첨가하고 상온으로 천천히 올려 1시간 교반 후 환류 교반하였다. 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 중간체 A-2 28.6 g (수율 68%)를 얻었다.42 g of A-1 was dissolved in 1000 ml of THF, and the temperature was lowered to 0 ° C. 167 ml of CH 3 MgBr was slowly added and slowly raised to room temperature, followed by stirring for 1 hour, followed by stirring under reflux. The organic layer was extracted with MC, filtered under reduced pressure and purified by column to obtain 28.6 g of Intermediate A-2 (yield 68%).
[A의 합성][Synthesis of A]
상기 A-2 28 g에 아세트산 280 ml와 염산 1.0 ml를 넣은 후 24시간 동안 환류 교반시킨 후 상온으로 온도를 내렸다. 석출된 고체를 필터 후 컬럼정제하여 중간체 A 15.3 g (수율 60%)를 얻었다.280 ml of acetic acid and 1.0 ml of hydrochloric acid were added to 28 g of A-2, and the mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The precipitated solid was filtered and then column purified to obtain 15.3 g of Intermediate A (yield 60%).
중간체 B의 합성Synthesis of Intermediate B
Figure PCTKR2014011227-appb-I000029
Figure PCTKR2014011227-appb-I000029
[B-1의 합성][Synthesis of B-1]
둥근바닥플라스크에 (1H-indol-3-yl)boronic acid 24.7 g, methyl 2-bromobenzoate 30 g을 톨루엔 350 ml에 녹이고 K2CO3(2M) 210 ml와 Pd(PPh3)4 4.84 g을 넣은 후 환류 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결시켰다. 유기층을 EA로 추출하고 감압여과한 후 컬럼정제하여 중간체 B-1 25.2 g (수율 72%)를 얻었다.In a round bottom flask, 24.7 g of (1H-indol-3-yl) boronic acid and 30 g of methyl 2-bromobenzoate were dissolved in 350 ml of toluene, and 210 ml of K 2 CO 3 (2M) and 4.84 g of Pd (PPh 3 ) 4 were added. After stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 25.2 g (72% yield) of intermediate B-1.
[B-2의 합성]Synthesis of B-2
상기 B-1 42 g을 THF 600 ml에 녹인 후, 0 ℃까지 온도를 내렸다. PhMgBr 99 ml를 천천히 첨가하고 상온으로 천천히 올려 1시간 교반 후 환류 교반하였다. 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 중간체 B-2 26.5 g (수율 71%)를 얻었다.42 g of B-1 was dissolved in 600 ml of THF, and the temperature was lowered to 0 ° C. PhMgBr 99 ml was slowly added, slowly raised to room temperature, and stirred for 1 hour, followed by stirring under reflux. The organic layer was extracted with MC, filtered under reduced pressure and purified by column to obtain 26.5 g of intermediate B-2 (yield 71%).
[B의 합성][Synthesis of B]
상기 B-2 26 g에 아세트산 260 ml와 염산 1.0 ml를 넣은 후 24시간 동안 환류 교반시킨 후 상온으로 온도를 내렸다. 석출된 고체를 필터 후 컬럼정제하여 중간체 B 16.6 g (수율 67%)를 얻었다.260 ml of acetic acid and 1.0 ml of hydrochloric acid were added to 26 g of B-2, and the mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The precipitated solid was filtered and then purified by column to obtain 16.6 g of Intermediate B (yield 67%).
실시예 1: 화합물 1의 합성Example 1 Synthesis of Compound 1
Figure PCTKR2014011227-appb-I000030
Figure PCTKR2014011227-appb-I000030
상기 중간체 A 2.5 g, 4-bromo-2,6-diphenylpyridine 3.99 g, t-BuONa 1.54 g, Pd2(dba)3 0.40 g, (t-Bu)3P 0.5 ml를 톨루엔 40 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 화합물 1 2.58 g (수율 52%)를 얻었다.2.5 g of Intermediate A, 3.99 g of 4-bromo-2,6-diphenylpyridine, 1.54 g of t-BuONa, 0.40 g of Pd 2 (dba) 3 and 0.5 ml of (t-Bu) 3 P were dissolved in 40 ml of toluene and refluxed. Stirred. After completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 2.58 g (yield 52%) of compound 1.
m/z: 462.21 (100.0%), 463.21 (37.5%), 464.22 (6.7%)m / z: 462.21 (100.0%), 463.21 (37.5%), 464.22 (6.7%)
실시예 2: 화합물 2의 합성Example 2: Synthesis of Compound 2
4-bromo-2,6-diphenylpyridine을 2-bromo-4,6-diphenylpyridine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 2를 합성하였다. Compound 2 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyridine.
m/z: 462.21 (100.0%), 463.21 (37.5%), 464.22 (6.7%)m / z: 462.21 (100.0%), 463.21 (37.5%), 464.22 (6.7%)
실시예 3: 화합물 3의 합성Example 3: Synthesis of Compound 3
Figure PCTKR2014011227-appb-I000031
Figure PCTKR2014011227-appb-I000031
4-bromo-2,6-diphenylpyridine을 4-bromo-2,6-diphenylpyrimidine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 3을 합성하였다.Compound 3 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4-bromo-2,6-diphenylpyrimidine.
m/z: 463.20 (100.0%), 464.21 (36.0%), 465.21 (6.7%), 464.20 (1.1%)m / z: 463.20 (100.0%), 464.21 (36.0%), 465.21 (6.7%), 464.20 (1.1%)
실시예 4: 화합물 4의 합성Example 4: Synthesis of Compound 4
Figure PCTKR2014011227-appb-I000032
Figure PCTKR2014011227-appb-I000032
4-bromo-2,6-diphenylpyridine을 2-bromo-4,6-diphenylpyrimidine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 4를 합성하였다.Compound 4 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyrimidine.
m/z: 463.20 (100.0%), 464.21 (36.0%), 465.21 (6.7%), 464.20 (1.1%)m / z: 463.20 (100.0%), 464.21 (36.0%), 465.21 (6.7%), 464.20 (1.1%)
실시예 5: 화합물 5의 합성Example 5: Synthesis of Compound 5
Figure PCTKR2014011227-appb-I000033
Figure PCTKR2014011227-appb-I000033
상기 중간체 A 2.5 g, NaH 0.31 g을 DMF 25 ml에 넣고 교반하였다. 여기에 2-chloro-4,6-diphenyl-1,3,5-triazine 3.44 g을 DMF 35 ml에 녹인 후 천천히 적가하였다. 상온에서 교반 후 TLC로 반응 종결을 확인하고 실리카 필터 후 재결정하여 화합물 5 2.44 g (수율 49%)를 얻었다.2.5 g of the intermediate A and 0.31 g of NaH were added to 25 ml of DMF and stirred. 3.44 g of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 35 ml of DMF, and then slowly added dropwise thereto. After stirring at room temperature, the reaction was terminated by TLC, and recrystallized after a silica filter to obtain 2.44 g of a compound 5 (yield 49%).
m/z: 464.20 (100.0%), 465.20 (36.1%), 466.21 (5.9%)m / z: 464.20 (100.0%), 465.20 (36.1%), 466.21 (5.9%)
실시예 6: 화합물 6의 합성Example 6: Synthesis of Compound 6
Figure PCTKR2014011227-appb-I000034
Figure PCTKR2014011227-appb-I000034
4-bromo-2,6-diphenylpyridine을 4-(3-bromophenyl)-2,6-diphenylpyrimidine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 6을 합성하였다.Compound 6 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4- (3-bromophenyl) -2,6-diphenylpyrimidine.
m/z: 539.24 (100.0%), 540.24 (42.5%), 541.24 (9.1%), 542.25 (1.2%), 540.23 (1.1%)m / z: 539.24 (100.0%), 540.24 (42.5%), 541.24 (9.1%), 542.25 (1.2%), 540.23 (1.1%)
실시예 7: 화합물 7의 합성Example 7: Synthesis of Compound 7
Figure PCTKR2014011227-appb-I000035
Figure PCTKR2014011227-appb-I000035
4-bromo-2,6-diphenylpyridine을 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 7을 합성하였다.Compound 7 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine.
m/z: 540.23 (100.0%), 541.23 (42.6%), 542.24 (8.4%), 543.24 (1.2%)m / z: 540.23 (100.0%), 541.23 (42.6%), 542.24 (8.4%), 543.24 (1.2%)
실시예 8: 화합물 8의 합성Example 8: Synthesis of Compound 8
Figure PCTKR2014011227-appb-I000036
Figure PCTKR2014011227-appb-I000036
상기 중간체 A 대신 중간체 B로, 4-bromo-2,6-diphenylpyridine을 2-bromo-4,6-diphenylpyridine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 8을 합성하였다.Compound 8 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyridine as intermediate B instead of intermediate A.
m/z: 587.24 (100.0%), 588.24 (46.8%), 589.24 (11.1%), 590.25 (1.6%), 588.23 (1.1%)m / z: 587.24 (100.0%), 588.24 (46.8%), 589.24 (11.1%), 590.25 (1.6%), 588.23 (1.1%)
실시예 9: 화합물 9의 합성Example 9: Synthesis of Compound 9
Figure PCTKR2014011227-appb-I000037
Figure PCTKR2014011227-appb-I000037
상기 중간체 A 대신 중간체 B로 반응한 것을 제외하고는 화합물 5와 같은 방법으로 화합물 9를 합성하였다. Compound 9 was synthesized in the same manner as in compound 5 except for reacting with intermediate B instead of intermediate A.
m/z: 588.23 (100.0%), 589.23 (46.9%), 590.24 (10.2%), 591.24 (1.6%)m / z: 588.23 (100.0%), 589.23 (46.9%), 590.24 (10.2%), 591.24 (1.6%)
실시예 10: 화합물 10의 합성Example 10 Synthesis of Compound 10
Figure PCTKR2014011227-appb-I000038
Figure PCTKR2014011227-appb-I000038
상기 중간체 A 대신 중간체 B로, 4-bromo-2,6-diphenylpyridine을 4-(3-bromophenyl)-2,6-diphenylpyrimidine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 10을 합성하였다. Compound 10 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4- (3-bromophenyl) -2,6-diphenylpyrimidine as Intermediate B instead of Intermediate A.
m/z: 663.27 (100.0%), 664.27 (53.4%), 665.27 (14.3%), 666.28 (2.4%), 664.26 (1.1%)m / z: 663.27 (100.0%), 664.27 (53.4%), 665.27 (14.3%), 666.28 (2.4%), 664.26 (1.1%)
실시예 11: 화합물 11의 합성Example 11: Synthesis of Compound 11
Figure PCTKR2014011227-appb-I000039
Figure PCTKR2014011227-appb-I000039
상기 중간체 A 대신 중간체 B로, 4-bromo-2,6-diphenylpyridine을 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 11을 합성하였다.Intermediate B instead of Intermediate A, except that 4-bromo-2,6-diphenylpyridine reacted with 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine Compound 11 was synthesized by the method.
m/z: 664.26 (100.0%), 665.27 (52.3%), 666.27 (13.4%), 667.27 (2.4%), 665.26 (1.5%)m / z: 664.26 (100.0%), 665.27 (52.3%), 666.27 (13.4%), 667.27 (2.4%), 665.26 (1.5%)
실시예 12: 화합물 12의 합성Example 12: Synthesis of Compound 12
Figure PCTKR2014011227-appb-I000040
Figure PCTKR2014011227-appb-I000040
4-bromo-2,6-diphenylpyridine을 9-(3-bromophenyl)-9H-carbazole으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 12를 합성하였다. Compound 12 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 9- (3-bromophenyl) -9H-carbazole.
m/z: 474.21 (100.0%), 475.21 (38.6%), 476.22 (7.1%)m / z: 474.21 (100.0%), 475.21 (38.6%), 476.22 (7.1%)
실시예 13: 화합물 13의 합성Example 13: Synthesis of Compound 13
Figure PCTKR2014011227-appb-I000041
Figure PCTKR2014011227-appb-I000041
4-bromo-2,6-diphenylpyridine을 3-bromo-9-phenyl-9H-carbazole으로 반응한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 13을 합성하였다. Compound 13 was synthesized in the same manner as in compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 3-bromo-9-phenyl-9H-carbazole.
m/z: 474.21 (100.0%), 475.21 (38.6%), 476.22 (7.1%)m / z: 474.21 (100.0%), 475.21 (38.6%), 476.22 (7.1%)
유기발광소자의 제조Fabrication of Organic Light Emitting Diode
도 1에 기재된 구조에 따라 유기발광소자를 제조하였다. 유기발광소자는 아래로부터 양극(정공주입전극(11))/정공주입층(12)/정공수송층(13)/발광층(14)/전자전달층(15)/음극(전자주입전극(16)) 순으로 적층시켰다.An organic light emitting device was manufactured according to the structure of FIG. 1. The organic light emitting element is formed from the bottom of the anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transfer layer 15 / cathode (electron injection electrode 16) It was laminated in order.
실시예 및 비교예의 정공주입층(12), 정공전달층(13), 발광층(14), 전자전달층(15)는 아래와 같은 물질을 사용하였다.The hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples used the following materials.
Figure PCTKR2014011227-appb-I000042
Figure PCTKR2014011227-appb-I000042
Figure PCTKR2014011227-appb-I000043
Figure PCTKR2014011227-appb-I000043
실시예 14Example 14
인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층 HT01 600 Å, 정공수송층으로 NPB 250 Å를 제막하였다. 다음으로 발광층으로 상기 화합물 1: Ir(ppy)3 10%로 도핑하여 250 Å 제막하였다. 다음으로 전자전달층으로 ET01:Liq(1:1) 300 Å 제막한 후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브박스에서 밀봉(Encapsulation)함으로써 녹색 유기발광소자를 제작하였다.A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes by using an oxygen plasma. Using an evaporator, NPB 250 주 was formed into a hole injection layer HT01 600 Å and a hole transport layer. Next, the light emitting layer was doped with 10% of Compound 1: Ir (ppy) 3 to form 250 Å. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막, which were encapsulated in a glove box to produce a green organic light emitting device. .
실시예 15 내지 실시예 26Examples 15-26
실시예 1과 같은 방법으로 발광층 호스트로 화합물 1을 대신하여 각각 화합물 2 내지 11을 사용하여 제막한 녹색 유기발광소자를 제작하였다.In the same manner as in Example 1, a green organic light emitting diode was manufactured by using Compounds 2 to 11 instead of Compound 1 as a light emitting layer host.
비교예 1 Comparative Example 1
상기 실시예 1의 발광층 호스트로 화합물1을 대신하여 CBP로 사용한 것을 제외하고는 동일한 방법으로 녹색 유기발광소자를 제작하였다.A green organic light emitting diode was manufactured according to the same method as a light emitting layer host of Example 1, except that Compound 1 was used as CBP.
비교예 2 Comparative Example 2
상기 실시예 1의 발광층 호스트로 화합물 1을 대신하여 비교화합물 1을 사용한 것을 제외하고는 동일한 방법으로 녹색 유기발광소자를 제작하였다.A green organic light emitting diode was manufactured according to the same method as Comparative Example 1, except that Compound 1 was used as the emission layer host of Example 1.
유기발광소자의 성능평가Performance Evaluation of Organic Light Emitting Diode
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit) 으로 전압을 인가하여 전자 및 정공을 주입하고 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 표 1에 나타내었다.Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.
표 1
Op. V QE(%) Cd/A lm/w CIEx CIEy 수명@1000nit
실시예1 6.931 17.33 45.98 19.81 0.301 0.621 42
실시예2 6.987 17.10 47.13 21.03 0.299 0.619 38
실시예3 7.023 16.98 50.20 20.04 0.298 0.620 39
실시예4 6.940 17.54 47.22 19.98 0.300 0.623 37
실시예5 7.085 16.85 48.39 21.23 0.298 0.614 42
실시예6 7.121 17.26 46.83 18.72 0.298 0.609 51
실시예7 7.343 17.01 49.17 22.46 0.297 0.618 49
실시예8 6.920 17.07 45.55 21.98 0.302 0.609 53
실시예9 7.010 16.93 43.62 20.76 0.300 0.620 48
실시예10 7.193 17.36 47.45 18.99 0.299 0.622 40
실시예11 7.110 17.28 51.11 19.54 0.299 0.619 52
실시예12 7.101 16.87 45.62 18.01 0.301 0.631 42
실시예13 7.100 16.79 44.55 18.12 0.301 0.633 41
비교예1 7.824 12.43 38.12 13.72 0.301 0.623 25
비교예2 7.328 14.56 39.98 17.60 0.300 0.613 36
Table 1
Op. V QE (%) Cd / A lm / w CIEx CIEy Lifespan @ 1000nit
Example 1 6.931 17.33 45.98 19.81 0.301 0.621 42
Example 2 6.987 17.10 47.13 21.03 0.299 0.619 38
Example 3 7.023 16.98 50.20 20.04 0.298 0.620 39
Example 4 6.940 17.54 47.22 19.98 0.300 0.623 37
Example 5 7.085 16.85 48.39 21.23 0.298 0.614 42
Example 6 7.121 17.26 46.83 18.72 0.298 0.609 51
Example 7 7.343 17.01 49.17 22.46 0.297 0.618 49
Example 8 6.920 17.07 45.55 21.98 0.302 0.609 53
Example 9 7.010 16.93 43.62 20.76 0.300 0.620 48
Example 10 7.193 17.36 47.45 18.99 0.299 0.622 40
Example 11 7.110 17.28 51.11 19.54 0.299 0.619 52
Example 12 7.101 16.87 45.62 18.01 0.301 0.631 42
Example 13 7.100 16.79 44.55 18.12 0.301 0.633 41
Comparative Example 1 7.824 12.43 38.12 13.72 0.301 0.623 25
Comparative Example 2 7.328 14.56 39.98 17.60 0.300 0.613 36
상기 표 1에 나타나는 바와 같이 본 발명의 실시예는 비교예 1 내지 2에 비하여 유기발광소자 모두에서 물성이 우수함을 확인할 수 있다. As shown in Table 1, the embodiment of the present invention can be confirmed that the physical properties in all the organic light emitting device as compared to Comparative Examples 1 to 2.
본 발명의 발광 화합물은 전하전달 특성이 우수하고, 동시에 높은 삼중항 에너지 및 높은 Tg를 가져, 유기발광소자에 적용시 낮은 구동전압, 고효율, 저소비전력, 장수명을 가지게 할 수 있다.The light emitting compound of the present invention has excellent charge transfer characteristics, and at the same time has a high triplet energy and a high Tg, and can have a low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.

Claims (6)

  1. 하기 화학식 1로 표시되는 발광 화합물 :A light emitting compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2014011227-appb-I000044
    Figure PCTKR2014011227-appb-I000044
    상기 식에서,Where
    X는 각각 독립적으로 CR0 또는 N이며, R0는 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,Each X is independently CR 0 or N, and R 0 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
    Y는 C 또는 Si이며,Y is C or Si,
    R1은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-36의 아릴기, 또는 C2-36의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-36의 아릴기, 또는 C2-36의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,R 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade A C 6-50 aryl group optionally substituted with a C 6-36 aryl group, or a C 2-36 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-36 aryl group, or a C 2-36 heteroaryl group,
    R2, R3, R4 및 R5는 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며, 선택적으로 R4 및 R5는 고리를 형성할 수 있다.R 2 , R 3, R 4 and R 5 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl jade C 6-50 aryl group which is unsubstituted or substituted with a C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl Or a C 2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group, optionally R 4 and R 5 may form a ring.
  2. 제1항에 있어서,The method of claim 1,
    하기 구조들 중 어느 하나로 표시되는 것을 특징으로 하는 발광 화합물:A luminescent compound characterized by represented by any one of the following structures:
    Figure PCTKR2014011227-appb-I000045
    Figure PCTKR2014011227-appb-I000045
    상기 구조들에서 X, R4 및 R5는 화학식 1에서 정의한 바와 같으며, X, R 4 and R 5 in the above structures are as defined in Formula 1,
    Z는 CR8 또는 N이며, R8은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,Z is CR 8 or N, and R 8 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
    A는 O, S, Se, TE, N-Ar1이며 여기서 Ar1은 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며,A is O, S, Se, TE, N-Ar 1 where Ar 1 is hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
    Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C6-38의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-30의 알킬기, C2-30의 알케닐기, C2-30의 알키닐기, C1-30의 알콕시기, C6-30의 아릴옥시기, C6-30의 아릴기, 또는 C2-30의 헤테로아릴기로 치환되거나 치환되지 않은 C2-38의 헤테로아릴기이며,Ar is each independently deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6 A C 6-38 aryl group which is optionally substituted with an aryloxy group of -30 , an C 6-30 aryl group, or a C 2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C 1-30 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 1-30 alkoxy group, C 6-30 aryl oxy group, a heteroaryl group, a C 6-30 aryl group, or an C 2-30 aryl group optionally substituted heteroaryl of C 2-38,
    R6 및 R7은 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 헤테로아릴기이며, R 6 and R 7 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-30 heteroaryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group,
    n은 2 내지 6의 정수이다.n is an integer of 2-6.
  3. 제1항에 있어서,The method of claim 1,
    하기 화학식들 중 어느 하나로 표시되는 것을 특징으로 하는 발광 화합물:A light emitting compound, characterized in that represented by any one of the following formula:
    Figure PCTKR2014011227-appb-I000046
    Figure PCTKR2014011227-appb-I000046
    Figure PCTKR2014011227-appb-I000047
    Figure PCTKR2014011227-appb-I000047
    Figure PCTKR2014011227-appb-I000048
    Figure PCTKR2014011227-appb-I000048
    Figure PCTKR2014011227-appb-I000049
    Figure PCTKR2014011227-appb-I000049
    Figure PCTKR2014011227-appb-I000050
    Figure PCTKR2014011227-appb-I000050
    Figure PCTKR2014011227-appb-I000051
    Figure PCTKR2014011227-appb-I000051
    Figure PCTKR2014011227-appb-I000052
    Figure PCTKR2014011227-appb-I000052
    Figure PCTKR2014011227-appb-I000053
    Figure PCTKR2014011227-appb-I000053
    Figure PCTKR2014011227-appb-I000054
    Figure PCTKR2014011227-appb-I000054
    Figure PCTKR2014011227-appb-I000055
    Figure PCTKR2014011227-appb-I000055
    Figure PCTKR2014011227-appb-I000056
    Figure PCTKR2014011227-appb-I000056
    Figure PCTKR2014011227-appb-I000057
    Figure PCTKR2014011227-appb-I000057
    Figure PCTKR2014011227-appb-I000058
    Figure PCTKR2014011227-appb-I000058
    Figure PCTKR2014011227-appb-I000059
    Figure PCTKR2014011227-appb-I000059
    Figure PCTKR2014011227-appb-I000060
    Figure PCTKR2014011227-appb-I000060
    Figure PCTKR2014011227-appb-I000061
    Figure PCTKR2014011227-appb-I000061
    Figure PCTKR2014011227-appb-I000062
    Figure PCTKR2014011227-appb-I000062
    Figure PCTKR2014011227-appb-I000063
    Figure PCTKR2014011227-appb-I000063
    Figure PCTKR2014011227-appb-I000064
    Figure PCTKR2014011227-appb-I000064
    Figure PCTKR2014011227-appb-I000065
    Figure PCTKR2014011227-appb-I000065
    Figure PCTKR2014011227-appb-I000066
    Figure PCTKR2014011227-appb-I000066
  4. 하기 반응식 1로 표시되는 단계를 포함하는 특징으로 하는 화학식 1의 제조방법:Method for preparing a formula 1 characterized in that it comprises the step represented by Scheme 1:
    [반응식 1]Scheme 1
    Figure PCTKR2014011227-appb-I000067
    Figure PCTKR2014011227-appb-I000067
    상기 반응식들에서 X, R1, R2, R3, R4 및 R5는 각각 화학식 1에서 정의한 바와 같다.X, R 1 , R 2 , R 3, R 4 and R 5 in the schemes are as defined in Formula 1, respectively.
  5. 애노드(anode), 캐소드(cathode) 및 두 전극 사이에 제1항 기재의 화합물을 함유하는 1층 이상의 유기물층을 포함하는 유기발광소자.An organic light emitting device comprising an anode, a cathode and at least one organic layer containing the compound of claim 1 between two electrodes.
  6. 제5항에 있어서,The method of claim 5,
    상기 유기물층이 제1항의 화합물을 발광 호스트 또는 도펀트로서 함유하는 것을 특징으로 하는 유기발광소자.An organic light emitting device, characterized in that the organic layer contains the compound of claim 1 as a light emitting host or dopant.
PCT/KR2014/011227 2013-11-20 2014-11-20 Novel light emission compound and organic light emitting device comprising same WO2015076601A1 (en)

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