WO2015076600A1 - 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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WO2015076600A1
WO2015076600A1 PCT/KR2014/011226 KR2014011226W WO2015076600A1 WO 2015076600 A1 WO2015076600 A1 WO 2015076600A1 KR 2014011226 W KR2014011226 W KR 2014011226W WO 2015076600 A1 WO2015076600 A1 WO 2015076600A1
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deuterium
halogen
nitrile
substituted
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PCT/KR2014/011226
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Korean (ko)
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함호완
김봉기
안현철
김동준
한정우
김근태
이형진
임동환
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주식회사 동진쎄미켐
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Priority to CN201480063383.5A priority Critical patent/CN105765031B/en
Priority claimed from KR1020140162267A external-priority patent/KR20150058082A/en
Publication of WO2015076600A1 publication Critical patent/WO2015076600A1/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, wherein at least one of X is 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nit
  • Y is S, O, Se, Te or -NAr 1 , wherein 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group,
  • R 1 is 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 C 6-50 aryl group which is unsubstituted or substituted with an aryloxy group, C 6-30 aryl group, or 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,
  • R 2 and R 3 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsub
  • 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, wherein at least one of X is 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nit
  • Y is S, O, Se, Te or -NAr 1 , wherein 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group,
  • R 1 is 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 C 6-50 aryl group which is unsubstituted or substituted with an aryloxy group, C 6-30 aryl group, or 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,
  • R 2 and R 3 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsub
  • the compound represented by Formula 1 may have a structure as follows.
  • Z is CR 6 or N, and R 6 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroary
  • Ar is 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 C 6-38 aryl group which is unsubstituted or substituted with an aryloxy group, 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 6-38 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group,
  • Y 1 is S, O, Se, Te or —NAr 2 , wherein Ar 2 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,
  • R 4 and R 5 are each independently hydrogen; heavy hydrogen; Deuterium, halogen, amino group, nitrile group, nitro group substituted or unsubstituted C 1-30 alkyl group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group, or the like; 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 unsub
  • n is an integer of 1 to 6, and when n is 1, at least one of X is N.
  • 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.
  • Scheme 1 may be the following Scheme 1-1 as a specific example.
  • 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 TCTA (4,4 ′, 4 ′′ -tri (N-carbazolyl) tree, which is a phthalocyanine compound or starburst type amine derivative such as copper phthalocyanine disclosed in US Pat. No. 4,356,429.
  • 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.
  • the intermediate was synthesized by cyclization after the Suzuki reaction according to the following synthesis method.
  • Compound 8 was synthesized by the same method as Compound 7 using Intermediate 30 and 2-bromodibenzo [b, d] furan.
  • Compound 9 was synthesized by the same method as Compound 7 using the intermediate 26 and 2,8-dibromodibenzo [b, d] thiophene.
  • Compound 10 was synthesized by the same method as Compound 7 using Intermediate 04 and 3-bromo-9-phenyl-9H-carbazole.
  • Compound 11 was synthesized in the same manner as Compound 7 using Intermediate 11 and 3-bromo-9-phenyl-9H-carbazole.
  • Compound 12 was synthesized by the same method as Compound 7 using the intermediate 01 and 3,6-dibromo-9-phenyl-9H-carbazole.
  • Compound 20 was synthesized in the same manner as in compound 18, using Intermediate 29 and 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine.
  • 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., dried and transferred to a plasma cleaner, and then cleaned the substrate using oxygen plasma for 5 minutes and then a thermal vacuum evaporator (thermal Using an evaporator, NPB 250 ⁇ was formed into a hole injection layer HT01 600 ⁇ and a hole transport layer. Next, the light emitting layer was doped with Compound 1: Firpic 10% to form 250 ⁇ .
  • ITO indium tin oxide
  • Example 26 In the same manner as in Example 26, a blue organic light emitting diode was manufactured by using a compound 2 to 12 as a light emitting layer host.
  • 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 the compound 13: 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 by using a compound 14 to 25 as a light emitting layer host.
  • a blue 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 mCP.
  • a blue organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 1 was used as Comparative Compound 1 instead of Compound 1 as the emission layer host.
  • a green organic light emitting diode was manufactured according to the same method as a light emitting layer host of Example 13, except that Compound 13 was used as CBP.
  • a green organic light emitting diode was manufactured according to the same method as Example 13 except for using Compound 1 as the light emitting layer host of Example 13.
  • the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects of the organic light emitting device compared to Comparative Examples 1 to 4.
  • Comparative Compounds 2 and 4 when applied to the blue phosphor, it was confirmed that the luminous efficiency was lower due to the lower triplet energy than the blue dopant, which means that the compound of the present invention is high in the application of the blue and green phosphors. It can be seen that the luminous efficiency due to energy is improved.
  • 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 유기발광소자 Novel 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 PCTKR2014011226-appb-I000001
Figure PCTKR2014011226-appb-I000001
상기 식에서,Where
X는 각각 독립적으로 CR0 또는 N이며, 여기서 X중 적어도 하나는 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,Each X is independently CR 0 or N, wherein at least one of X is 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
Y는 S, O, Se, Te 또는 -NAr1이며, 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,Y is S, O, Se, Te or -NAr 1 , wherein 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1은 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 헤테로아릴기이고,R 1 is 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 C 6-50 aryl group which is unsubstituted or substituted with an aryloxy group, C 6-30 aryl group, or 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 및 R3은 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 2 and R 3 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
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 PCTKR2014011226-appb-I000002
Figure PCTKR2014011226-appb-I000002
상기 식에서,Where
X는 각각 독립적으로 CR0 또는 N이며, 여기서 X중 적어도 하나는 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,Each X is independently CR 0 or N, wherein at least one of X is 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
Y는 S, O, Se, Te 또는 -NAr1이며, 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,Y is S, O, Se, Te or -NAr 1 , wherein 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1은 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 헤테로아릴기이고, R 1 is 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 C 6-50 aryl group which is unsubstituted or substituted with an aryloxy group, C 6-30 aryl group, or 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 및 R3은 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 2 and R 3 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
본 발명에 있어서, 상기 화학식 1로 표시되는 화합물은 하기와 같은 구조일 수 있다.In the present invention, the compound represented by Formula 1 may have a structure as follows.
Figure PCTKR2014011226-appb-I000003
Figure PCTKR2014011226-appb-I000003
상기 구조들에서 X, Y는 상기 화학식 1에서 정의한 바와 같으며, X, Y in the structures are as defined in Formula 1,
Z는 CR6 또는 N이며, R6는 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고, Z is CR 6 or N, and R 6 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
Ar은 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 C6-38의 헤테로아릴기이며,Ar is 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 C 6-38 aryl group which is unsubstituted or substituted with an aryloxy group, 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 6-38 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group,
Y1은 S, O, Se, Te 또는 -NAr2이며, 여기서 Ar2는 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 헤테로아릴기이고, Y 1 is S, O, Se, Te or —NAr 2 , wherein Ar 2 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 unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R4 및 R5는 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, 로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기 로 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 4 and R 5 are each independently hydrogen; heavy hydrogen; Deuterium, halogen, amino group, nitrile group, nitro group substituted or unsubstituted C 1-30 alkyl group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group, or the like; 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 1 내지 6의 정수이며, n이 1인 경우 X 중 적어도 하나는 N이다.n is an integer of 1 to 6, and when n is 1, at least one of X is N.
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 PCTKR2014011226-appb-I000004
Figure PCTKR2014011226-appb-I000004
Figure PCTKR2014011226-appb-I000005
Figure PCTKR2014011226-appb-I000005
Figure PCTKR2014011226-appb-I000006
Figure PCTKR2014011226-appb-I000006
Figure PCTKR2014011226-appb-I000007
Figure PCTKR2014011226-appb-I000007
Figure PCTKR2014011226-appb-I000008
Figure PCTKR2014011226-appb-I000008
Figure PCTKR2014011226-appb-I000009
Figure PCTKR2014011226-appb-I000009
Figure PCTKR2014011226-appb-I000010
Figure PCTKR2014011226-appb-I000010
Figure PCTKR2014011226-appb-I000011
Figure PCTKR2014011226-appb-I000011
Figure PCTKR2014011226-appb-I000012
Figure PCTKR2014011226-appb-I000012
Figure PCTKR2014011226-appb-I000013
Figure PCTKR2014011226-appb-I000013
Figure PCTKR2014011226-appb-I000014
Figure PCTKR2014011226-appb-I000014
Figure PCTKR2014011226-appb-I000015
Figure PCTKR2014011226-appb-I000015
Figure PCTKR2014011226-appb-I000016
Figure PCTKR2014011226-appb-I000016
Figure PCTKR2014011226-appb-I000017
Figure PCTKR2014011226-appb-I000017
Figure PCTKR2014011226-appb-I000018
Figure PCTKR2014011226-appb-I000018
Figure PCTKR2014011226-appb-I000019
Figure PCTKR2014011226-appb-I000019
Figure PCTKR2014011226-appb-I000020
Figure PCTKR2014011226-appb-I000020
Figure PCTKR2014011226-appb-I000021
Figure PCTKR2014011226-appb-I000021
Figure PCTKR2014011226-appb-I000022
Figure PCTKR2014011226-appb-I000022
Figure PCTKR2014011226-appb-I000023
Figure PCTKR2014011226-appb-I000023
Figure PCTKR2014011226-appb-I000024
Figure PCTKR2014011226-appb-I000024
Figure PCTKR2014011226-appb-I000025
Figure PCTKR2014011226-appb-I000025
Figure PCTKR2014011226-appb-I000026
Figure PCTKR2014011226-appb-I000026
Figure PCTKR2014011226-appb-I000027
Figure PCTKR2014011226-appb-I000028
Figure PCTKR2014011226-appb-I000027
Figure PCTKR2014011226-appb-I000028
Figure PCTKR2014011226-appb-I000029
Figure PCTKR2014011226-appb-I000029
Figure PCTKR2014011226-appb-I000030
Figure PCTKR2014011226-appb-I000030
Figure PCTKR2014011226-appb-I000031
Figure PCTKR2014011226-appb-I000031
Figure PCTKR2014011226-appb-I000032
Figure PCTKR2014011226-appb-I000032
Figure PCTKR2014011226-appb-I000033
Figure PCTKR2014011226-appb-I000033
Figure PCTKR2014011226-appb-I000034
Figure PCTKR2014011226-appb-I000034
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 1과 같은 단계를 포함하여 제조될 수 있다:In addition, the present invention can be prepared including the steps of Scheme 1 below:
[반응식 1]Scheme 1
Figure PCTKR2014011226-appb-I000035
Figure PCTKR2014011226-appb-I000035
상기 반응식 1은 구체적인 일예로 하기 반응식 1-1일 수 있다.Scheme 1 may be the following Scheme 1-1 as a specific example.
[반응식 1-1]Scheme 1-1
Figure PCTKR2014011226-appb-I000036
Figure PCTKR2014011226-appb-I000036
상기 반응식들에서 정의되지 않은 부분은 화학식 1에서 정의된 바와 같다. Portions not defined in the above schemes are as defined in Formula 1.
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 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.The hole injection layer material is not particularly limited, and TCTA (4,4 ′, 4 ″ -tri (N-carbazolyl) tree, which is a phthalocyanine compound or starburst type amine derivative such as copper phthalocyanine disclosed in US Pat. No. 4,356,429. Phenylamine), 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 can 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 합성Intermediate synthesis
하기 합성법에 따라 스즈키 반응 후 고리화하여 중간체를 합성한다.The intermediate was synthesized by cyclization after the Suzuki reaction according to the following synthesis method.
Figure PCTKR2014011226-appb-I000037
Figure PCTKR2014011226-appb-I000037
[중간체 01의 합성][Synthesis of Intermediate 01]
Figure PCTKR2014011226-appb-I000038
Figure PCTKR2014011226-appb-I000038
[중간체 1-1의 합성][Synthesis of Intermediate 1-1]
둥근바닥플라스크에 benzofuran-3-ylboronic acid 95.7 g, 2-bromo-3-nitropyridine 100 g을 톨루엔 1000 ml에 녹이고 K2CO3(2M) 730 ml와 Pd(PPh3)4 17.1 g을 넣은 후 환류 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결시켰다. 유기층을 EA로 추출하고 감압여과한 후 컬럼정제하여 중간체 1-1 93.4 g (수율 79%)를 얻었다.In a round bottom flask, 95.7 g of benzofuran-3-ylboronic acid and 100 g of 2-bromo-3-nitropyridine were dissolved in 1000 ml of toluene, 730 ml of K 2 CO 3 (2M) and 17.1 g of Pd (PPh 3 ) 4 were added. Stirred. 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 93.4 g (79%) of intermediate 1-1.
[중간체 01의 합성][Synthesis of Intermediate 01]
상기 중간체 1-1 93 g을 1,2-dichlorobenzene 460 ml에 녹인 후 P(OEt)3 380 ml를 첨가하여 환류 교반하였다. 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 중간체 01 28.2 g (수율 35%)를 얻었다.93 g of the intermediate 1-1 was dissolved in 460 ml of 1,2-dichlorobenzene, and 380 ml of P (OEt) 3 was added thereto, followed by stirring under reflux. The organic layer was extracted with MC, filtered under reduced pressure and purified by column to obtain 28.2 g of intermediate 01 (yield 35%).
[기타 중간체의 합성][Synthesis of Other Intermediates]
중간체 01의 합성과 같은 방법으로 benzofuran-3-ylboronic acid 대신 benzo[b]thiophen-3-ylboronic acid, (1-phenyl-1H-indol-3-yl)boronic acid, 3-bromofuro[3,2-b]pyridine, 3-bromofuro[2,3-b]pyridine, 3-bromofuro[2,3-c]pyridine, 3-bromofuro[3,2-c]pyridine, 7-bromofuro[3,2-d]pyrimidine, 5-bromofuro[2,3-d]pyrimidine, 7-bromofuro[2,3-b]pyrazine, 3-bromothieno[3,2-b]pyridine, 3-bromothieno[2,3-b]pyridine, 3-bromothieno[2,3-c]pyridine, 3-bromothieno[3,2-c]pyridine, 7-bromothieno[3,2-d]pyrimidine, 5-bromothieno[2,3-d]pyrimidine, 7-bromothieno[2,3-b]pyrazine을 사용하고, 2-bromo-3-nitropyridine 대신 3-bromo-2-nitropyridine, 4-bromo-3-nitropyridine, 3-bromo-4-nitropyridine, 4-bromo-5-nitropyrimidine, 5-bromo-4-nitropyrimidine, 2-bromo-3-nitropyrazine을 사용하여 하기 중간체 02 내지 135를 합성하였다.Benzo [b] thiophen-3-ylboronic acid, (1-phenyl-1H-indol-3-yl) boronic acid, 3-bromofuro [3,2- instead of benzofuran-3-ylboronic acid b] pyridine, 3-bromofuro [2,3-b] pyridine, 3-bromofuro [2,3-c] pyridine, 3-bromofuro [3,2-c] pyridine, 7-bromofuro [3,2-d] pyrimidine, 5-bromofuro [2,3-d] pyrimidine, 7-bromofuro [2,3-b] pyrazine, 3-bromothieno [3,2-b] pyridine, 3-bromothieno [2,3-b] pyridine, 3-bromothieno [2,3-c] pyridine, 3-bromothieno [3,2-c] pyridine, 7-bromothieno [3,2-d] pyrimidine, 5-bromothieno [2,3-d] pyrimidine, 7- Use bromothieno [2,3-b] pyrazine, and instead of 2-bromo-3-nitropyridine, 3-bromo-2-nitropyridine, 4-bromo-3-nitropyridine, 3-bromo-4-nitropyridine, 4-bromo-5 The following intermediates 02 to 135 were synthesized using -nitropyrimidine, 5-bromo-4-nitropyrimidine and 2-bromo-3-nitropyrazine.
Figure PCTKR2014011226-appb-I000039
Figure PCTKR2014011226-appb-I000039
Figure PCTKR2014011226-appb-I000040
Figure PCTKR2014011226-appb-I000040
Figure PCTKR2014011226-appb-I000041
Figure PCTKR2014011226-appb-I000041
Figure PCTKR2014011226-appb-I000042
Figure PCTKR2014011226-appb-I000042
Figure PCTKR2014011226-appb-I000043
Figure PCTKR2014011226-appb-I000043
Figure PCTKR2014011226-appb-I000044
Figure PCTKR2014011226-appb-I000044
Figure PCTKR2014011226-appb-I000045
Figure PCTKR2014011226-appb-I000045
Figure PCTKR2014011226-appb-I000046
Figure PCTKR2014011226-appb-I000046
실시예 1: 화합물 1의 합성Example 1 Synthesis of Compound 1
Figure PCTKR2014011226-appb-I000047
Figure PCTKR2014011226-appb-I000047
상기 중간체 01 2.0 g, 9-(3'-bromo-[1,1'-biphenyl]-3-yl)-9H-carbazole 4.6 g, t-BuONa 1.4 g, Pd2(dba)3 0.35 g, (t-Bu)3P 0.5 ml를 톨루엔 30 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 화합물 1 1.77 g (수율 35%)를 얻었다.The intermediate 01 2.0 g, 9- (3'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole, 4.6 g, t-BuONa 1.4 g, Pd 2 (dba) 3 0.35 g, ( t-Bu) 3 P 0.5 ml was dissolved in 30 ml of toluene and stirred under reflux. After completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 1.77 g (yield 35%) of compound 1.
m/z: 525.18 (100.0%), 526.19 (40.3%), 527.19 (8.1%), 528.19 (1.2%), 526.18 (1.1%)m / z: 525.18 (100.0%), 526.19 (40.3%), 527.19 (8.1%), 528.19 (1.2%), 526.18 (1.1%)
실시예 2: 화합물 2의 합성Example 2: Synthesis of Compound 2
Figure PCTKR2014011226-appb-I000048
Figure PCTKR2014011226-appb-I000048
상기 중간체 05를 사용한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 2를 합성하였다.Compound 2 was synthesized in the same manner as Compound 1, except that Intermediate 05 was used.
m/z: 526.18 (100.0%), 527.18 (40.5%), 528.19 (7.5%), 529.19 (1.0%)m / z: 526.18 (100.0%), 527.18 (40.5%), 528.19 (7.5%), 529.19 (1.0%)
실시예 3: 화합물 3의 합성Example 3: Synthesis of Compound 3
Figure PCTKR2014011226-appb-I000049
Figure PCTKR2014011226-appb-I000049
상기 중간체 33을 사용한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 3을 합성하였다.Compound 3 was synthesized in the same manner as Compound 1, except that Intermediate 33 was used.
m/z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)m / z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)
실시예 4: 화합물 4의 합성Example 4: Synthesis of Compound 4
Figure PCTKR2014011226-appb-I000050
Figure PCTKR2014011226-appb-I000050
상기 중간체 86을 사용한 것을 제외하고는 화합물 1과 같은 방법으로 화합물 4를 합성하였다.Compound 4 was synthesized in the same manner as Compound 1, except that Intermediate 86 was used.
m/z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)m / z: 542.16 (100.0%), 543.16 (40.0%), 544.16 (8.3%), 544.15 (4.5%), 545.16 (1.9%), 543.15 (1.5%)
실시예 5: 화합물 5의 합성Example 5: Synthesis of Compound 5
Figure PCTKR2014011226-appb-I000051
Figure PCTKR2014011226-appb-I000051
상기 중간체 29 3.0 g, 3,3'-dibromo-1,1'-biphenyl 4.3 g, t-BuONa 2.1 g, Pd2(dba)3 0.53 g, (t-Bu)3P 0.3 ml를 톨루엔 45 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 화합물 5 2.69 g (수율 33%)를 얻었다.Intermediate 29 3.0 g, 3,3'-dibromo-1,1'-biphenyl 4.3 g, t-BuONa 2.1 g, Pd 2 (dba) 3 0.53 g, (t-Bu) 3 P 0.3 ml 45 ml of toluene It was dissolved in and stirred under reflux. After completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 2.69 g (yield 33%) of compound 5.
m/z: 598.13 (100.0%), 599.13 (44.4%), 600.12 (9.0%), 600.14 (8.3%), 601.13 (4.0%), 600.13 (1.3%), 601.14 (1.1%)m / z: 598.13 (100.0%), 599.13 (44.4%), 600.12 (9.0%), 600.14 (8.3%), 601.13 (4.0%), 600.13 (1.3%), 601.14 (1.1%)
실시예 6: 화합물 6의 합성Example 6: Synthesis of Compound 6
Figure PCTKR2014011226-appb-I000052
Figure PCTKR2014011226-appb-I000052
상기 중간체 18을 사용한 것을 제외하고는 화합물 5와 같은 방법으로 화합물 6을 합성하였다.Compound 6 was synthesized in the same manner as Compound 5, except that Intermediate 18 was used.
m/z: 716.27 (100.0%), 717.27 (56.3%), 718.28 (14.5%), 719.28 (2.5%), 718.27 (1.2%)m / z: 716.27 (100.0%), 717.27 (56.3%), 718.28 (14.5%), 719.28 (2.5%), 718.27 (1.2%)
실시예 7: 화합물 7의 합성Example 7: Synthesis of Compound 7
Figure PCTKR2014011226-appb-I000053
Figure PCTKR2014011226-appb-I000053
상기 중간체 01 3.0 g, 2-bromodibenzo[b,d]thiophene 3.8 g, t-BuONa 1.7 g, Pd2(dba)3 0.44 g, (t-Bu)3P 0.6 ml를 톨루엔 40 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 화합물 7 1.78g (수율 38%)를 얻었다.3.0 g of the intermediate 01, 3.8 g of 2-bromodibenzo [b, d] thiophene, 1.7 g of t-BuONa, 0.44 g of Pd 2 (dba) 3 and 0.6 ml of (t-Bu) 3 P were dissolved in 40 ml of toluene and refluxed. Stirred. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure and purified by column to obtain compound 1.78g (yield 38%).
m/z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)m / z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)
실시예 8: 화합물 8의 합성Example 8: Synthesis of Compound 8
Figure PCTKR2014011226-appb-I000054
Figure PCTKR2014011226-appb-I000054
상기 중간체 30과 2-bromodibenzo[b,d]furan을 이용하여 화합물 7과 같은 방법으로 화합물 8을 합성하였다.Compound 8 was synthesized by the same method as Compound 7 using Intermediate 30 and 2-bromodibenzo [b, d] furan.
m/z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)m / z: 390.08 (100.0%), 391.09 (27.2%), 392.08 (4.7%), 392.09 (4.0%), 391.08 (1.5%), 393.08 (1.3%)
실시예 9: 화합물 9의 합성Example 9: Synthesis of Compound 9
Figure PCTKR2014011226-appb-I000055
Figure PCTKR2014011226-appb-I000055
상기 중간체 26과 2,8-dibromodibenzo[b,d]thiophene을 이용하여 화합물 7과 같은 방법으로 화합물 9를 합성하였다.Compound 9 was synthesized by the same method as Compound 7 using the intermediate 26 and 2,8-dibromodibenzo [b, d] thiophene.
m/z: 598.12 (100.0%), 599.12 (42.0%), 600.13 (7.9%), 600.12 (5.7%), 601.12 (2.0%), 601.13 (1.1%)m / z: 598.12 (100.0%), 599.12 (42.0%), 600.13 (7.9%), 600.12 (5.7%), 601.12 (2.0%), 601.13 (1.1%)
실시예 10: 화합물 10의 합성Example 10 Synthesis of Compound 10
Figure PCTKR2014011226-appb-I000056
Figure PCTKR2014011226-appb-I000056
상기 중간체 04와 3-bromo-9-phenyl-9H-carbazole을 이용하여 화합물 7과 같은 방법으로 화합물 10을 합성하였다. Compound 10 was synthesized by the same method as Compound 7 using Intermediate 04 and 3-bromo-9-phenyl-9H-carbazole.
m/z: 449.15 (100.0%), 450.16 (33.8%), 451.16 (5.7%), 450.15 (1.1%)m / z: 449.15 (100.0%), 450.16 (33.8%), 451.16 (5.7%), 450.15 (1.1%)
실시예 11: 화합물 11의 합성Example 11: Synthesis of Compound 11
Figure PCTKR2014011226-appb-I000057
Figure PCTKR2014011226-appb-I000057
상기 중간체 11과 3-bromo-9-phenyl-9H-carbazole을 이용하여 화합물 7과 같은 방법으로 화합물 11을 합성하였다. Compound 11 was synthesized in the same manner as Compound 7 using Intermediate 11 and 3-bromo-9-phenyl-9H-carbazole.
m/z: 465.13 (100.0%), 466.13 (35.4%), 467.14 (5.5%), 467.13 (5.2%), 468.13 (1.6%)m / z: 465.13 (100.0%), 466.13 (35.4%), 467.14 (5.5%), 467.13 (5.2%), 468.13 (1.6%)
실시예 12: 화합물 12의 합성Example 12: Synthesis of Compound 12
Figure PCTKR2014011226-appb-I000058
Figure PCTKR2014011226-appb-I000058
상기 중간체 01와 3,6-dibromo-9-phenyl-9H-carbazole을 이용하여 화합물 7과 같은 방법으로 화합물 12를 합성하였다. Compound 12 was synthesized by the same method as Compound 7 using the intermediate 01 and 3,6-dibromo-9-phenyl-9H-carbazole.
m/z: 655.20 (100.0%), 656.20 (49.4%), 657.21 (11.7%), 658.21 (1.9%)m / z: 655.20 (100.0%), 656.20 (49.4%), 657.21 (11.7%), 658.21 (1.9%)
실시예 13: 화합물 13의 합성Example 13: Synthesis of Compound 13
Figure PCTKR2014011226-appb-I000059
Figure PCTKR2014011226-appb-I000059
상기 중간체 01 3.0 g, NaH 0.41 g을 DMF 30 ml에 넣고 교반하였다. 여기에 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7 g을 DMF 45 ml에 녹인 후 천천히 적가하였다. 상온에서 교반 후 TLC로 반응 종결을 확인하고 실리카 필터 후 재결정하여 화합물 13 3.36 g (수율 53%)를 얻었다.3.0 g of the intermediate 01 and 0.41 g of NaH were added to 30 ml of DMF and stirred. 4.7 g of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 45 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 3.36 g (yield 53%) of compound 13.
m/z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)m / z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)
실시예 14: 화합물 14의 합성Example 14 Synthesis of Compound 14
Figure PCTKR2014011226-appb-I000060
Figure PCTKR2014011226-appb-I000060
상기 중간체 02를 사용한 것을 제외하고는 화합물 13과 같은 방법으로 화합물 14를 합성하였다. Compound 14 was synthesized in the same manner as Compound 13, except that Intermediate 02 was used.
m/z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)m / z: 439.14 (100.0%), 440.15 (30.5%), 441.15 (4.7%), 440.14 (1.8%)
실시예 15: 화합물 15의 합성Example 15 Synthesis of Compound 15
Figure PCTKR2014011226-appb-I000061
Figure PCTKR2014011226-appb-I000061
상기 중간체 08을 사용한 것을 제외하고는 화합물 13과 같은 방법으로 화합물 15를 합성하였다. Compound 15 was synthesized in the same manner as Compound 13, except that Intermediate 08 was used.
m/z: 455.12 (100.0%), 456.12 (32.9%), 457.12 (5.3%), 457.13 (4.5%), 458.12 (1.5%)m / z: 455.12 (100.0%), 456.12 (32.9%), 457.12 (5.3%), 457.13 (4.5%), 458.12 (1.5%)
실시예 16: 화합물 16의 합성Example 16: Synthesis of Compound 16
Figure PCTKR2014011226-appb-I000062
Figure PCTKR2014011226-appb-I000062
상기 중간체 19를 사용한 것을 제외하고는 화합물 13과 같은 방법으로 화합물 16을 합성하였다. Compound 16 was synthesized in the same manner as Compound 13, except that Intermediate 19 was used.
m/z: 514.19 (100.0%), 515.19 (39.0%), 516.20 (6.7%)m / z: 514.19 (100.0%), 515.19 (39.0%), 516.20 (6.7%)
실시예 17: 화합물 17의 합성Example 17 Synthesis of Compound 17
Figure PCTKR2014011226-appb-I000063
Figure PCTKR2014011226-appb-I000063
상기 중간체 01과 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole을 이용하여 화합물 13과 같은 방법으로 화합물 17을 합성하였다.Compound 17 was synthesized in the same manner as in compound 13, using Intermediate 01 and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole.
m/z: 528.17 (100.0%), 529.17 (39.0%), 530.18 (6.7%), 530.17 (1.0%)m / z: 528.17 (100.0%), 529.17 (39.0%), 530.18 (6.7%), 530.17 (1.0%)
실시예 18: 화합물 18의 합성Example 18: Synthesis of Compound 18
Figure PCTKR2014011226-appb-I000064
Figure PCTKR2014011226-appb-I000064
상기 중간체 01 2.5 g, 4-(3-bromophenyl)-2,6-diphenylpyrimidine 5.6 g, t-BuONa 1.7 g, Pd2(dba)3 0.45 g, (t-Bu)3P 0.6 ml를 톨루엔 40 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 컬럼정제하여 화합물 18 2.47 g (수율 40%)를 얻었다.The intermediate 01 2.5 g, 4- (3-bromophenyl) -2,6-diphenylpyrimidine 5.6 g, t-BuONa 1.7 g, Pd 2 (dba) 3 0.45 g, (t-Bu) 3 P 0.6 ml 40 ml of toluene It was dissolved in and stirred under reflux. After completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and then purified by column to obtain 2.47 g (yield 40%) of compound 18.
m/z: 514.18 (100.0%), 515.18 (39.4%), 516.19 (7.1%)m / z: 514.18 (100.0%), 515.18 (39.4%), 516.19 (7.1%)
실시예 19: 화합물 19의 합성Example 19: Synthesis of Compound 19
Figure PCTKR2014011226-appb-I000065
Figure PCTKR2014011226-appb-I000065
상기 중간체 01과 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine을 이용하여 화합물 18과 같은 방법으로 화합물 19를 합성하였다.Compound 19 was synthesized in the same manner as in compound 18, using Intermediate 01 and 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine.
m/z: 515.17 (100.0%), 516.18 (37.1%), 517.18 (7.6%), 516.17 (1.8%)m / z: 515.17 (100.0%), 516.18 (37.1%), 517.18 (7.6%), 516.17 (1.8%)
실시예 20: 화합물 20의 합성Example 20 Synthesis of Compound 20
Figure PCTKR2014011226-appb-I000066
Figure PCTKR2014011226-appb-I000066
상기 중간체 29와 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine을 이용하여 화합물 18과 같은 방법으로 화합물 20을 합성하였다.Compound 20 was synthesized in the same manner as in compound 18, using Intermediate 29 and 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine.
m/z: 531.15 (100.0%), 532.16 (37.0%), 533.16 (6.7%), 533.15 (5.5%), 532.15 (2.6%), 534.15 (1.7%)m / z: 531.15 (100.0%), 532.16 (37.0%), 533.16 (6.7%), 533.15 (5.5%), 532.15 (2.6%), 534.15 (1.7%)
실시예 21: 화합물 21의 합성Example 21: Synthesis of Compound 21
Figure PCTKR2014011226-appb-I000067
Figure PCTKR2014011226-appb-I000067
상기 중간체 05 2.0 g, 2-(3-bromophenyl)triphenylene 4.4 g, t-BuONa 1.4 g, Pd2(dba)3 0.35 g, (t-Bu)3P 0.5 ml를 톨루엔 30 ml에 녹인 후 환류 교반하였다. TLC로 반응 종결을 확인한 후 유기층을 MC로 추출하고 감압여과한 후 실리카 필터 후 재결정하여 화합물 21 2.1 g (수율 43%)를 얻었다.2.0 g of the intermediate 05, 4.4 g of 2- (3-bromophenyl) triphenylene, 1.4 g of t-BuONa, 0.35 g of Pd 2 (dba) 3 , and 0.5 ml of (t-Bu) 3 P were dissolved in 30 ml of toluene, followed by stirring under reflux. It was. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and recrystallized after a silica filter to obtain 2.1 g (yield 43%) of compound 21.
m/z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)m / z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)
실시예 22: 화합물 22의 합성Example 22: Synthesis of Compound 22
Figure PCTKR2014011226-appb-I000068
Figure PCTKR2014011226-appb-I000068
상기 중간체 12를 사용한 것을 제외하고는 화합물 21과 같은 방법으로 화합물 22를 합성하였다. Compound 22 was synthesized in the same manner as Compound 21, except that Intermediate 12 was used.
m/z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)m / z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)
실시예 23: 화합물 23의 합성Example 23: Synthesis of Compound 23
Figure PCTKR2014011226-appb-I000069
Figure PCTKR2014011226-appb-I000069
상기 중간체 26을 사용한 것을 제외하고는 화합물 21과 같은 방법으로 화합물 23을 합성하였다.Compound 23 was synthesized in the same manner as Compound 21, except that Intermediate 26 was used.
m/z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)m / z: 511.17 (100.0%), 512.17 (40.3%), 513.18 (7.5%), 514.18 (1.0%)
실시예 24: 화합물 24의 합성Example 24: Synthesis of Compound 24
Figure PCTKR2014011226-appb-I000070
Figure PCTKR2014011226-appb-I000070
상기 중간체 33을 사용한 것을 제외하고는 화합물 21과 같은 방법으로 화합물 24를 합성하였다.Compound 24 was synthesized in the same manner as Compound 21, except that Intermediate 33 was used.
m/z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)m / z: 527.15 (100.0%), 528.15 (40.0%), 529.15 (8.1%), 529.14 (4.5%), 530.14 (1.8%), 528.14 (1.1%)
실시예 25: 화합물 25의 합성Example 25 Synthesis of Compound 25
Figure PCTKR2014011226-appb-I000071
Figure PCTKR2014011226-appb-I000071
상기 중간체 115를 사용한 것을 제외하고는 화합물 21과 같은 방법으로 화합물 25를 합성하였다.Compound 25 was synthesized in the same manner as Compound 21, except that Intermediate 115 was used.
m/z: 528.14 (100.0%), 529.14 (40.1%), 530.15 (7.0%), 530.14 (5.4%), 531.14 (1.8%)m / z: 528.14 (100.0%), 529.14 (40.1%), 530.15 (7.0%), 530.14 (5.4%), 531.14 (1.8%)
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 PCTKR2014011226-appb-I000072
Figure PCTKR2014011226-appb-I000072
Figure PCTKR2014011226-appb-I000073
Figure PCTKR2014011226-appb-I000073
실시예 26Example 26
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 이송시킨 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:Firpic 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 청색 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., dried and transferred to a plasma cleaner, and then cleaned the substrate using oxygen plasma for 5 minutes and then a thermal vacuum evaporator (thermal 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 Compound 1: Firpic 10% to form 250 Å. Next, 300 유기 of ET01: Liq (1: 1) was deposited using an electron transport layer, followed by film formation of LiF 10 Å and 1000 1000 of aluminum (Al), and the device was encapsulated in a glove box to fabricate a blue organic light emitting device. .
실시예 27 내지 실시예 37Examples 27-37
상기 실시예 26과 같은 방법으로 발광층 호스트로 각각 화합물 2 내지 12를 사용하여 제막한 청색 유기발광소자를 제작하였다.In the same manner as in Example 26, a blue organic light emitting diode was manufactured by using a compound 2 to 12 as a light emitting layer host.
실시예 38Example 38
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 13: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 the compound 13: 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 39 내지 실시예 50Examples 39-50
실시예 38과 같은 방법으로 발광층 호스트로 각각 화합물 14 내지 25를 사용하여 제막한 녹색 유기발광소자를 제작하였다.In the same manner as in Example 38, a green organic light emitting diode was manufactured by using a compound 14 to 25 as a light emitting layer host.
비교예 1 Comparative Example 1
상기 실시예 1의 발광층 호스트로 화합물 1을 대신하여 mCP로 사용한 것을 제외하고는 동일한 방법으로 청색 유기발광소자를 제작하였다.A blue 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 mCP.
비교예 2 Comparative Example 2
상기 실시예 1의 발광층 호스트로 화합물 1을 대신하여 비교화합물 1로 사용한 것을 제외하고는 동일한 방법으로 청색 유기발광소자를 제작하였다.A blue organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 1 was used as Comparative Compound 1 instead of Compound 1 as the emission layer host.
비교예 3 Comparative Example 3
상기 실시예 13의 발광층 호스트로 화합물 13을 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 13, except that Compound 13 was used as CBP.
비교예 4 Comparative Example 4
상기 실시예 13의 발광층 호스트로 화합물 13을 대신하여 비교화합물 1로 사용한 것을 제외하고는 동일한 방법으로 녹색 유기발광소자를 제작하였다.A green organic light emitting diode was manufactured according to the same method as Example 13 except for using Compound 1 as the light emitting layer host of Example 13.
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
실시예 26 7.241 12.92 20.09 8.89 0.173 0.293 21
실시예 27 7.052 13.10 21.25 8.81 0.171 0.297 20
실시예 28 7.003 12.80 22.98 8.96 0.172 0.292 23
실시예 29 7.021 13.19 20.95 8.94 0.173 0.291 30
실시예 30 7.112 12.79 21.10 8.92 0.175 0.296 29
실시예 31 7.103 13.21 20.94 8.94 0.170 0.293 27
실시예 32 7.195 13.13 20.17 8.99 0.170 0.297 28
실시예 33 7.317 12.88 20.10 8.69 0.170 0.296 29
실시예 34 7.018 13.10 21.13 8.64 0.172 0.290 26
실시예 35 7.159 12.98 22.89 8.84 0.171 0.295 31
실시예 36 7.303 13.10 21.99 8.77 0.175 0.296 30
실시예 37 7.207 13.13 23.10 8.79 0.171 0.298 31
실시예 38 7.142 13.76 20.23 8.85 0.172 0.292 28
비교예 1 8.032 10.12 13.97 7.26 0.179 0.134 12
비교예 2 7.596 3.32 3.98 2.71 0.179 0.234 -
실시예 39 6.931 17.33 45.98 19.81 0.301 0.621 42
실시예 40 6.987 17.10 47.13 21.03 0.299 0.619 38
실시예 41 7.023 16.98 50.20 20.04 0.298 0.620 39
실시예 42 6.940 17.54 47.22 19.98 0.300 0.623 37
실시예 43 7.085 16.85 48.39 21.23 0.298 0.614 42
실시예 44 7.121 17.26 46.83 18.72 0.298 0.609 51
실시예 45 7.343 17.01 49.17 22.46 0.297 0.618 49
실시예 46 6.920 17.07 45.55 21.98 0.302 0.609 53
실시예 47 7.010 16.93 43.62 20.76 0.300 0.620 48
실시예 48 7.193 17.36 47.45 18.99 0.299 0.622 40
실시예 49 7.110 17.28 51.11 19.54 0.299 0.619 52
실시예 50 6.998 17.49 50.29 20.67 0.297 0.620 49
비교예 3 7.824 12.43 38.12 15.74 0.301 0.623 25
비교예 4 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 26 7.241 12.92 20.09 8.89 0.173 0.293 21
Example 27 7.052 13.10 21.25 8.81 0.171 0.297 20
Example 28 7.003 12.80 22.98 8.96 0.172 0.292 23
Example 29 7.021 13.19 20.95 8.94 0.173 0.291 30
Example 30 7.112 12.79 21.10 8.92 0.175 0.296 29
Example 31 7.103 13.21 20.94 8.94 0.170 0.293 27
Example 32 7.195 13.13 20.17 8.99 0.170 0.297 28
Example 33 7.317 12.88 20.10 8.69 0.170 0.296 29
Example 34 7.018 13.10 21.13 8.64 0.172 0.290 26
Example 35 7.159 12.98 22.89 8.84 0.171 0.295 31
Example 36 7.303 13.10 21.99 8.77 0.175 0.296 30
Example 37 7.207 13.13 23.10 8.79 0.171 0.298 31
Example 38 7.142 13.76 20.23 8.85 0.172 0.292 28
Comparative Example 1 8.032 10.12 13.97 7.26 0.179 0.134 12
Comparative Example 2 7.596 3.32 3.98 2.71 0.179 0.234 -
Example 39 6.931 17.33 45.98 19.81 0.301 0.621 42
Example 40 6.987 17.10 47.13 21.03 0.299 0.619 38
Example 41 7.023 16.98 50.20 20.04 0.298 0.620 39
Example 42 6.940 17.54 47.22 19.98 0.300 0.623 37
Example 43 7.085 16.85 48.39 21.23 0.298 0.614 42
Example 44 7.121 17.26 46.83 18.72 0.298 0.609 51
Example 45 7.343 17.01 49.17 22.46 0.297 0.618 49
Example 46 6.920 17.07 45.55 21.98 0.302 0.609 53
Example 47 7.010 16.93 43.62 20.76 0.300 0.620 48
Example 48 7.193 17.36 47.45 18.99 0.299 0.622 40
Example 49 7.110 17.28 51.11 19.54 0.299 0.619 52
Example 50 6.998 17.49 50.29 20.67 0.297 0.620 49
Comparative Example 3 7.824 12.43 38.12 15.74 0.301 0.623 25
Comparative Example 4 7.328 14.56 39.98 17.60 0.300 0.613 36
상기 표 1에 나타나는 바와 같이 본 발명의 실시예들은 비교예 1 내지 4에 비하여 유기발광소자의 모든 면에서 물성이 우수함을 확인할 수 있다. 특히 비교화합물 2 및 4의 경우 청색인광소자에 적용하였을 경우 청색 도판트보다 낮은 삼중항 에너지로 발광 효율이 낮음을 확인할 수 있었으며, 이는 본 발명의 화합물이 청색 및 녹색인광소자 적용에 있어 높은 삼중항 에너지로 인한 발광효율이 개선됨을 알 수 있다.As shown in Table 1, the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects of the organic light emitting device compared to Comparative Examples 1 to 4. In particular, in the case of Comparative Compounds 2 and 4, when applied to the blue phosphor, it was confirmed that the luminous efficiency was lower due to the lower triplet energy than the blue dopant, which means that the compound of the present invention is high in the application of the blue and green phosphors. It can be seen that the luminous efficiency due to energy is improved.
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 PCTKR2014011226-appb-I000074
    Figure PCTKR2014011226-appb-I000074
    상기 식에서,Where
    X는 각각 독립적으로 CR0 또는 N이며, 여기서 X중 적어도 하나는 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며,Each X is independently CR 0 or N, wherein at least one of X is 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
    Y는 S, O, Se, Te 또는 -NAr1이며, 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,Y is S, O, Se, Te or -NAr 1 , wherein 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
    R1은 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 헤테로아릴기이고, R 1 is 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 C 6-50 aryl group which is unsubstituted or substituted with an aryloxy group, C 6-30 aryl group, or 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 및 R3은 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 2 and R 3 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
  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 PCTKR2014011226-appb-I000075
    Figure PCTKR2014011226-appb-I000075
    상기 구조들에서 X, Y는 상기 화학식 1에서 정의한 바와 같으며, X, Y in the structures are as defined in Formula 1,
    Z는 CR6 또는 N이며, R6는 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 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고, Z is CR 6 or N, and R 6 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 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
    Ar은 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 C6-38의 헤테로아릴기이며,Ar is 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 C 6-38 aryl group which is unsubstituted or substituted with an aryloxy group, 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 6-38 heteroaryl group which is unsubstituted or substituted with an oxy group, a C 6-30 aryl group, or a C 2-30 heteroaryl group,
    Y1은 S, O, Se, Te 또는 -NAr2이며, 여기서 Ar2는 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 헤테로아릴기이고, Y 1 is S, O, Se, Te or —NAr 2 , wherein Ar 2 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 unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
    R4 및 R5는 각각 독립적으로 수소; 중수소; 중수소, 할로겐, 아미노기, 니트R 4 and R 5 are each independently hydrogen; heavy hydrogen; Deuterium, halogen, amino group, knit
    릴기, 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 C 1-30 alkyl group unsubstituted or substituted with a aryl group and a 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 1 내지 6의 정수이며, n이 1인 경우 X 중 적어도 하나는 N이다.n is an integer of 1 to 6, and when n is 1, at least one of X is N.
  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 PCTKR2014011226-appb-I000076
    Figure PCTKR2014011226-appb-I000077
    Figure PCTKR2014011226-appb-I000076
    Figure PCTKR2014011226-appb-I000077
    Figure PCTKR2014011226-appb-I000078
    Figure PCTKR2014011226-appb-I000079
    Figure PCTKR2014011226-appb-I000080
    Figure PCTKR2014011226-appb-I000081
    Figure PCTKR2014011226-appb-I000082
    Figure PCTKR2014011226-appb-I000078
    Figure PCTKR2014011226-appb-I000079
    Figure PCTKR2014011226-appb-I000080
    Figure PCTKR2014011226-appb-I000081
    Figure PCTKR2014011226-appb-I000082
    Figure PCTKR2014011226-appb-I000083
    Figure PCTKR2014011226-appb-I000083
    Figure PCTKR2014011226-appb-I000084
    Figure PCTKR2014011226-appb-I000084
    Figure PCTKR2014011226-appb-I000085
    Figure PCTKR2014011226-appb-I000085
    Figure PCTKR2014011226-appb-I000086
    Figure PCTKR2014011226-appb-I000086
    Figure PCTKR2014011226-appb-I000087
    Figure PCTKR2014011226-appb-I000087
    Figure PCTKR2014011226-appb-I000088
    Figure PCTKR2014011226-appb-I000088
    Figure PCTKR2014011226-appb-I000089
    Figure PCTKR2014011226-appb-I000089
    Figure PCTKR2014011226-appb-I000090
    Figure PCTKR2014011226-appb-I000090
    Figure PCTKR2014011226-appb-I000091
    Figure PCTKR2014011226-appb-I000091
    Figure PCTKR2014011226-appb-I000092
    Figure PCTKR2014011226-appb-I000092
    Figure PCTKR2014011226-appb-I000093
    Figure PCTKR2014011226-appb-I000093
    Figure PCTKR2014011226-appb-I000094
    Figure PCTKR2014011226-appb-I000094
    Figure PCTKR2014011226-appb-I000095
    Figure PCTKR2014011226-appb-I000095
    Figure PCTKR2014011226-appb-I000096
    Figure PCTKR2014011226-appb-I000096
    Figure PCTKR2014011226-appb-I000097
    Figure PCTKR2014011226-appb-I000098
    Figure PCTKR2014011226-appb-I000099
    Figure PCTKR2014011226-appb-I000097
    Figure PCTKR2014011226-appb-I000098
    Figure PCTKR2014011226-appb-I000099
    Figure PCTKR2014011226-appb-I000100
    Figure PCTKR2014011226-appb-I000100
  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 PCTKR2014011226-appb-I000101
    Figure PCTKR2014011226-appb-I000101
    상기 반응식 1에서 Ar은 상기 화학식 1에서 정의한 바와 같다.Ar in Scheme 1 is as defined in Chemical Formula 1.
  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/KR2014/011226 2013-11-20 2014-11-20 Novel light emission compound and organic light emitting device comprising same WO2015076600A1 (en)

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