WO2011013959A2 - Novel phenanthrene-based compound, and organic light-emitting device comprising same - Google Patents

Novel phenanthrene-based compound, and organic light-emitting device comprising same Download PDF

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WO2011013959A2
WO2011013959A2 PCT/KR2010/004878 KR2010004878W WO2011013959A2 WO 2011013959 A2 WO2011013959 A2 WO 2011013959A2 KR 2010004878 W KR2010004878 W KR 2010004878W WO 2011013959 A2 WO2011013959 A2 WO 2011013959A2
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compound
light emitting
layer
emitting device
organic light
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PCT/KR2010/004878
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French (fr)
Korean (ko)
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WO2011013959A3 (en
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배호기
안현철
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주식회사 동진쎄미켐
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Priority claimed from KR1020100071718A external-priority patent/KR101786498B1/en
Publication of WO2011013959A2 publication Critical patent/WO2011013959A2/en
Publication of WO2011013959A3 publication Critical patent/WO2011013959A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/27—Polycyclic condensed hydrocarbons containing three rings
    • C07C15/30—Phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems

Definitions

  • the present invention relates to a novel phenanthrene-based compound having excellent blue light emission characteristics and an organic light emitting device including the same in the light emitting layer.
  • 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 organic light emitting device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and an organic layer between the two electrodes.
  • the organic layer may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL) in addition to the light emitting layer (EML).
  • an electron injection layer and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to the light emission characteristics of the light emitting layer.
  • a light emitting dye may be doped into the light emitting layer (host).
  • the present invention provides a compound represented by any one of the following Chemical Formulas 1 to 3:
  • Ar 1 is anthryl substituted with Ar 2 ,
  • Ar 3 is C 6-30 aryl, optionally substituted with Ar 4 ,
  • Ar 2 and Ar 4 is a C 6-30 aryl are each independently optionally substituted with one or more C 1-4 alkyl or C 6-30 aryl or substituted.
  • the present invention provides an organic light emitting device comprising a compound represented by any one of Formulas 1 to 3 or a mixture of two or more in the light emitting layer as a light emitting material.
  • the compound of the present invention Since the compound of the present invention has excellent blue light emission characteristics and excellent hole transport characteristics and electron transport characteristics compared to the existing materials, the compound of the present invention is used as a light emitting material of an organic light emitting device, thereby significantly improving driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device. You can.
  • the compound of the present invention represented by any one of Formulas 1 to 3 is characterized in that it has a specific substituent at positions 1, 6, 1, 8 or 1,9 of phenanthrene.
  • Ar 3 is Ar 4 is phenyl, naphthyl, phenanthryl or anthryl optionally substituted by, Ar 2 and Ar 4 are each independently a phenyl, methylphenyl, dimethylphenyl, Trimethylphenyl, butylphenyl, naphthyl, phenanthryl, phenylphenanthryl or naphthylphenanthryl.
  • the compound of any one of Formulas 1 to 3 according to the present invention may be prepared based on the well-known Suzuki-coupling reaction of the aromatic boron compound and the aromatic halogen compound in the carbon-carbon coupling reaction.
  • each of the compounds of Formulas 1, 2, 3, 2a, and 3a of the present invention can be prepared as shown in Schemes 1-5 below.
  • Ar 2 and Ar 3 are as defined above.
  • the present invention provides an organic light emitting device comprising a compound represented by any one of Formulas 1 to 3 or a mixture of two or more in the light emitting layer as a light emitting material.
  • the organic light emitting device of the present invention includes one or more organic thin film layers including a compound represented by any one of Formulas 1 to 3 or a mixture of two or more, and the method of manufacturing the organic light emitting device is as follows.
  • the organic light emitting device includes an organic thin film 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 include 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, in particular, it is 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.
  • HIL hole injection layer
  • LB Langmuir-Blodgett
  • the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the desired hole injection layer, and generally, a deposition temperature of 50 to 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.
  • a hole transport layer (HTL) material may be formed on the hole injection layer by a vacuum deposition method, a spin coating method, a cast method, an LB method, etc., but it is easy to obtain a uniform film quality and difficult to generate pin holes. It is preferable to form by the vacuum deposition method at the point.
  • 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 (EML) material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by the vacuum deposition method. 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 be used alone or as a host, a compound represented by any one of formulas 1 to 3 of the present invention or a mixture represented by two or more mixtures.
  • a light emitting layer may be formed 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, green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6] -Difluorophenyl) -pyridinato-N, C2 '] picolinate), 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 blocking material (HBL) is further laminated by vacuum deposition or spin coating.
  • 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) can be used.
  • An electron transport layer is formed on the light emitting layer formed as described 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 an electron injection electrode, and the type thereof is not particularly limited.
  • 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)
  • EIL electron injection layer
  • 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 (EIL) 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 the vacuum deposition method.
  • EIL electron injection layer
  • the 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 and IZO may be used to obtain a top emitting element.
  • the organic light emitting device of the present invention has an organic structure of an anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), a cathode (cathode) structure
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electron transport layer
  • EIL electron injection layer
  • cathode cathode
  • each organic thin film layer formed according to the present invention as described above 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 thin film layer including the compound represented by any one of Formulas 1 to 3 or a mixture of two or more thereof has a uniform surface and excellent shape stability because the thickness of the organic thin film layer can be adjusted in molecular units.
  • the light emitting material of the present invention is excellent in electrical stability, has a high luminous efficiency and luminous luminance and can be implemented long life, it can be usefully used as a light emitting material of the organic light emitting device.
  • reaction product was recrystallized from toluene and n-hexane to obtain 5.3 g (49%) of 10- (naphthalen-2-yl) anthracene-9-yl boronic acid as a white crystal.
  • Triphenylphosphine 3.14 g (12 mmol) was mixed with 3.0 g (12 mmol) of 2-bromobenzyl bromide to obtain 5.8 g of phosphonium salt, followed by Wittig reaction with 2.09 (11.3 mmol) of 2-bromobenzaldehyde.
  • the obtained product was then recrystallized from ethanol to obtain 3.74 g (98%) of (E) -2,2'-dibromotytilbene.
  • Example 1 to 6 was repeated using 1-bromobenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (2) having the following structure.
  • Example 1 to 6 was repeated using 1-bromo-4-methylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (3) having the following structure.
  • Example 1-6 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (4) having the following structure.
  • Example 1-6 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (5) having the following structure.
  • Example 1-6 was repeated using 1-bromonaphthalene instead of 2-bromonaphthalene in Example 1 to obtain compound (6) having the following structure.
  • Example 1 the method of Example 12 was repeated using 1-bromobenzene instead of 2-bromonaphthalene to obtain Compound (8) having the following structure.
  • Example 1 the method of Example 12 was repeated using 1-bromo-4-methylbenzene instead of 2-bromonaphthalene to obtain Compound (9) having the following structure.
  • Example 1 the method of Example 12 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene to obtain a compound (10) having the following structure.
  • Example 1 the method of Example 12 was repeated using 1-bromo-4-tert-butylbenzene instead of 2-bromonaphthalene to obtain Compound (11) having the following structure.
  • An organic light emitting diode was manufactured according to a conventional method using the compound (1) to compound (12) obtained in Examples 6 to 17 as a light emitting host material. First, a 650 ⁇ hole injection layer (hole injection layer material: HI-406 (N 1 , N 1 '-(biphenyl-4,4'-diyl) on a 1500 ⁇ thick ITO layer (anode) formed on a glass substrate.
  • hole injection layer material: HI-406 N 1 , N 1 '-(biphenyl-4,4'-diyl
  • the luminous efficiency of the prepared organic light emitting device was measured and shown in Table 1 below.
  • the compound of the present invention is excellent in electrical stability, has a high luminous efficiency and luminous luminance and can be implemented long life, it is used as a light emitting material of the organic light emitting device to improve the luminous efficiency and life of the organic light emitting device Can be significantly improved.
  • the compound of the present invention Since the compound of the present invention has excellent blue light emission characteristics and excellent hole transport characteristics and electron transport characteristics compared to the existing materials, the compound of the present invention is used as a light emitting material of an organic light emitting device, thereby significantly improving driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device. You can.

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a novel phenanthrene-based compound and to an organic light-emitting device comprising same. More particularly, the compound of the present invention has superior blue color light-emitting characteristics, hole transport characteristics and electron transport characteristics, and thus can be used as a light-emitting material for an organic light-emitting device to provide the organic light-emitting device with low voltage driving characteristics, high luminance, and a long lifespan.

Description

신규한 페난트렌계 화합물 및 이를 포함하는 유기발광소자Novel phenanthrene compound and organic light emitting device comprising the same
본 발명은 우수한 청색 발광 특성을 갖는 신규 페난트렌계 화합물 및 이를 발광층에 포함하는 유기발광소자에 관한 것이다.The present invention relates to a novel phenanthrene-based compound having excellent blue light emission characteristics and an organic light emitting device including the same in the light emitting layer.
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.
일반적으로, 유기발광소자는 음극(전자주입전극)과 양극(정공주입전극), 및 상기 두 전극 사이에 유기층을 포함하는 구조를 갖는다. 이때, 유기층은 발광층(EML, light emitting layer) 이외에, 정공주입층(HIL, hole injection layer), 정공수송층(HTL, hole transport layer), 전자수송층(ETL, electron transport layer) 또는 전자주입층(EIL, electron injection layer)을 포함할 수 있으며, 발광층의 발광특성상 전자차단층(EBL, electron blocking layer) 또는 정공차단층(HBL, hole blocking layer)을 추가로 포함할 수 있다.In general, the organic light emitting device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and an organic layer between the two electrodes. In this case, the organic layer may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL) in addition to the light emitting layer (EML). , an electron injection layer, and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to the light emission characteristics of the light emitting layer.
이러한 구조의 유기발광소자에 전기장이 가해지면, 양극으로부터 정공이 주입되고, 음극으로부터 전자가 주입되어, 정공과 전자는 각각 정공수송층과 전자수송층을 거쳐 발광층에서 재조합(recombination)하게 되어 발광여기자(exitons)를 형성한다. 형성된 발광여기자는 바닥상태(ground states)로 전이하면서 빛을 방출한다. 발광 상태의 효율과 안정성을 증가시키기 위하여, 발광 색소(도펀트)를 발광층(호스트)에 도핑하기도 한다.When an electric field is applied to the organic light emitting device having such a structure, holes are injected from the anode, electrons are injected from the cathode, and holes and electrons are recombined in the light emitting layer through the hole transport layer and the electron transport layer, respectively, thereby excitons ). The formed light exciton emits light as it transitions to ground states. In order to increase the efficiency and stability of the light emitting state, a light emitting dye (dopant) may be doped into the light emitting layer (host).
유기발광소자의 발광층에 사용되는 물질로서 다양한 화합물들이 알려져 있으나, 이제까지 알려진 발광물질을 이용한 유기발광소자의 경우 높은 구동전압, 낮은 효율 및 짧은 수명으로 인해 실용화하는 데에 많은 어려움이 있었다. 따라서, 우수한 발광특성을 갖는 물질을 이용하여 저전압 구동, 고휘도 및 장수명을 갖는 유기발광소자를 개발하려는 노력이 지속되어 왔다.Various materials are known as materials used in the light emitting layer of the organic light emitting device, but the organic light emitting device using the known light emitting material has 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 diodes having low voltage driving, high brightness and long life using materials having excellent light emitting characteristics.
따라서, 본 발명의 목적은 구동전압이 우수하고 높은 발광효율과 발광휘도를 가지며 장수명 구현이 가능한 발광물질 및 이를 포함하는 유기발광소자를 제공하는 것이다.Accordingly, it is an object of the present invention to provide a light emitting material having excellent driving voltage, high luminous efficiency and luminous luminance, and a long lifetime, and an organic light emitting device including the same.
상기 목적을 달성하기 위하여 본 발명은 하기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by any one of the following Chemical Formulas 1 to 3:
화학식 1
Figure PCTKR2010004878-appb-C000001
 Formula 1
Figure PCTKR2010004878-appb-C000001
화학식 2
Figure PCTKR2010004878-appb-C000002
 Formula 2
Figure PCTKR2010004878-appb-C000002
화학식 3
Figure PCTKR2010004878-appb-C000003
 Formula 3
Figure PCTKR2010004878-appb-C000003
상기 식에서,Where
Ar1은 Ar2로 치환된 안트릴이고,Ar 1 is anthryl substituted with Ar 2 ,
Ar3는 Ar4로 치환되거나 치환되지 않은 C6-30 아릴이고,Ar 3 is C 6-30 aryl, optionally substituted with Ar 4 ,
상기 Ar2 및 Ar4는 각각 독립적으로 하나 이상의 C1-4 알킬 또는 C6-30 아릴로 치환되거나 치환되지 않은 C6-30 아릴이다.It said Ar 2 and Ar 4 is a C 6-30 aryl are each independently optionally substituted with one or more C 1-4 alkyl or C 6-30 aryl or substituted.
또한, 본 발명은 상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물을 발광물질로서 발광층에 포함하는 유기발광소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising a compound represented by any one of Formulas 1 to 3 or a mixture of two or more in the light emitting layer as a light emitting material.
본 발명의 화합물은 기존 물질에 비해 청색 발광 특성이 우수하면서도 정공 전달 특성 및 전자 전달 특성이 우수하므로, 유기발광소자의 발광물질로 사용되어 유기발광소자의 구동전압, 발광효율 및 수명 특성을 현저히 개선시킬 수 있다.Since the compound of the present invention has excellent blue light emission characteristics and excellent hole transport characteristics and electron transport characteristics compared to the existing materials, the compound of the present invention is used as a light emitting material of an organic light emitting device, thereby significantly improving driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device. You can.
상기 화학식 1 내지 3 중 어느 하나로 표시되는 본 발명의 화합물은 페난트렌의 1,6번, 1,8번 또는 1,9번 위치에 특정 치환기를 갖는 것을 특징으로 한다. 본 발명의 화합물에 있어서, 바람직하게는, Ar3는 Ar4로 치환되거나 치환되지 않은 페닐, 나프틸, 페난트릴 또는 안트릴이고, Ar2 및 Ar4는 각각 독립적으로 페닐, 메틸페닐, 디메틸페닐, 트리메틸페닐, 부틸페닐, 나프틸, 페난트릴, 페닐페난트릴 또는 나프틸페난트릴이다.The compound of the present invention represented by any one of Formulas 1 to 3 is characterized in that it has a specific substituent at positions 1, 6, 1, 8 or 1,9 of phenanthrene. In the compounds of the present invention, preferably, Ar 3 is Ar 4 is phenyl, naphthyl, phenanthryl or anthryl optionally substituted by, Ar 2 and Ar 4 are each independently a phenyl, methylphenyl, dimethylphenyl, Trimethylphenyl, butylphenyl, naphthyl, phenanthryl, phenylphenanthryl or naphthylphenanthryl.
또한, 상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물의 구체적인 예로서 하기 구조의 화합물들을 들 수 있다:In addition, specific examples of the compound represented by any one of Formulas 1 to 3 may include compounds having the following structure:
Figure PCTKR2010004878-appb-I000001
Figure PCTKR2010004878-appb-I000001
Figure PCTKR2010004878-appb-I000002
Figure PCTKR2010004878-appb-I000002
Figure PCTKR2010004878-appb-I000003
Figure PCTKR2010004878-appb-I000003
Figure PCTKR2010004878-appb-I000004
Figure PCTKR2010004878-appb-I000004
본 발명에 따른 화학식 1 내지 3 중 어느 하나의 화합물은 방향족 보론 화합물과 방향족 할로겐 화합물을 탄소-탄소 짝지음 반응 중 널리 알려진 스즈끼-짝지음(Suzuki-coupling) 반응에 근거하여 제조할 수 있다. 예를 들어, 본 발명의 화학식 1, 2, 3, 2a 및 3a의 화합물 각각은 하기 반응식 1 내지 5에 나타낸 바와 같이 제조할 수 있다.The compound of any one of Formulas 1 to 3 according to the present invention may be prepared based on the well-known Suzuki-coupling reaction of the aromatic boron compound and the aromatic halogen compound in the carbon-carbon coupling reaction. For example, each of the compounds of Formulas 1, 2, 3, 2a, and 3a of the present invention can be prepared as shown in Schemes 1-5 below.
[반응식 1]Scheme 1
Figure PCTKR2010004878-appb-I000005
Figure PCTKR2010004878-appb-I000005
[반응식 2]Scheme 2
Figure PCTKR2010004878-appb-I000006
Figure PCTKR2010004878-appb-I000006
[반응식 3]Scheme 3
Figure PCTKR2010004878-appb-I000007
Figure PCTKR2010004878-appb-I000007
[반응식 4]Scheme 4
Figure PCTKR2010004878-appb-I000008
Figure PCTKR2010004878-appb-I000008
[반응식 5]Scheme 5
Figure PCTKR2010004878-appb-I000009
Figure PCTKR2010004878-appb-I000009
상기 식에서,Where
Ar2 및 Ar3는 상기 정의한 바와 같다.Ar 2 and Ar 3 are as defined above.
상기 반응식 1 내지 5에 있어서, 화학식 1, 2, 3, 2a 및 3a의 화합물 각각의 제조에 출발물질로서 사용되는 방향족 보론 화합물과 방향족 할로겐 화합물은 통상적인 방법에 따라 하기 반응식 6에 나타낸 바와 같이 제조될 수 있다.In the above Reaction Schemes 1 to 5, the aromatic boron compound and the aromatic halogen compound used as starting materials for the preparation of the compounds of Formulas 1, 2, 3, 2a and 3a are prepared as shown in Scheme 6 below according to a conventional method. Can be.
[반응식 6]Scheme 6
[규칙 제91조에 의한 정정 07.09.2010]　
Figure WO-DOC-38
[Revision under Rule 91 07.09.2010]
Figure WO-DOC-38
[규칙 제91조에 의한 정정 07.09.2010]　
Figure WO-DOC-39
[Revision under Rule 91 07.09.2010]
Figure WO-DOC-39
또한, 본 발명은 상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물을 발광물질로서 발광층에 포함하는 유기발광소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising a compound represented by any one of Formulas 1 to 3 or a mixture of two or more in the light emitting layer as a light emitting material.
또한 본 발명의 유기발광소자는 상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물을 포함하는 1층 이상의 유기박막층을 포함하는 바, 상기 유기발광소자의 제조방법을 설명하면 다음과 같다.In addition, the organic light emitting device of the present invention includes one or more organic thin film layers including a compound represented by any one of Formulas 1 to 3 or a mixture of two or more, 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 유기박막층을 1 개 이상 포함할 수 있다.The organic light emitting device includes an organic thin film 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 include one or more.
먼저, 기판 상부에 높은 일함수를 갖는 애노드(anode) 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 유리기판 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, in particular, it is 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(HIL) 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.Thereafter, a hole injection layer (HIL) material may be formed on the anode by vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB), but it is easy to obtain a uniform film quality. In addition, it is preferable to form by the vacuum evaporation method from the point which pinholes hardly 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 characteristics of the desired hole injection layer, and generally, a deposition temperature of 50 to 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 (N1- (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(HTL) 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, a hole transport layer (HTL) material may be formed on the hole injection layer by a vacuum deposition method, a spin coating method, a cast method, an LB method, etc., but it is easy to obtain a uniform film quality and difficult to generate pin holes. It is preferable to form by the vacuum deposition method at the point. 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(EML) 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 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물로 표시되는 화합물을 단독으로 사용하거나 또는 호스트로 사용할 수 있다.Thereafter, the light emitting layer (EML) material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by the vacuum deposition method. 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 be used alone or as a host, a compound represented by any one of formulas 1 to 3 of the present invention or a mixture represented by two or more mixtures.
상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물을 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 도판트 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 using the compound represented by any one of Formulas 1 to 3 or a mixture of two or more as a light emitting host, a light emitting layer may be formed 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, green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6] -Difluorophenyl) -pyridinato-N, C2 '] picolinate), 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 전자수송층(HTL)으로 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, in the case of using the phosphorescent dopant in the light emitting layer, in order to prevent the triplet excitons or holes from diffusing into the electron transport layer (HTL), the hole blocking material (HBL) is further laminated by vacuum deposition or spin coating. desirable. 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 전자수송층(ETL)이 형성되는데, 이때 상기 전자수송층은 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다. An electron transport layer (ETL) is formed on the light emitting layer formed as described 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 전자주입전극(cathode)으로부터 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 an electron injection electrode, and the type thereof is not particularly limited. For example, 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) Can be. 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 전자수송층(ETL)의 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 (ETL) 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(EIL) 물질을 형성할 수 있으며, 이때 상기 전자수송층은 통상의 전자주입층 물질을 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다.Thereafter, an electron injection layer (EIL) 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 the vacuum deposition method.
마지막으로 전자주입층 상부에 캐소드 형성용 금속을 진공증착법이나 스퍼터링법 등의 방법에 의해 형성하고 캐소드(cathode)로 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 발광 소자를 얻기 위하여 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다. Finally, the 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 and IZO may be used to obtain a top emitting element.
본 발명의 유기발광소자는 애노드(anode), 정공주입층(HIL), 정공수송층(HTL), 발광층(EML), 전자수송층(ETL), 전자주입층(EIL), 캐소드(cathode) 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 has an organic structure of an anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), a cathode (cathode) structure Not only the light emitting device, but also the structure of the organic light emitting device of various structures is possible, it is also possible to further form one or two intermediate layers as needed.
상기와 같이 본 발명에 따라 형성되는 각 유기박막층의 두께는 요구되는 정도에 따라 조절할 수 있으며, 바람직하게는 10 내지 1,000 ㎚이며, 더욱 바람직하게는 20 내지 150 ㎚인 것이 좋다. The thickness of each organic thin film layer formed according to the present invention as described above 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 1 내지 3 중 어느 하나로 표시되는 화합물 또는 둘 이상의 혼합물을 포함하는 유기박막층은 유기박막층의 두께를 분자 단위로 조절할 수 있기 때문에 표면이 균일하며, 형태안정성이 뛰어난 장점이 있다.In addition, the present invention has an advantage that the organic thin film layer including the compound represented by any one of Formulas 1 to 3 or a mixture of two or more thereof has a uniform surface and excellent shape stability because the thickness of the organic thin film layer can be adjusted in molecular units.
본 발명의 발광물질은 전기적 안정성이 우수하고 높은 발광효율과 발광휘도를 가지며 장수명 구현이 가능하여, 유기발광소자의 발광물질로서 유용하게 사용될 수 있다.The light emitting material of the present invention is excellent in electrical stability, has a high luminous efficiency and luminous luminance and can be implemented long life, it can be usefully used as a light emitting material of the organic light emitting device.
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.
[실시예] : 본 발명의 화합물의 제조EXAMPLES Preparation of the Compound of the Present Invention
실시예 1. 9-(나프탈렌-2-일)안트라센 합성Example 1. 9- (naphthalen-2-yl) anthracene synthesis
질소기류하에서 2-브로모나프탈렌 20 g(96.6 mmol)을 THF 500 ㎖에 녹이고 -78 ℃에서 30분 동안 냉각시켰다. 여기에 2.5M의 n-뷰틸리튬 39 ㎖를 -78 ℃에서 30분 동안 서서히 적가시킨 후 30 분 동안 교반하였다. 그 다음, 반응물인 안트론 16.5 g(85 mmol)을 THF에 300 ㎖에 녹여서 15 분간 적가한 후 20 분 뒤에 상온에서 교반하였다. 반응의 진행정도는 TLC로 확인하였으며, 반응이 더 이상 진행되지 않으면 반응혼합액에 6M HCl 300 ㎖를 가하고 에틸아세테이트 200 ㎖로 3 회 추출하고, 이를 합한 후 무수황산마그네슘으로 물을 제거하여 감압증류하였다. 이렇게 얻어진 반응물을 에탄올로 재결정하여 연한 갈색의 결정인 9-(나프탈렌-2-일)안트라센 16.48 g(63.6%)을 얻었다.Under a stream of nitrogen, 20 g (96.6 mmol) of 2-bromonaphthalene was dissolved in 500 mL of THF and cooled at -78 ° C for 30 minutes. To this was added 39 ml of 2.5M n-butyllithium slowly dropwise at -78 ° C for 30 minutes followed by stirring for 30 minutes. Then, 16.5 g (85 mmol) of anthrone, which was a reactant, was dissolved in 300 ml of THF and added dropwise thereto for 15 minutes, followed by stirring at room temperature after 20 minutes. The progress of the reaction was confirmed by TLC, and if the reaction was not proceeded further, 300 ml of 6M HCl was added to the reaction mixture, extracted three times with 200 ml of ethyl acetate, the mixture was combined, and water was removed with anhydrous magnesium sulfate, followed by distillation under reduced pressure. . The reaction product thus obtained was recrystallized with ethanol to obtain 16.48 g (63.6%) of 9- (naphthalen-2-yl) anthracene as light brown crystals.
실시예 2. 9-브로모-10-나프탈렌-2-일-안트라센 합성Example 2. 9-Bromo-10-naphthalen-2-yl-anthracene synthesis
질소기류하에서 9-(나프탈렌-2-일)안트라센 9.64 g(31.7 mmol)을 DMF 660 ㎖에 녹이고, 상온에서 DMF 70 ㎖에 녹인 NBS 6.21 g(34.9 mmol)을 서서히 가하였다. 반응의 진행정도는 TLC로 확인하였으며, 반응이 더 이상 진행되지 않으면 반응 혼합물에 증류수 1200 ㎖를 넣어 생긴 침전물을 감압여과하여 회수한 다음, 메틸렌클로라이드에 녹인 후 무수황산마그네슘으로 탈수시켜 감압증류하였다. 이렇게 얻어진 반응물을 에탄올로 재결정하여 9-브로모-10-나프탈렌-2-일-안트라센 8.3 g(69%)를 얻었다. Under nitrogen stream, 9.64 g (31.7 mmol) of 9- (naphthalen-2-yl) anthracene was dissolved in 660 mL of DMF, and 6.21 g (34.9 mmol) of NBS dissolved in 70 mL of DMF at room temperature was slowly added. The progress of the reaction was confirmed by TLC. If the reaction was not proceeded further, the precipitate formed by adding 1200 ml of distilled water to the reaction mixture was collected by filtration under reduced pressure, dissolved in methylene chloride, dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. The reaction product thus obtained was recrystallized from ethanol to obtain 8.3 g (69%) of 9-bromo-10-naphthalen-2-yl-anthracene.
실시예 3. 10-(나프탈렌-2-일)안트라센-9-일 보론산 합성Example 3. 10- (naphthalen-2-yl) anthracene-9-yl boronic acid synthesis
질소기류하에서 9-브로모-10-나프탈렌-2-일-안트라센 12 g(31.3 mmol)을 THF 160 ㎖에 녹인 후 -78 ℃에서 30 분 동안 냉각시켰다. 여기에 2.5M의 n-뷰틸리튬 13.8 ㎖를 -78 ℃에서 30 분 동안 서서히 적가시킨 후 30분 동안 교반하였다. 그 다음, 트리메틸 보레이트 4.2 ㎖(37.6 mmol)을 15 분간 적가한 후 20 분 뒤에 상온에서 교반하였다. 반응의 진행정도는 TLC로 확인하였으며, 반응이 더 이상 진행되지 않으면 반응혼합액에 2M HCl 100 ㎖를 가하고 에틸아세테이트 60 ㎖로 3회 추출하여 이를 합한 후, 무수황산마그네슘으로 물을 제거한 다음 감압증류하였다. 이렇게 얻어진 반응물을 톨루엔과 n-헥산으로 재결정하여 미백색의 결정인 10-(나프탈렌-2-일)안트라센-9-일 보론산 5.3 g(49%)을 얻었다.Under a stream of nitrogen, 12 g (31.3 mmol) of 9-bromo-10-naphthalen-2-yl-anthracene was dissolved in 160 mL of THF and cooled at -78 ° C for 30 minutes. 13.8 mL of 2.5M n-butyllithium was slowly added dropwise at −78 ° C. for 30 minutes, followed by stirring for 30 minutes. Then, 4.2 ml (37.6 mmol) of trimethyl borate was added dropwise for 15 minutes, followed by 20 minutes of stirring at room temperature. The progress of the reaction was confirmed by TLC. If the reaction did not proceed any further, 100 ml of 2M HCl was added to the reaction mixture, and extracted three times with 60 ml of ethyl acetate, which were combined, and then dried over anhydrous magnesium sulfate, and then distilled under reduced pressure. . The reaction product thus obtained was recrystallized from toluene and n-hexane to obtain 5.3 g (49%) of 10- (naphthalen-2-yl) anthracene-9-yl boronic acid as a white crystal.
실시예 4. (E)-2,2'-디브로모스틸벤의 합성Example 4.Synthesis of (E) -2,2'-dibromostilbene
2-브로모벤질브로마이드 3.0g(12mmol)에 트리페닐포스핀 3.14g(12mmol)을 혼합하여 포스포늄 염 5.8g 을 얻은 후, 2-브로모벤즈알데히드 2.09(11.3mmol)과 Wittig 반응하여 흰색 고체를 얻은 다음 수득물을 에탄올로 재결정하여 (E)-2,2'-디브로모스틸벤 3.74 g(98%)을 얻었다.Triphenylphosphine 3.14 g (12 mmol) was mixed with 3.0 g (12 mmol) of 2-bromobenzyl bromide to obtain 5.8 g of phosphonium salt, followed by Wittig reaction with 2.09 (11.3 mmol) of 2-bromobenzaldehyde. The obtained product was then recrystallized from ethanol to obtain 3.74 g (98%) of (E) -2,2'-dibromotytilbene.
실시예 5. 1,8-디브로모페난트렌의 합성Example 5. Synthesis of 1,8-dibromophenanthrene
(E)-2,2'-디브로모스틸벤 5.0g(14.8mmol), 아이오딘 3.81g(15.0mmol), 프로필렌옥사이드 174.2g(3.0 mol)을 사이클로헥산 560ml에 녹인 후, 광 반응기에서 7시간동안 UV-램프를 조사하였다. 용매를 감압증류하여 제거한 후 노란색 고체를 얻은 다음 수득물을 에탄올/톨루엔으로 재결정하여 흰색 고체의 1,8-디브로모페난트렌 4.93 g(98%)을 얻었다.5.0 g (14.8 mmol) of (E) -2,2'-dibromostilbene, 3.81 g (15.0 mmol) of iodine, and 174.2 g (3.0 mol) of propylene oxide were dissolved in 560 ml of cyclohexane, and then UV-lamps were irradiated for hours. After distilling off the solvent under reduced pressure, a yellow solid was obtained and the obtained product was recrystallized from ethanol / toluene to obtain 4.93 g (98%) of 1,8-dibromophenanthrene as a white solid.
실시예 6. 1,8-비스(10-나프탈렌-2-일)안트라센-9-일)페난트렌 합성 [화합물 (1)]Example 6. Synthesis of 1,8-bis (10-naphthalen-2-yl) anthracene-9-yl) phenanthrene [Compound (1)]
질소분위기하에서 실시예 5에서 제조된 1,8-디브로모페난트렌 4 g(11.9 mmol), 실시예 3에서 제조된 10-(나프탈렌-2-일)안트라센-9-일 보론산 9.12 g(26.2 mmol), Pd(PPh3)4 0.28 g(0.238 mmol) 및 소디움카보네이트 7.57 g(71.4 mmol)을 넣은 후, 여기에 DME 300 ㎖를 넣고 교반하였다. 상기 혼합물에 에탄올 180 ㎖와 글리세린 90 ㎖를 넣고 격렬하게 교반한 후 환류반응시켰다. 상기 반응물을 상온으로 식히고 침전물을 여과한 후, 침전물을 증류수와 메탄올로 씻어주었다. 분홍색의 고체를 다시 메탄올(methanol)에 재결정하여 하기 구조의 화합물 (1)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C62H38=782 에 대하여 m/z(측정치)=782 임을 확인했다.4 g (11.9 mmol) of 1,8-dibromophenanthrene prepared in Example 5 under a nitrogen atmosphere, 9.12 g of 10- (naphthalen-2-yl) anthracene-9-yl boronic acid prepared in Example 3 ( 26.2 mmol), 0.28 g (0.238 mmol) of Pd (PPh 3 ) 4 and 7.57 g (71.4 mmol) of sodium carbonate were added thereto, followed by stirring with 300 mL of DME. 180 mL of ethanol and 90 mL of glycerin were added to the mixture, followed by vigorous stirring, followed by reflux reaction. After the reaction was cooled to room temperature and the precipitate was filtered, the precipitate was washed with distilled water and methanol. The pink solid was recrystallized in methanol again to obtain compound (1) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 782 for C 62 H 38 = 782.
[화합물(1)][Compound (1)]
Figure PCTKR2010004878-appb-I000012
Figure PCTKR2010004878-appb-I000012
실시예 7. 1,8-비스(10-페닐안트라센-9-일)페난트렌 합성 [화합물 (2)]Example 7. Synthesis of 1,8-bis (10-phenylanthracene-9-yl) phenanthrene [Compound (2)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모벤젠을 사용하여 상기실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (2)를 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C54H34=682 에 대하여 m/z(측정치)=682 임을 확인했다.Example 1 to 6 was repeated using 1-bromobenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (2) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 682 for C 54 H 34 = 682.
[화합물 (2)][Compound (2)]
Figure PCTKR2010004878-appb-I000013
Figure PCTKR2010004878-appb-I000013
실시예 8. 1,8-비스(10-p-톨릴안트라센-9-일)페난트렌 합성 [화합물 (3)]Example 8. Synthesis of 1,8-bis (10-p-tolylanthracene-9-yl) phenanthrene [Compound (3)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모-4-메틸벤젠을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (3)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C56H38=710 에 대하여 m/z(측정치)=710 임을 확인했다.Example 1 to 6 was repeated using 1-bromo-4-methylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (3) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 710 for C 56 H 38 = 710.
[화합물 (3)][Compound (3)]
Figure PCTKR2010004878-appb-I000014
Figure PCTKR2010004878-appb-I000014
실시예 9. 1,8-비스(10-(3,4-디메틸페닐)안트라센-9-일)페난트렌 합성 [화합물 (4)]Example 9. Synthesis of 1,8-bis (10- (3,4-dimethylphenyl) anthracene-9-yl) phenanthrene [Compound (4)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 4-브로모-1,2-디메틸벤젠을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (4)를 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C58H42=738 에 대하여 m/z(측정치)=738 임을 확인했다.Example 1-6 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (4) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 738 for C 58 H 42 = 738.
[화합물 (4)][Compound (4)]
Figure PCTKR2010004878-appb-I000015
Figure PCTKR2010004878-appb-I000015
실시예 10. 1,8-비스(10-(4-tert-부틸페닐)안트라센-9-일)페난트렌 합성 [화합물 (5)]Example 10 Synthesis of 1,8-bis (10- (4-tert-butylphenyl) anthracene-9-yl) phenanthrene [Compound (5)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 4-브로모-1,2-디메틸벤젠을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (5)를 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C62H50=795 에 대하여 m/z(측정치)=795 임을 확인했다.Example 1-6 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene in Example 1 to obtain compound (5) having the following structure. Field desorption mass spectrum (FD-MS) was carried out on the obtained compound, and it was confirmed that m / z (measured value) = 795 for C 62 H 50 = 795.
[화합물 (5)][Compound (5)]
Figure PCTKR2010004878-appb-I000016
Figure PCTKR2010004878-appb-I000016
실시예 11. 1,8-비스(10-(나프탈렌-1-일)안트라센-9-일)페난트렌 합성 [화합물 (6)]Example 11. Synthesis of 1,8-bis (10- (naphthalen-1-yl) anthracene-9-yl) phenanthrene [Compound (6)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모나프탈렌을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (6)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C62H38=782 에 대하여 m/z(측정치)=782 임을 확인했다.Example 1-6 was repeated using 1-bromonaphthalene instead of 2-bromonaphthalene in Example 1 to obtain compound (6) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 782 for C 62 H 38 = 782.
[화합물 (6)][Compound (6)]
Figure PCTKR2010004878-appb-I000017
Figure PCTKR2010004878-appb-I000017
실시예 12. 1-(10-(나프탈렌-2-일)안트라센-9-일)-9-페닐페난트렌 합성 [화합물 (7)]Example 12 Synthesis of 1- (10- (naphthalen-2-yl) anthracene-9-yl) -9-phenylphenanthrene [Compound (7)]
상기 실시예 4에서 2-브로모벤즈알데히드 대신에 벤조페논을, 상기 실시예 5에서 (E)-2,2'-디브로모스틸벤 대신 (2-(2-브로모페닐)에텐-1,1-디일)디벤젠을, 상기 실시예 6에서 1,8-디브로모페난트렌 대신 1-브로모-9-페닐페난트렌을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (7)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C44H28==557 에 대하여 m/z(측정치)=557 임을 확인했다.Benzophenone instead of 2-bromobenzaldehyde in Example 4, and (2- (2-bromophenyl) ethene-1, instead of (E) -2,2'-dibromostilbene in Example 5, 1-diyl) dibenzene was repeated in Example 6 to 1-bromo-9-phenylphenanthrene instead of 1,8-dibromophenanthrene in Example 6. Compound (7) was obtained. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 557 for C 44 H 28 = = 557.
[화합물 (7)][Compound (7)]
Figure PCTKR2010004878-appb-I000018
Figure PCTKR2010004878-appb-I000018
실시예 13. 9-페닐-1-(10-(페닐안트라센-9-일)페난트렌 합성 [화합물 (8)]Example 13. 9-phenyl-1- (10- (phenylanthracene-9-yl) phenanthrene synthesis [Compound (8)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모벤젠을 사용하여 상기 실시예 12의 방법을 반복하여 하기 구조의 화합물 (8)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C40H26=506 에 대하여 m/z(측정치)=506 임을 확인했다.In Example 1, the method of Example 12 was repeated using 1-bromobenzene instead of 2-bromonaphthalene to obtain Compound (8) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 506 for C 40 H 26 = 506.
[화합물 (8)][Compound (8)]
Figure PCTKR2010004878-appb-I000019
Figure PCTKR2010004878-appb-I000019
실시예 14. 9-페닐-1-(10-p-톨릴안트라센-9-일)페난트렌 합성 [화합물 (9)]Example 14 Synthesis of 9-phenyl-1- (10-p-tolylanthracene-9-yl) phenanthrene [Compound (9)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모-4-메틸벤젠을 사용하여 상기 실시예 12의 방법을 반복하여 하기 구조의 화합물 (9)를 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C41H28=521 에 대하여 m/z(측정치)=521 임을 확인했다.In Example 1, the method of Example 12 was repeated using 1-bromo-4-methylbenzene instead of 2-bromonaphthalene to obtain Compound (9) having the following structure. Field desorption mass spectrum (FD-MS) was carried out on the obtained compound, and it was confirmed that m / z (measured value) was 521 for C 41 H 28 = 521.
[화합물 (9)][Compound (9)]
Figure PCTKR2010004878-appb-I000020
Figure PCTKR2010004878-appb-I000020
실시예 15. 1-(10-(3,4-디메틸페닐)안트라센-9-일)페난트렌 합성 [화합물 (10)]Example 15 Synthesis of 1- (10- (3,4-dimethylphenyl) anthracene-9-yl) phenanthrene [Compound (10)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 4-브로모-1,2-디메틸벤젠을 사용하여 상기 실시예 12의 방법을 반복하여 하기 구조의 화합물 (10)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C42H30=534 에 대하여 m/z(측정치)=534 임을 확인했다.In Example 1, the method of Example 12 was repeated using 4-bromo-1,2-dimethylbenzene instead of 2-bromonaphthalene to obtain a compound (10) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 534 for C 42 H 30 = 534.
[화합물 (10)][Compound (10)]
Figure PCTKR2010004878-appb-I000021
Figure PCTKR2010004878-appb-I000021
실시예 16. 1-(10-(4-tert-부틸페닐)안트라센-9-일)페난트렌 합성 [화합물 (11)]Example 16 Synthesis of 1- (10- (4-tert-butylphenyl) anthracene-9-yl) phenanthrene [Compound (11)]
상기 실시예 1에서 2-브로모나프탈렌 대신에 1-브로모-4-tert-부틸벤젠을 사용하여 상기 실시예 12의 방법을 반복하여 하기 구조의 화합물 (11)을 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C44H34=563 에 대하여 m/z(측정치)=563 임을 확인했다.In Example 1, the method of Example 12 was repeated using 1-bromo-4-tert-butylbenzene instead of 2-bromonaphthalene to obtain Compound (11) having the following structure. Field desorption mass spectrum (FD-MS) was carried out with respect to the obtained compound, and it was confirmed that m / z (measured value) = 563 for C 44 H 34 = 563.
[화합물 (11)][Compound (11)]
Figure PCTKR2010004878-appb-I000022
Figure PCTKR2010004878-appb-I000022
실시예 17. 1-(10-(나프탈렌-2-일)안트라센-9-일)-9-페닐페난트렌 합성 [화합물 (12)]Example 17. Synthesis of 1- (10- (naphthalen-2-yl) anthracene-9-yl) -9-phenylphenanthrene [Compound (12)]
상기 실시예 4에서 2-브로모벤즈알데히드 대신에 4-브로모벤즈알데히드를, 상기 실시예 5에서 (E)-2,2'-디브로모스틸벤 대신 (Z)-1-브로모-2-(4-브로모스티릴)벤젠을, 상기 실시예 6에서 1,8-디브로모페난트렌 대신 1,6-디브로모페난트렌을 사용하여 상기 실시예 1 - 6의 방법을 반복하여 하기 구조의 화합물 (12)를 얻었다. 얻은 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C62H38==783 에 대하여, m/z(측정치)=783 임을 확인했다.4-bromobenzaldehyde in place of 2-bromobenzaldehyde in Example 4, and (Z) -1-bromo-2- in place of (E) -2,2'-dibromostilbene in Example 5 (4-bromostyryl) benzene was repeated in the above Example 1-6 using 1,6-dibromophenanthrene instead of 1,8-dibromophenanthrene in Example 6 to repeat the following structure Compound (12) was obtained. Field desorption mass spectrum (FD-MS) was carried out on the obtained compound, and C 62 H 38 = = 783, and m / z (measured value) = 783 was confirmed.
[화합물 (12)][Compound (12)]
Figure PCTKR2010004878-appb-I000023
Figure PCTKR2010004878-appb-I000023
[시험예] : 유기발광소자의 물성 측정[Test Example]: Measurement of physical properties of organic light emitting device
상기 실시예 6 내지 실시예 17에서 얻은 화합물 (1) 내지 화합물 (12)를 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기발광소자를 제작하였다. 먼저, 유리 기판에 형성된 1500 Å 두께의 ITO층(애노드) 위에 650 Å 두께의 정공주입층 (정공주입층 물질: HI-406(N1,N1'-(비페닐-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민)), 200 Å 두께의 정공수송층 (정공수송층 물질: 비스(N-(1-나프틸-n-페닐))벤지딘(α-NPB)), 350 Å 두께의 BD142가 도핑된 발광층(BD142: N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸크리센-6,12-디아민), 200Å 두께의 전자수송층 (전자수송층 물질: ET4(6,6'-(3,4-디메시틸-1,1-디메틸-1H-실올-2,5-디일)디-2,2'-비피리딘)) 및 1000/10Å 두께의 알루미늄/LiF 캐소드를 순차적으로 증착시켜 유기발광소자를 제작하였다. 이때, 발광층에 사용된 도펀트 BD142의 양을 호스트 100중량부에 대해 0, 3, 5 및 7중량부로 변화시켰다. An organic light emitting diode was manufactured according to a conventional method using the compound (1) to compound (12) obtained in Examples 6 to 17 as a light emitting host material. First, a 650 의 hole injection layer (hole injection layer material: HI-406 (N 1 , N 1 '-(biphenyl-4,4'-diyl) on a 1500 Å thick ITO layer (anode) formed on a glass substrate. ) Bis (N1- (naphthalen-1-yl) -N 4 , N 4 -diphenylbenzene-1,4-diamine), 200 Å thick hole transport layer (hole transport layer material: bis (N- (1-naph) Tyl-n-phenyl)) benzidine (α-NPB)), light emitting layer (BD142: N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -di doped with 350 Å thick BD142 Mesitylcrissen-6,12-diamine), 200 Å thick electron transport layer (electron transport layer material: ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2, 5-diyl) di-2,2'-bipyridine)) and 1000/10 / thick aluminum / LiF cathode were sequentially deposited to fabricate an organic light emitting device, wherein the amount of the dopant BD142 used in the light emitting layer was determined by the host 100. The weight was changed to 0, 3, 5 and 7 parts by weight.
제조된 유기발광소자의 발광효율을 측정하여 하기 표 1에 나타내었다. The luminous efficiency of the prepared organic light emitting device was measured and shown in Table 1 below.
표 1
구분 발광효율(cd/A) 구분 발광효율(cd/A)
화합물 (1) 10.1 화합물 (8) 10.3
화합물 (2) 9.5 화합물 (9) 10.2
화합물 (3) 9.6 화합물 (10) 10.2
화합물 (4) 9.6 화합물 (11) 10.4
화합물 (5) 9.8 화합물 (12) 8.8
화합물 (6) 9.9 ADN (기존물질) 7.5
화합물 (7) 10.5
Table 1
division Luminous Efficiency (cd / A) division Luminous Efficiency (cd / A)
Compound (1) 10.1 Compound (8) 10.3
Compound (2) 9.5 Compound (9) 10.2
Compound (3) 9.6 Compound (10) 10.2
Compound (4) 9.6 Compound (11) 10.4
Compound (5) 9.8 Compound (12) 8.8
Compound (6) 9.9 ADN (existing material) 7.5
Compound (7) 10.5
상기 표 1로부터 알 수 있듯이, 본 발명의 화합물은 전기적 안정성이 우수하고 높은 발광효율과 발광휘도를 가지며 장수명 구현이 가능하므로, 유기발광소자의 발광물질로 사용되어 유기발광소자의 발광효율 및 수명을 현저히 개선시킬 수 있다.As can be seen from Table 1, the compound of the present invention is excellent in electrical stability, has a high luminous efficiency and luminous luminance and can be implemented long life, it is used as a light emitting material of the organic light emitting device to improve the luminous efficiency and life of the organic light emitting device Can be significantly improved.
본 발명의 화합물은 기존 물질에 비해 청색 발광 특성이 우수하면서도 정공 전달 특성 및 전자 전달 특성이 우수하므로, 유기발광소자의 발광물질로 사용되어 유기발광소자의 구동전압, 발광효율 및 수명 특성을 현저히 개선시킬 수 있다.Since the compound of the present invention has excellent blue light emission characteristics and excellent hole transport characteristics and electron transport characteristics compared to the existing materials, the compound of the present invention is used as a light emitting material of an organic light emitting device, thereby significantly improving driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device. You can.

Claims (7)

  1. 하기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물:A compound represented by any one of the following Chemical Formulas 1 to 3:
    [화학식 1][Formula 1]
    Figure PCTKR2010004878-appb-I000024
    Figure PCTKR2010004878-appb-I000024
    [화학식 2][Formula 2]
    Figure PCTKR2010004878-appb-I000025
    Figure PCTKR2010004878-appb-I000025
    [화학식 3][Formula 3]
    Figure PCTKR2010004878-appb-I000026
    Figure PCTKR2010004878-appb-I000026
    상기 식에서,Where
    Ar1은 Ar2로 치환된 안트릴이고,Ar 1 is anthryl substituted with Ar 2 ,
    Ar3는 Ar4로 치환되거나 치환되지 않은 C6-30 아릴이고,Ar 3 is C 6-30 aryl, optionally substituted with Ar 4 ,
    상기 Ar2 및 Ar4는 각각 독립적으로 하나 이상의 C1-4 알킬 또는 C6-30 아릴로 치환되거나 치환되지 않은 C6-30 아릴이다.It said Ar 2 and Ar 4 is a C 6-30 aryl are each independently optionally substituted with one or more C 1-4 alkyl or C 6-30 aryl or substituted.
  2. 제1항에 있어서,The method of claim 1,
    상기 Ar3가 Ar4로 치환되거나 치환되지 않은 페닐, 나프틸, 페난트릴 또는 안트릴이고, 상기 Ar2 및 Ar4가 각각 독립적으로 페닐, 메틸페닐, 디메틸페닐, 트리메틸페닐, 부틸페닐, 나프틸, 페난트릴, 페닐페난트릴 또는 나프틸페난트릴인 것을 특징으로 하는 화합물.Ar 3 is phenyl, naphthyl, phenanthryl or anthryl unsubstituted or substituted with Ar 4 , and Ar 2 and Ar 4 are each independently phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, butylphenyl, naphthyl, Phenanthryl, phenylphenanthryl or naphthylphenanthryl.
  3. 제1항에 있어서,The method of claim 1,
    상기 화학식 1 내지 3 중 어느 하나로 표시되는 화합물이 하기 구조의 화합물중 하나인 것을 특징으로 하는 화합물:Compounds characterized in that the compound represented by any one of Formula 1 to 3 is one of the compounds of the following structure:
    Figure PCTKR2010004878-appb-I000027
    Figure PCTKR2010004878-appb-I000027
    Figure PCTKR2010004878-appb-I000028
    Figure PCTKR2010004878-appb-I000028
    Figure PCTKR2010004878-appb-I000029
    Figure PCTKR2010004878-appb-I000029
    Figure PCTKR2010004878-appb-I000030
    Figure PCTKR2010004878-appb-I000030
  4. 애노드(anode), 캐소드(cathode) 및 두 전극 사이에 제 1 항의 화합물 또는 둘 이상의 혼합물을 함유하는 발광층을 포함하는 유기발광소자.An organic light emitting device comprising an anode, a cathode and a light emitting layer containing a compound of claim 1 or a mixture of two or more between two electrodes.
  5. 제4항에 있어서,The method of claim 4, wherein
    애노드, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 및 캐소드가 순차적으로 적층된 구조를 갖는 것을 특징으로 하는 유기발광소자.An organic light emitting device comprising: a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked.
  6. 제5항에 있어서,The method of claim 5,
    상기 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층이 각각 10 내지 1,000 ㎚의 두께를 갖는 것을 특징으로 하는 유기발광소자. And the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer each have a thickness of 10 to 1,000 nm.
  7. 제4항에 있어서,The method of claim 4, wherein
    상기 발광층이 제 1 항의 화합물 또는 둘 이상의 혼합물을 발광 호스트로서 함유하고, 이 호스트 100 중량부 대비 0.01 내지 15 중량부의 도펀트를 추가로 함유하는 것을 특징으로 하는 유기발광소자. The organic light-emitting device characterized in that the light emitting layer contains the compound of claim 1 or a mixture of two or more as a light emitting host, and further contains 0.01 to 15 parts by weight dopant relative to 100 parts by weight of the host.
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