WO2012115394A2 - Compound, organic electronic device using same, and electronic device thereof - Google Patents

Compound, organic electronic device using same, and electronic device thereof Download PDF

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WO2012115394A2
WO2012115394A2 PCT/KR2012/001191 KR2012001191W WO2012115394A2 WO 2012115394 A2 WO2012115394 A2 WO 2012115394A2 KR 2012001191 W KR2012001191 W KR 2012001191W WO 2012115394 A2 WO2012115394 A2 WO 2012115394A2
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group
substituted
unsubstituted
organic
aryl
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PCT/KR2012/001191
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French (fr)
Korean (ko)
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WO2012115394A3 (en
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김동하
이선희
문성윤
이범성
최대혁
박정환
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덕산하이메탈(주)
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Priority claimed from KR1020120012490A external-priority patent/KR101982749B1/en
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Publication of WO2012115394A2 publication Critical patent/WO2012115394A2/en
Publication of WO2012115394A3 publication Critical patent/WO2012115394A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a compound, an organic electronic device using the same, and an electronic device thereof.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions.
  • the light emitting material may be classified into a polymer type and a low molecular type 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. Can be.
  • the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.
  • the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect.
  • a host / dopant system may be used.
  • the principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing 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 to be used.
  • a material constituting the organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material.
  • a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.
  • An object of the present invention is to provide a compound capable of improving high luminous efficiency, low driving voltage, color purity, and lifetime of an element, an organic electric element using the same, and an electronic device thereof.
  • the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device represented by the formula (1) to provide.
  • L is a single bond; C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy and amino groups Ren group; C 2 -C 60 hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group and an amino group Ring groups; And divalent substituted or unsubstituted aliphatic hydrocarbons.
  • B is directly bonded to A.
  • L may be bonded to at least one position of Ar 1 , R 1 to R 6 , and may be one selected from the group consisting of the following formulae.
  • n is an integer of 1-7. Since L is bonded to L when L is not a single bond, the maximum value of n may be determined according to the substituent type of L. In addition, when L is a single bond (not present), since B is directly bonded to A, the value of n may be 1 to 7 , and L may be bonded to a position of R 1 to R 7 .
  • Ar 1 to Ar 3 , R 1 to R 6 are the same as or different from each other, and each independently
  • Hydrogen, deuterium, halogen group C 1 ⁇ C 60 alkyl group, C 1 ⁇ C 60 alkoxy group, C 1 ⁇ C 60 alkylamine group, C 1 ⁇ C 60 arylamine group, C 1 ⁇ C 60 Alkyl thiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ⁇ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a
  • Arylamine group C 6 ⁇ C 60 aryl group, C 6 ⁇ C 20 aryl group substituted with deuterium, C 7 ⁇ C 20 arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 2 ⁇ C 20 It is selected from the group consisting of; C 2 ⁇ C 20 Alkenyl group unsubstituted or substituted with one or more substituents in the group consisting of a heterocyclic group, a nitrile group and an acetylene group.
  • X is one of NR 10 , O, S, P, Si (R 11 ) (R 12 ), C (R 13 ) (R 14 ),
  • R 10 to R 14 are the same as or different from each other, and each independently
  • Hydrogen atom Halogen atom; A substituted or unsubstituted C 1 -C 20 alkyl group;
  • Hydrogen, deuterium, halogen group C 1 ⁇ C 60 alkyl group, C 1 ⁇ C 60 alkoxy group, C 1 ⁇ C 60 alkylamine group, C 1 ⁇ C 60 arylamine group, C 1 ⁇ C 60 Alkylthiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ⁇ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substitute
  • It is selected from the group consisting of a condensed ring group of C 6 ⁇ C 60 aromatic ring and C 4 ⁇ C 60 Aliphatic ring.
  • Ar 1 to Ar 3 , R 1 to R 6 may be bonded to adjacent groups, respectively, to form a substituted or unsubstituted saturated or unsaturated ring.
  • the term 'neighborhood group' includes not only a substituent attached to the mother nucleus but also the mother nucleus itself.
  • R 1 and R 4 may form a saturated or unsaturated ring by combining or reacting with a neighboring substituent or functional group, a functional group forming the mother nucleus, or carbon included in the mother nucleus.
  • Saturated or unsaturated ring is a concept including alicyclic, aromatic, heterocycle, heterocyclic ring and the like.
  • the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device to the compound represented by the formula (2) to provide.
  • Ar One To Ar 3 , R One To R 6 , X, L are the same as defined in the formula (1).
  • the linking group L group in which the amine group is bonded may be bonded to one of the carbons of the five-membered heterocycle including X. That is, connector L group is R 5 Or R 6 Can be coupled to a location.
  • the formula (1) represents a compound represented by one of the following formula.
  • the compounds represented by Chemical Formula 1 may be one of the compounds represented by Chemical Formula, but are not limited thereto.
  • each substituent of the compounds represented by the formula (1) is practically difficult to exemplify all the compounds in a broad relationship, exemplary compounds have been described by way of example, but compounds represented by the formula (1) not shown in the above example formula Can be part of.
  • the present invention provides an organic electroluminescent device including the organic material layer comprising the above compound and an electronic device thereof.
  • the present invention can be used as at least one of hole injection, hole transport, electron injection, electron transport, light emitting material or passivation (kepping) material in the organic electronic device as a compound.
  • the present invention can be used as a host or a dopant in the light emitting material and the host / dopant, can be used as a hole injection, a hole transport layer.
  • the compound of the present invention improves the efficiency, life and stability of the organic electronic device, and lowers the driving voltage.
  • the present invention can provide a hole injection layer and a transport layer material having low driving voltage characteristics, high heat resistance and long life, an organic electric element including the same, and an electronic device thereof.
  • aryl group means a monocyclic or heterocyclic monovalent aromatic hydrocarbon group, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
  • heterocyclic group means an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom (heteroatom) instead of a carbon forming a ring, a hetero formed by neighboring substituents participating in the bond or reaction Aromatic or cycloaliphatic rings.
  • the intermediate b, the intermediate 4c, and Pd (PPh 3 ) 4 were added with K 2 CO 3 in 500 ml of THF and 250 ml of water, and refluxed for 24 hours.
  • the obtained solid was washed with water and methanol and then separated by silica gel column chromatography to give the product A-8, a white solid, in 71% yield.
  • Table 2 shows the results of confirming the composition by mass spectrometry (FD-MS) of the final compounds synthesized according to the above preparation examples.
  • the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product in 65% yield.
  • Table 4 shows the results of confirming the composition by mass spectrometry (FD-MS) of the final compounds synthesized according to the above preparation examples.
  • an organic light emitting device was manufactured according to a conventional method.
  • 4T-NATA 4,4'4 "tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine
  • 2T-NATA 4,4'4 "tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine
  • 2T-NATA 4,4'4 "tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine
  • the compound according to the invention was then vacuum deposited to a thickness of 30 nm as the hole transport compound to form a hole transport layer.
  • a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X is blue fluorescent light) 9,10-di (naphthalene-2-anthracene (AND)) was used as the dopant and the light emitting host material.
  • BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum
  • BAlq (2-methyl-8-quinolineoleito) aluminum
  • BAlq 3 Tris (8-quinolinol) aluminum
  • LiF an alkali metal halide
  • Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.
  • an organic electroluminescent device having the same structure as that of the experimental example was manufactured using a compound represented by the following formula (hereinafter abbreviated as NPB) as a hole transport material instead of the compound of the present invention.
  • NPB a compound represented by the following formula
  • the organic electroluminescent device using the organic electroluminescent device material of the present invention has high efficiency and color purity as well as long life blue light emission is obtained as a hole transporting material of the organic electroluminescent device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.
  • Triphenylphosphinepalladium was added to 2-neck in Sub 1-1 dissolved in oxodichlorobenzene, and the mixture was refluxed and stirred for 24 hours. Thereafter, the mixture was heated to room temperature, concentrated and separated by silica gel column chromatography to obtain Sub 1-2 as 85%.
  • Ar-Br examples of Ar-Br are as follows, but are not necessarily limited thereto.
  • Sub 2 is as follows, but is not limited thereto.
  • L is specifically a single bond; C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy and amino groups Ren group; C 2 -C 60 hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group and an amino group Ring groups; And divalent substituted or unsubstituted aliphatic hydrocarbons.
  • a group consisting of divalent functional groups such as phenylene, biphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazinylene, piperidinylene, piperazinylene, pyrrolidenylene, pyrrolene, fluoreneylene and the like
  • the synthesis method is the same.
  • An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a hole transport layer.
  • 2T-NATA 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine
  • 2T-NATA 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine
  • a light emitting layer 7% doped with BD-052X (Idemitus Co., Ltd.) having a thickness of 45 nm (where BD-052X is a blue fluorescent dopant, and 9,10-die (naphthalene-2) is used as a light emitting host material.
  • Anthracene (AND) was used as (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (abbreviated as BAlq) as the hole blocking layer.
  • Vacuum deposition was carried out to a thickness of 10 nm, and then tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq3) was deposited to a thickness of 40 nm with an electron injection layer. Thereafter, LiF, an alkali metal halide, was deposited at a thickness of 0.2 nm, and then Al was deposited at a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic EL device.
  • Alq3 tris (8-quinolinol) aluminum
  • An organic light emitting diode was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material of a light emitting layer.
  • a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.
  • 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl hereinafter abbreviated as -NPD was vacuum-deposited to a thickness of 30 nm as a hole transporting compound on the membrane to form a hole transport layer. Formed.
  • the compound according to the present invention was deposited on the hole transport layer as a phosphorescent host material to form a light emitting layer, and then tris (2-phenylpyridine) iridium (hereinafter, I r) was used as a phosphorescent Ir metal complex dopant. (abbreviated to (ppy) 3)). At this time, the concentration of Ir (ppy) 3 in the light emitting layer was 5% by weight.
  • As a hole blocking layer (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and electron injection was performed.
  • Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited into the layer to a thickness of 40 nm. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to manufacture an organic light emitting device using the Al / LiF as a cathode.
  • the organic light emitting device using the organic light emitting device material of the present invention can be used as a light emitting host, a hole transporting material can significantly improve the low driving voltage, color purity, high luminous efficiency and lifespan. have.
  • the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
  • each of the substituents of the compounds represented by the formula (1) has a broad relationship, exemplarily described the synthesis examples of the representative compounds, the compounds represented by the formula (1) not illustrated by way of example as a synthesis example Can be configured.
  • the compound which has the intrinsic property of the introduced substituent can be synthesize
  • substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.
  • the compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.
  • the compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
  • the organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.
  • the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
  • the compound of the present invention can be used in a soluble process.
  • the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process.
  • the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
  • Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
  • organic electroluminescent device As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described.
  • OLED organic electroluminescent device
  • the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
  • Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
  • 1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
  • the organic electroluminescent device except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • a hole injection layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electron injection layer
  • ETL electron transport layer
  • the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located.
  • the protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
  • the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
  • the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form.
  • the organic layer may be used not only in one layer but also in two or more layers.
  • it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
  • the organic electroluminescent device is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon.
  • PVD physical vapor deposition
  • an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
  • the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
  • the organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
  • the substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.
  • the positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer.
  • Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the hole injection layer is located on the anode.
  • the conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
  • the hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • HOMO occupied molecular orbital
  • Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is positioned on the hole injection layer.
  • the hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons.
  • applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
  • NPD NPB
  • spiro-arylamine compounds perylene-arylamine compounds
  • azacycloheptatriene compounds bis (diphenylvinylphenyl) anthracene and silicon germanium oxide.
  • the organic light emitting layer is positioned on the hole transport layer.
  • the organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency.
  • the light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.
  • Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; D
  • DCJTB [2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H
  • doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile
  • a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer.
  • the electron transport layer is positioned on the organic light emitting layer.
  • the electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
  • Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron injection layer is stacked on the electron transport layer.
  • the electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like.
  • the electron injection layer may be formed in a thickness range of 100 ⁇ 300 ⁇ .
  • the cathode is positioned on the electron injection layer. This cathode serves to inject electrons.
  • the material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection.
  • a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used.
  • electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 ⁇ m or less may also be used.
  • the compound of the present invention can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
  • the organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
  • the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device.
  • This terminal means a current or future wired or wireless communication terminal.
  • the terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

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Abstract

The present invention relates to a compound, to an organic electronic device using same, and to an electronic device thereof.

Description

화합물 및 이를 이용한 유기전기소자, 그 전자장치Compound, organic electric element using same, electronic device thereof
본 발명은 화합물 및 이를 이용한 유기전기소자, 그 전자장치에 관한 것이다.The present invention relates to a compound, an organic electronic device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
여기서 유기물층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions.
그리고, 상기 발광 재료는 분자량에 따라 고분자형과 저분자형으로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있다. The light emitting material may be classified into a polymer type and a low molecular type 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. Can be.
또한, 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다.In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.
한편, 발광 재료로서 하나의 물질만 사용하는 경우 분자간 상호 작용에 의하여 최대 발광 파장이 장파장으로 이동하고 색순도가 떨어지거나 발광 감쇄 효과로 소자의 효율이 감소되는 문제가 발생하므로, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여 발광 재료로서 호스트/도판트 계를 사용할 수 있다. On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used.
그 원리는 발광층을 형성하는 호스트보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing 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 to be used.
전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.
본 발명은 소자의 높은 발광효율, 낮은 구동전압, 색순도, 및 수명을 향상시킬 수 있는 화합물 및 이를 이용한 유기전기소자, 그 전자 장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound capable of improving high luminous efficiency, low driving voltage, color purity, and lifetime of an element, an organic electric element using the same, and an electronic device thereof.
구체적으로, 본 발명은 전술한 종래 기술의 문제점을 해결하고, 소자의 높은 발광효율, 낮은 구동전압, 색순도, 안정성 및 수명의 향상이라는 본 발명의 목적을 달성하기 위하여 하기 화학식 1 로 표시되는 화합물을 제공한다.Specifically, the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device represented by the formula (1) to provide.
[화학식 1][Formula 1]
Figure PCTKR2012001191-appb-I000001
Figure PCTKR2012001191-appb-I000001
상기 화학식에서,In the above formula,
(1) A 는
Figure PCTKR2012001191-appb-I000002
이고, B는
Figure PCTKR2012001191-appb-I000003
이다.(1) A is
Figure PCTKR2012001191-appb-I000002
And B is
Figure PCTKR2012001191-appb-I000003
to be.
(2) L은 단일결합; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기; 및 2가의 치환 또는 비치환된 지방족 탄화수소로 구성된 군에서 선택된다. L이 단일결합인 경우에는 B가 A에 직접 결합된다. 상기 L은 Ar1, R1 내지 R6 중 적어도 하나의 위치에 결합될 수 있으며, 하기 화학식으로 이루어진 군에서 선택된 하나일 수 있다.(2) L is a single bond; C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy and amino groups Ren group; C 2 -C 60 hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group and an amino group Ring groups; And divalent substituted or unsubstituted aliphatic hydrocarbons. When L is a single bond, B is directly bonded to A. L may be bonded to at least one position of Ar 1 , R 1 to R 6 , and may be one selected from the group consisting of the following formulae.
Figure PCTKR2012001191-appb-I000004
Figure PCTKR2012001191-appb-I000004
(3) n은 1 내지 7의 정수이다. L이 단일결합이 아닌 경우 B가 L에 결합되므로, n의 최대값은 L의 치환기 종류에 따라 결정될 수 있다. 그리고, L이 단일결합(부존재)인 경우 B가 A에 직접 결합되므로 n의 값은 1~7이 될 수 있으며, R1 내지 R7의 위치에 L이 결합될 수 있다. (3) n is an integer of 1-7. Since L is bonded to L when L is not a single bond, the maximum value of n may be determined according to the substituent type of L. In addition, when L is a single bond (not present), since B is directly bonded to A, the value of n may be 1 to 7 , and L may be bonded to a position of R 1 to R 7 .
(4) Ar1 내지 Ar3, R1 내지 R6은 서로 같거나 상이하고, 각각 독립적으로 (4) Ar 1 to Ar 3 , R 1 to R 6 are the same as or different from each other, and each independently
수소; 할로겐; 치환 또는 비치환된 지방족 탄화 수소기;Hydrogen; halogen; Substituted or unsubstituted aliphatic hydrocarbon group;
수소, 중수소, 할로겐기, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~ C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1~ C60의 알킬 티오펜기, C6 ~ C60의 아릴 티오펜기, C2 ~ C60의 알케닐기, C2 ~ C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 치환 또는 비치환된 C2 ~ C60의 헤테로고리기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환된 C6 ~ C60의 아릴기; Hydrogen, deuterium, halogen group, C 1 ~ C 60 alkyl group, C 1 ~ C 60 alkoxy group, C 1 ~ C 60 alkylamine group, C 1 ~ C 60 arylamine group, C 1 ~ C 60 Alkyl thiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ~ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C 2 ~ C 60 heterocyclic group;
수소, 중수소, 할로겐, CN, NO2, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1 ~ C60의 알킬티오기, C2 ~ C60의 알케닐기, C2 ~C60의 알키닐기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C3 ~ C60의 시클로알킬기, C7 ~ C60의 아릴알킬기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 C2 ~ C60의 헤테로고리기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 아세틸렌기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환되고 O, N, S, Si, P 중 적어도 하나를 포함하는 C2 ~C60의 헤테로고리기; Hydrogen, deuterium, halogen, CN, NO 2 , C 1 to C 60 alkyl group, C 1 to C 60 alkoxy group, C 1 to C 60 alkylamine group, C 1 to C 60 arylamine group, C 1 - an alkylthio group of C 60, C 2 ~ C 60 alkenyl group, C 2 - C 60 alkynyl group, a C 6 ~ C 60 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 60 of the aryl group, C 3 ~ C 60 cycloalkyl group, C 7 ~ C 60 arylalkyl group, C 8 ~ C 60 aryl alkenyl group, substituted or unsubstituted C 2 ~ C 60 heterocyclic group, substituted or unsubstituted silane group, substitution Or unsubstituted or substituted with at least one group selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and an acetylene group, C 2 ~ C 60 containing at least one of O, N, S, Si, P Heterocyclic group of;
C6 ~ C60의 방향족 고리와 C4 ~ C60의 지방족 고리의 축합 고리기; 및Condensed ring groups of C 6 -C 60 aromatic rings and C 4 -C 60 aliphatic rings; And
아릴아민기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C20의 아릴기, C7 ~ C20의 아릴알킬기, C8 ~ C20의 아릴알케닐기, C2 ~ C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환된 C2 ~ C20의 알케닐기;로 구성된 군에서 선택된다.Arylamine group, C 6 ~ C 60 aryl group, C 6 ~ C 20 aryl group substituted with deuterium, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 2 ~ C 20 It is selected from the group consisting of; C 2 ~ C 20 Alkenyl group unsubstituted or substituted with one or more substituents in the group consisting of a heterocyclic group, a nitrile group and an acetylene group.
(5) X는 NR10, O, S, P, Si(R11)(R12), C(R13)(R14) 중 하나이며, (5) X is one of NR 10 , O, S, P, Si (R 11 ) (R 12 ), C (R 13 ) (R 14 ),
여기서 R10 내지 R14는 서로 같거나 상이하고, 각각 독립적으로Wherein R 10 to R 14 are the same as or different from each other, and each independently
수소원자; 할로겐 원자; 치환 또는 비치환된 C1~C20의 알킬기; Hydrogen atom; Halogen atom; A substituted or unsubstituted C 1 -C 20 alkyl group;
수소, 중수소, 할로겐기, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~ C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1~ C60의 알킬티오펜기, C6 ~ C60의 아릴 티오펜기, C2 ~ C60의 알케닐기, C2 ~ C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 치환 또는 비치환된 C2 ~ C60의 헤테로고리기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환된 C6 ~ C60의 아릴기; Hydrogen, deuterium, halogen group, C 1 ~ C 60 alkyl group, C 1 ~ C 60 alkoxy group, C 1 ~ C 60 alkylamine group, C 1 ~ C 60 arylamine group, C 1 ~ C 60 Alkylthiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ~ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C 2 ~ C 60 heterocyclic group;
수소, 중수소, 할로겐, CN, NO2, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1 ~ C60의 알킬티오기, C2 ~ C60의 알케닐기, C2 ~C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, 치환 또는 비치환된 C2 ~ C60의 헤테로고리기, 아세틸렌기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환되고 O, N, S, Si, P 중 적어도 하나를 이종 원자로 포함하는 C2 ~C60의 헤테로고리기; 및Hydrogen, deuterium, halogen, CN, NO 2 , C 1 to C 60 alkyl group, C 1 to C 60 alkoxy group, C 1 to C 60 alkylamine group, C 1 to C 60 arylamine group, C 1 ~ C import of 60 alkylthio, C 2 ~ C 60 alkenyl group, C 2 ~ C 60 alkynyl group, C 3 ~ C 60 cycloalkyl group, C 6 ~ C 60 of the aryl group, a C 6 substituted with deuterium ~ C 60 aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, substituted or unsubstituted C 2 ~ C 60 heterocyclic group, acetylene group, substituted or unsubstituted silane C 2 to C substituted or unsubstituted with one or more groups selected from the group consisting of a group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and containing at least one of O, N, S, Si, and P as hetero atoms. 60 heterocyclic group; And
C6 ~ C60의 방향족 고리와 C4 ~ C60의 지방족 고리의 축합 고리기;로 이루어진 군에서 선택된다.It is selected from the group consisting of a condensed ring group of C 6 ~ C 60 aromatic ring and C 4 ~ C 60 Aliphatic ring.
(6) Ar1 내지 Ar3, R1 내지 R6은 각각 인접한 기와 결합하여 치환 또는 비치환된 포화 또는 불포화 고리를 형성할 수 있다. 이때, '이웃한 기'라 함은 모핵에 결합된 치환기뿐만 아니라 모핵 자체를 포함한다. 따라서, R1, R4는 이웃한 치환기나 작용기(functional group), 또는 모핵을 형성하는 작용기 또는 모핵에 포함된 탄소 등과 결합 또는 반응하여 포화 또는 불포화고리를 형성할 수 있다. 포화 또는 불포화고리라 함은 지환족, 방향족, 복소환, 헤테로고리 등을 포함하는 개념이다.(6) Ar 1 to Ar 3 , R 1 to R 6 may be bonded to adjacent groups, respectively, to form a substituted or unsubstituted saturated or unsaturated ring. In this case, the term 'neighborhood group' includes not only a substituent attached to the mother nucleus but also the mother nucleus itself. Accordingly, R 1 and R 4 may form a saturated or unsaturated ring by combining or reacting with a neighboring substituent or functional group, a functional group forming the mother nucleus, or carbon included in the mother nucleus. Saturated or unsaturated ring is a concept including alicyclic, aromatic, heterocycle, heterocyclic ring and the like.
또한 본 발명은 전술한 종래 기술의 문제점을 해결하고, 소자의 높은 발광효율, 낮은 구동전압, 색순도, 안정성 및 수명의 향상이라는 본 발명의 목적을 달성하기 위하여 하기 화학식 2 내지 8로 표시되는 화합물을 제공한다. In addition, the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device to the compound represented by the formula (2) to provide.
[화학식 2][Formula 2]
Figure PCTKR2012001191-appb-I000005
Figure PCTKR2012001191-appb-I000005
상기 화학식에서 Ar1 내지 Ar3, R1 내지 R6, X, L 및 n은 화학식 (1)에서 정의된 것과 동일하다. 화학식 (2)에서 아민기가 결합된 연결기 L그룹을 상기와 같이 표시한 것은 연결기 그룹이 Ar1, R1 내지 R6 중 어느 위치에 결합될 수 있음을 나타내기 위함이다.remind Ar in the formulaOne To Ar3, ROne To R6, X, L and n are the same as defined in the formula (1). In the formula (2), the linking group L group having the amine group bonded as described above is represented by the linking group ArOne, ROne To R6 It is intended to indicate that any of the positions can be combined.
[화학식 3][Formula 3]
Figure PCTKR2012001191-appb-I000006
Figure PCTKR2012001191-appb-I000006
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X, L은 화학식 (1)에서 정의된 것과 동일하다.remind In the formula, ArOne To Ar3, ROne To R6, X, L are the same as defined in the formula (1).
[화학식 4][Formula 4]
Figure PCTKR2012001191-appb-I000007
Figure PCTKR2012001191-appb-I000007
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X, L은 화학식 (1)에서 정의된 것과 동일하다. 화학식 (4)에서 아민기가 결합된 연결기 L그룹은 X를 포함하는 오원자헤테로고리의 탄소 중 하나에 결합될 수 있다. 즉, 연결기 L그룹은 R5 또는 R6 위치에 결합될 수 있다.remind In the formula, ArOne To Ar3, ROne To R6, X, L are the same as defined in the formula (1). In the formula (4), the linking group L group in which the amine group is bonded may be bonded to one of the carbons of the five-membered heterocycle including X. That is, connector L group is R5 Or R6 Can be coupled to a location.
[화학식 5][Formula 5]
Figure PCTKR2012001191-appb-I000008
Figure PCTKR2012001191-appb-I000008
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X는 화학식 (1)에서 정의된 것과 동일하다.remind In the formula, ArOne To Ar3, ROne To R6, X is the same as defined in the formula (1).
[화학식 6][Formula 6]
Figure PCTKR2012001191-appb-I000009
Figure PCTKR2012001191-appb-I000009
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X는 화학식 (1)에서 정의된 것과 동일하다.remind In the formula, ArOne To Ar3, ROne To R6, X is the same as defined in the formula (1).
[화학식 7][Formula 7]
Figure PCTKR2012001191-appb-I000010
Figure PCTKR2012001191-appb-I000010
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X는 화학식 (1)에서 정의된 것과 동일하다.remind In the formula, ArOne To Ar3, ROne To R6, X is the same as defined in the formula (1).
[화학식 8][Formula 8]
Figure PCTKR2012001191-appb-I000011
Figure PCTKR2012001191-appb-I000011
상기 화학식에서, Ar1 내지 Ar3, R1 내지 R6, X는 화학식 (1)에서 정의된 것과 동일하다.remind In the formula, ArOne To Ar3, ROne To R6, X is the same as defined in the formula (1).
더욱 구체적으로, 상기 화학식 (1)은 하기 화학식 중 하나로 표시되는 화합물을 나타낸다.More specifically, the formula (1) represents a compound represented by one of the following formula.
Figure PCTKR2012001191-appb-I000012
Figure PCTKR2012001191-appb-I000012
Figure PCTKR2012001191-appb-I000013
Figure PCTKR2012001191-appb-I000013
Figure PCTKR2012001191-appb-I000014
Figure PCTKR2012001191-appb-I000014
Figure PCTKR2012001191-appb-I000015
Figure PCTKR2012001191-appb-I000015
Figure PCTKR2012001191-appb-I000016
Figure PCTKR2012001191-appb-I000016
Figure PCTKR2012001191-appb-I000017
Figure PCTKR2012001191-appb-I000017
Figure PCTKR2012001191-appb-I000018
Figure PCTKR2012001191-appb-I000018
Figure PCTKR2012001191-appb-I000019
Figure PCTKR2012001191-appb-I000019
Figure PCTKR2012001191-appb-I000020
Figure PCTKR2012001191-appb-I000020
Figure PCTKR2012001191-appb-I000021
Figure PCTKR2012001191-appb-I000021
Figure PCTKR2012001191-appb-I000022
Figure PCTKR2012001191-appb-I000022
Figure PCTKR2012001191-appb-I000023
Figure PCTKR2012001191-appb-I000023
Figure PCTKR2012001191-appb-I000024
Figure PCTKR2012001191-appb-I000024
Figure PCTKR2012001191-appb-I000025
Figure PCTKR2012001191-appb-I000025
Figure PCTKR2012001191-appb-I000026
Figure PCTKR2012001191-appb-I000026
Figure PCTKR2012001191-appb-I000027
Figure PCTKR2012001191-appb-I000027
Figure PCTKR2012001191-appb-I000028
Figure PCTKR2012001191-appb-I000028
Figure PCTKR2012001191-appb-I000029
Figure PCTKR2012001191-appb-I000029
Figure PCTKR2012001191-appb-I000030
Figure PCTKR2012001191-appb-I000030
상기 화학식 1로 표시되는 화합물들은 상기 화학식으로 제시된 화합물들 중 하나일 수 있으나 이에 제한되지 않는다. 이때 화학식 1로 표시되는 화합물들의 각 치환기들은 광범위한 관계로 모든 화합물들을 예시하는 것은 현실적으로 어려우므로 대표적인 화합물들을 예시적으로 설명한 것이나, 상기 예시적 화학식에 제시되지 않은 화학식 1로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다. The compounds represented by Chemical Formula 1 may be one of the compounds represented by Chemical Formula, but are not limited thereto. In this case, since each substituent of the compounds represented by the formula (1) is practically difficult to exemplify all the compounds in a broad relationship, exemplary compounds have been described by way of example, but compounds represented by the formula (1) not shown in the above example formula Can be part of.
또한 본 발명은 위 화합물을 포함하는 유기물층을 포함하는 유기전기소자치 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electroluminescent device including the organic material layer comprising the above compound and an electronic device thereof.
본 발명은 화합물로서 유기 전자 소자에서 정공 주입, 정공수송, 전자 주입, 전자 수송, 발광 물질 또는 패시베이션(케핑) 물질 중 적어도 하나로 사용될 수 있다. The present invention can be used as at least one of hole injection, hole transport, electron injection, electron transport, light emitting material or passivation (kepping) material in the organic electronic device as a compound.
본 발명은 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다. The present invention can be used as a host or a dopant in the light emitting material and the host / dopant, can be used as a hole injection, a hole transport layer.
본 발명의 화합물은 유기 전자 소자의 효율, 수명 및 안정성을 향상시키고, 구동전압을 하강시킨다.The compound of the present invention improves the efficiency, life and stability of the organic electronic device, and lowers the driving voltage.
본 발명은 낮은 구동전압 특성, 고내열성 및 장수명을 갖는 정공 주입층 및 수송층 재료 및 이를 포함하는 유기전기소자 및 그 전자장치를 제공할 수 있다. The present invention can provide a hole injection layer and a transport layer material having low driving voltage characteristics, high heat resistance and long life, an organic electric element including the same, and an electronic device thereof.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전계발광소자의1 to 6 of the organic light emitting device to which the compound of the present invention can be applied
예를 도시한 것이다.An example is shown.
이하에서 본 발명의 일부 실시예들을 예시적인 도면을 통해 상세하게 설명한다.Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".
한편, 본 명세서에서 '아릴기'는 단일환 또는 복소환의 1가의 방향족 탄화수소기를 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 링을 포함한다.Meanwhile, in the present specification, the "aryl group" means a monocyclic or heterocyclic monovalent aromatic hydrocarbon group, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
또한, '헤테로고리기'는 링을 형성하는 탄소 대신 이종원자(헤테로원자)를 포함하는 방향족 또는 지환족의 단일환 또는 복소환 고리를 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 헤테로 방향족 또는 지환족 고리를 포함한다.In addition, a "heterocyclic group" means an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom (heteroatom) instead of a carbon forming a ring, a hetero formed by neighboring substituents participating in the bond or reaction Aromatic or cycloaliphatic rings.
이하에서 제조예 및 실험예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 이하의 제조예 및 실험예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
이하에서 상기 화학식 1에 속하는 화합물들에 대한 제조예 또는 합성예를 설명한다. 다만, 화학식 1에 속하는 화합물들의 수가 많기 때문에 화학식 1에 속하는 화합물들 중 일부를 예시적으로 설명한다. 본 발명이 속하는 기술분야의 통상의 지식을 가진 자, 즉 당업자라면 하기에서 설명한 제조예들을 통해, 예시하지 않은 본 발명에 속하는 화합물을 제조할 수 있다.Hereinafter, preparation or synthesis examples of the compounds belonging to Chemical Formula 1 will be described. However, some of the compounds belonging to Formula 1 will be exemplarily described since the number of compounds belonging to Formula 1 is large. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.
[실시예 1]Example 1
중간체 합성 방법Intermediate Synthesis Method
[반응식 1]Scheme 1
Figure PCTKR2012001191-appb-I000031
Figure PCTKR2012001191-appb-I000031
<중간체 2a의 합성 방법><Synthesis method of intermediate 2a>
아르곤 분위기 하에서 나이트로벤젠과 중간체 1, 테트라키스 트리페닐 포스핀 팔라듐을 THF 500 ml, 물 250 ml에 K2CO3를 넣고 24시간 가열 환류한다. 수득된 고체를 물 및 메탄올로 세정한 후, 실리카겔 컬럼크로마토그래피로 분리하여 중간체 2a를 78%의 수율로 수득하였다.Under argon atmosphere, nitrobenzene, intermediate 1, and tetrakis triphenyl phosphine palladium were added to K 2 CO 3 in 500 ml of THF and 250 ml of water, and heated to reflux for 24 hours. The obtained solid was washed with water and methanol and then separated by silica gel column chromatography to give intermediate 2a in 78% yield.
<중간체 2b의 합성 방법><Synthesis method of intermediate 2b>
아르곤 분위기 하에서 2,4-다이브로모-1-나이트로벤젠과 중간체 1, 테트라키스 트리페닐 포스핀 팔라듐을 THF 500 ml, 물 250 ml에 K2CO3를 넣고 24시간 가열 환류한다. 수득된 고체를 물 및 메탄올로 세정한 후, 실리카겔 컬럼크로마토그래피로 분리하여 중간체 2b를 48%의 수율로 수득하였다.Under argon atmosphere, K 2 CO 3 was added to 2,4-dibromo-1-nitrobenzene, intermediate 1, and tetrakis triphenyl phosphine palladium in 500 ml of THF and 250 ml of water, and the mixture was heated and refluxed for 24 hours. The solid obtained was washed with water and methanol and then separated by silica gel column chromatography to give intermediate 2b in 48% yield.
<중간체 2c의 합성 방법><Synthesis method of intermediate 2c>
아르곤 분위기 하에서 1,4-다이브로모-2-나이트로벤젠과 중간체 1, 테트라키스 트리페닐 포스핀 팔라듐을 THF 500 ml, 물 250 ml에 K2CO3를 넣고 24시간 가열 환류한다. 수득된 고체를 물 및 메탄올로 세정한 후, 실리카겔 컬럼크로마토그래피로 분리하여 중간체 2c를 50%의 수율로 수득하였다.Under argon atmosphere, K 2 CO 3 was added to 1,4-dibromo-2-nitrobenzene, intermediate 1, and tetrakis triphenyl phosphine palladium in 500 ml of THF and 250 ml of water, and the mixture was heated and refluxed for 24 hours. The solid obtained was washed with water and methanol and then separated by silica gel column chromatography to give intermediate 2c in a yield of 50%.
<중간체 3a-3c의 합성 방법><Synthesis method of intermediate 3a-3c>
올소다이클로로벤젠에 녹인 화합물 2a 또는 2b 또는 2c와 트리페닐포스핀팔라듐을 2-neck에 넣고 환류하여 24시간 교반하면 노란색에서 갈색으로 용매색깔이 바뀐다. 그런 후 상온까지 온도를 올려서 농축하고 실리카겔 컬럼크로마토그래피로 분리하여 중간체 3a 또는 3b 또는 3c를 각각 85%, 84%, 89%의 수율로 수득하였다.Compound 2a or 2b or 2c and triphenylphosphine palladium dissolved in olsodichlorobenzene were added to 2-neck and refluxed for 24 hours to change the solvent color from yellow to brown. Thereafter, the mixture was heated to room temperature, concentrated and separated by silica gel column chromatography to obtain intermediates 3a or 3b or 3c in yields of 85%, 84% and 89%, respectively.
<중간체 4a-4c의 합성>Synthesis of Intermediate 4a-4c
250mL 2구 플라스크에 화합물 3a 또는 3b 또는 3c와 브로모벤젠을 넣은 다음, Pd2(dba)3, (t-Bu)3P, t-BuONa,toluene을 넣은 다음 환류시키면서 교반한다. Put compound 3a or 3b or 3c and bromobenzene in a 250 mL two-necked flask, add Pd 2 (dba) 3 , (t-Bu) 3 P, t-BuONa, toluene and stir while refluxing.
물과 MC를 넣고 추출한 다음, MgSO4로 건조하여 MC / Hexane(3:7)로 실리카겔 컬럼크로마토그래피로 분리한 후 Hexane으로 재결정하고 필터하여 중간체 4a또는 4b 또는 4c를 각각 73%, 64%, 71%의 수율로 수득하였다.Water and MC were extracted, dried over MgSO 4 , and separated by silica gel column chromatography with MC / Hexane (3: 7), recrystallized with Hexane, and filtered to obtain intermediates 4a or 4b or 4c at 73%, 64%, Obtained in the yield of 71%.
[반응식 2]Scheme 2
Figure PCTKR2012001191-appb-I000032
Figure PCTKR2012001191-appb-I000032
<중간체 5의 합성>Synthesis of Intermediate 5
100mL 2구 플라스크에 화합물4a와 NBS를 MC에 녹여 넣고 상온에서 5시간 교반한 다음 소듐바이카보네이트가 녹아있는 물과 MC로 추출하여 농축한 다음 헥산으로 세척하여 중간체 5를 98%의 수율로 얻었다.Compound 4a and NBS were dissolved in MC in a 100 mL two-neck flask, stirred at room temperature for 5 hours, extracted with water and MC with sodium bicarbonate, concentrated and washed with hexane to obtain intermediate 5 in a yield of 98%.
[실시예 2]Example 2
Product A-8의 합성 예시Synthesis Example of Product A-8
[반응식 3]Scheme 3
Figure PCTKR2012001191-appb-I000033
Figure PCTKR2012001191-appb-I000033
<중간체 a의 합성법>Synthesis of Intermediate a
N-(biphenyl-4-yl)-9,9-diphenyl-9H-fluoren-2-amine과 1-Bromo-4-iodobenzene, Pd2(dba)3, Triphenylphosphine, Sodium tert-butoxide를 toluene 용매에 넣고 130℃에서 24시간 환류 교반한다. 반응 종결 후 MC와 물로 추출하고, MgSO4로 건조하여 농축한 후 생성된 화합물을 컬럼크로마토그래피를 이용하여 분리해서 원하는 화합물인 중간체 a를 68%의 수율로 얻었다.N- (biphenyl-4-yl) -9,9-diphenyl-9H-fluoren-2-amine, 1-Bromo-4-iodobenzene, Pd 2 (dba) 3 , Triphenylphosphine and Sodium tert-butoxide in toluene Stir at reflux for 24 hours at 130 ° C. After completion of the reaction, the mixture was extracted with MC, water, dried over MgSO 4 and concentrated, and the resulting compound was separated by column chromatography to obtain intermediate a as a desired compound in a yield of 68%.
<중간체 b의 합성법>Synthesis of Intermediate b
중간체 a를 THF에 녹인 후 -78도에서 n-BuLi을 천천히 적하한 후 1시간 가량 교반한다. 그런 후 Triisopropylborate를 -78도에서 천천히 적하하여 교반한 후 1N HCl로 acid처리하여 물과 EA로 추출한 다음 MgSO4로 건조하여 Hexane으로 재결정 하여 중간체 b를 63% 수율로 얻었다.After dissolving intermediate a in THF, n-BuLi was slowly added dropwise at -78 ° C, followed by stirring for about 1 hour. Triisopropylborate was then slowly added dropwise at −78 ° C., stirred, acidified with 1N HCl, extracted with water and EA, dried over MgSO 4 and recrystallized with Hexane to give intermediate b in 63% yield.
상기 제조예에 따라 합성된 중간체는 하기와 같으며, 이들을 질량분석(FD-MS)하여 그 합성물을 확인한 결과를 표 1에 나타내었다. 질량분석은 일반적으로 사용되는 질량분석기를 이용하였다.Intermediates synthesized according to the preparation examples are as follows, and the results of confirming the compound by mass spectrometry (FD-MS) are shown in Table 1. Mass spectrometry used a commonly used mass spectrometer.
Figure PCTKR2012001191-appb-I000034
Figure PCTKR2012001191-appb-I000034
Figure PCTKR2012001191-appb-I000035
Figure PCTKR2012001191-appb-I000035
[표 1]TABLE 1
Figure PCTKR2012001191-appb-I000036
Figure PCTKR2012001191-appb-I000036
화합물 A-8의 합성법Synthesis of Compound A-8
중간체 b와 중간체 4c, Pd(PPh3)4을 THF 500 ml, 물 250 ml에 K2CO3를 넣고 24시간 가열 환류한다. 수득된 고체를 물 및 메탄올로 세정한 후, 실리카겔 컬럼 크로마토 그래피로 분리하여 흰색고체인 생성물 A-8을 71% 수율로 수득하였다.The intermediate b, the intermediate 4c, and Pd (PPh 3 ) 4 were added with K 2 CO 3 in 500 ml of THF and 250 ml of water, and refluxed for 24 hours. The obtained solid was washed with water and methanol and then separated by silica gel column chromatography to give the product A-8, a white solid, in 71% yield.
[실시예 3]Example 3
Product A-29의 합성 방법Synthesis Method of Product A-29
[반응식 4]Scheme 4
Figure PCTKR2012001191-appb-I000037
Figure PCTKR2012001191-appb-I000037
상기 중간체 a의 합성방법에서 N-(biphenyl-4-yl)-9,9-diphenyl-9H-fluoren-2-amine대신 bis(9,9-dimethyl-9H-fluoren-2-yl)amine를 1-Bromo-4-iodobenzene 대신 중간체 4c를 넣는 것을 제외하고는 동일하며, 수율은 73%였다.In the synthesis method of the intermediate a, bis (9,9-dimethyl-9H-fluoren-2-yl) amine instead of N- (biphenyl-4-yl) -9,9-diphenyl-9H-fluoren-2-amine 1 The yield was 73%, except that Intermediate 4c was added instead of -Bromo-4-iodobenzene.
표 2는 위 제조예들에 따라 합성된 최종 화합물들을 질량분석(FD-MS)하여 그 합성물을 확인한 결과를 나타낸 것이다. Table 2 shows the results of confirming the composition by mass spectrometry (FD-MS) of the final compounds synthesized according to the above preparation examples.
[표 2]TABLE 2
Figure PCTKR2012001191-appb-I000038
Figure PCTKR2012001191-appb-I000038
[실시예 4]Example 4
<중간체 합성 방법><Intermediate synthesis method>
[반응식 5]Scheme 5
Figure PCTKR2012001191-appb-I000039
Figure PCTKR2012001191-appb-I000039
<중간체 B의 합성법>Synthesis of Intermediate B
둥근바닥플라스크에 화합물 A(1당량), 아민화합물 (2당량), Pd2(dba)3 (0.06~0.1 mmol),PPh3 (0.2당량), NaOt-Bu (6당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 얻었다.Compound A (1 equiv), amine compound (2 equiv), Pd 2 (dba) 3 (0.06 ~ 0.1 mmol), PPh 3 (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5) mL / 1 mmol) and then proceed with the reaction at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product.
상기 합성법에 의해 합성된 화학식 중간체들은 하기와 같으며 이들을 질량분석(FD-MS)하여 그 합성물을 확인한 결과를 표 3에 나타내었다. Chemical intermediates synthesized by the synthesis method are as follows, and the results of confirming the compound by mass spectrometry (FD-MS) are shown in Table 3.
Figure PCTKR2012001191-appb-I000040
Figure PCTKR2012001191-appb-I000040
Figure PCTKR2012001191-appb-I000041
Figure PCTKR2012001191-appb-I000041
Figure PCTKR2012001191-appb-I000042
Figure PCTKR2012001191-appb-I000042
[표 3]TABLE 3
Figure PCTKR2012001191-appb-I000043
Figure PCTKR2012001191-appb-I000043
<중간체 C의 합성법>Synthesis of Intermediate C
둥근바닥플라스크에 B의 화합물(1당량), Bis(pinacolato)diboron (1당량), Pd(dppf)Cl2 (0.03당량). KOAc (3당량), DMF (6.3 mL / 1 mmol),을 넣은후에 130℃에서 가열, 환류반응을 진행한다. 반응이 완료되면 ether 와 물로 추출하고 얻어진 유기층을 MgSO4 로 건조, 농축한 후에 silicagel column 및 재결정하여 생성물을 얻었다. Compound B (1 equiv), Bis (pinacolato) diboron (1 equiv), Pd (dppf) Cl 2 (0.03 equiv) in a round bottom flask. KOAc (3 equiv), DMF (6.3 mL / 1 mmol) were added, followed by heating to reflux at 130 ° C. After completion of the reaction, the mixture was extracted with ether and water, and the obtained organic layer was dried over MgSO 4 , concentrated, and silicagel column and recrystallized to obtain a product.
[실시예 5]Example 5
[반응식 6]Scheme 6
Figure PCTKR2012001191-appb-I000044
Figure PCTKR2012001191-appb-I000044
Product B-3의 합성 방법Synthesis of Product B-3
둥근바닥플라스크에 4C의 화합물 (1당량)과 중간체 6 (1.1당량), Pd(PPh3)4 0.05당량, NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. In a round bottom flask, 4C compound (1 equiv) and intermediate 6 (1.1 equiv), Pd (PPh 3 ) 4 0.05 equiv, NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol) ).
그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시킨다. 그런 후에 메틸렌클로라이드와 물로 추출하고 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 65% 수율로 얻었다.After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product in 65% yield.
표 4는 위 제조예들에 따라 합성된 최종 화합물들을 질량분석(FD-MS)하여 그 합성물을 확인한 결과를 나타내었다. Table 4 shows the results of confirming the composition by mass spectrometry (FD-MS) of the final compounds synthesized according to the above preparation examples.
[표 4]TABLE 4
Figure PCTKR2012001191-appb-I000045
Figure PCTKR2012001191-appb-I000045
비교예Comparative example
유기 EL 소자의 제조 평가Manufacturing evaluation of organic electroluminescent element
합성을 통해 얻은 본 발명의 화합물을 각각 발광층의 발광 호스트 물질이나 정공 수송층으로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 4,4'4" 트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민 (이하 2T-NATA로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. Using the compound of the present invention obtained through the synthesis as a light emitting host material or a hole transport layer, respectively, an organic light emitting device was manufactured according to a conventional method. First, 4,4'4 "tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter referred to as 2T-NATA) as a hole injection layer first on the ITO layer (anode) formed on the glass substrate. Membrane) was vacuum deposited to form a thickness of 10 nm.
이어서, 정공수송 화합물로서 본 발명에 따른 화합물을 30 nm의 두께로 진공증착하여 홀 수송층을 형성하였다. 홀 수송층을 형성한 후, 본 발명에 따른 화합물을 홀 수송층으로 측정할 시에는 이 홀 수송층 상부에 45nm두께의 BD-052X(Idemitus사)가 7% 도핑된 발광층 (이때, BD-052X는 청색 형광 도펀트이고, 발광 호스트 물질로는 9,10-다이(나프탈렌-2-안트라센(AND))을 사용하였다.The compound according to the invention was then vacuum deposited to a thickness of 30 nm as the hole transport compound to form a hole transport layer. After the formation of the hole transport layer, when the compound according to the present invention was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X is blue fluorescent light) 9,10-di (naphthalene-2-anthracene (AND)) was used as the dopant and the light emitting host material.
홀 저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 의 두께로 진공증착하고, 이어서 전자주입층으로 트리스(8-퀴놀리놀) 알루미늄 (이하 Alq3로 약칭함)을 40 nm의 두께로 성막하였다. 이 후, 할로젠화 알칼리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 사용함으로서 유기전계 발광소자를 제조하였다.(1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited to an electron injection layer in a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.
비교실험예Comparative Experiment
비교를 위해 본 발명의 화합물 대신에 하기식으로 표시되는 화합물(이하 NPB로 약기함)을 정공수송 물질로 사용하여 실험예와 동일한 구조의 유기전계발광소자를 제작하였다.For comparison, an organic electroluminescent device having the same structure as that of the experimental example was manufactured using a compound represented by the following formula (hereinafter abbreviated as NPB) as a hole transport material instead of the compound of the present invention.
Figure PCTKR2012001191-appb-I000046
Figure PCTKR2012001191-appb-I000046
[표 5]TABLE 5
Figure PCTKR2012001191-appb-I000047
Figure PCTKR2012001191-appb-I000047
상기 표 5의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 고효율이면서 색순도가 향상될 뿐만 아니라 장수명인 청색 발광이 얻어지므로 유기전계발광소자의 정공수송재료로 사용되어 낮은 구동전압과 높은 발광효율 및 수명을 현저히 개선시킬 수 있다.As can be seen from the results of Table 5, the organic electroluminescent device using the organic electroluminescent device material of the present invention has high efficiency and color purity as well as long life blue light emission is obtained as a hole transporting material of the organic electroluminescent device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.
표 5에 실시예들의 화합물들의 발광효율과 수명이 현저히 개선된 것을 확인하였으나 실시예들 뿐만 아니라 다른 화합물도 실시예들과 동일 또는 실질적으로 동일한 효과를 나타내는 것을 확인하였다.In Table 5, it was confirmed that the luminous efficiency and lifespan of the compounds of the examples were significantly improved, but not only the examples but also other compounds showed the same or substantially the same effects as the examples.
상기 화학식 1에 속하는 화합물들에 대한 또 다른 제조예 또는 합성예를 설명한다.Another preparation or synthesis example for the compounds belonging to Formula 1 will be described.
본 발명에 따른 화합물 합성은 하기와 같은 방법으로 수행하였다. 하기에서는 황(S)을 포함하는 오원자헤테로고리를 예로 들어 설명하지만 S 대신 N, O, P 등의 경우에도 동일한 방법으로 합성될 수 있으므로 이에 대한 합성예는 생략한다.Compound synthesis according to the invention was carried out in the following manner. Hereinafter, the five-membered heterocyclic ring containing sulfur (S) will be described as an example, but in the case of N, O, P, etc. instead of S, the synthesis thereof is omitted.
Figure PCTKR2012001191-appb-I000048
Figure PCTKR2012001191-appb-I000048
[실시예 6]Example 6
Sub 1 합성법 예시 :Example of Sub 1 synthesis:
Sub 1-1 합성법Sub 1-1 Synthesis
아르곤 분위기 하에서 나이트로벤젠과 thiophen-2-ylboronic acid, 테트라키스 트리페포스핀 팔라듐을 THF 500 ml, 물 250 ml에 K2CO3를 넣고 24시간 가열 환류한다. 수득된 고체를 물 및 메탄올로 세정한 후, 실리카겔 컬럼크로마토그래피로 분리하여 Sub 1-1을 78%로 수득하였다.Benzene and thiophen-2-ylboronic acid, tetrakis page palladium nitro, under an argon atmosphere in 500 ml THF, 250 ml water into a K 2 CO 3 and heated under reflux for 24 hours. The obtained solid was washed with water and methanol, and then separated by silica gel column chromatography to obtain Sub 1-1 as 78%.
Sub 1-2 합성법Sub 1-2 synthesis
올소다이클로로벤젠에 녹인 Sub 1-1에 트리페닐포스핀팔라듐을 2-neck에 넣고 환류하여 24시간 교반한다. 그 후 상온까지 온도를 올려서 농축하고 실리카겔 컬럼 크로마토그래피로 분리하여 Sub 1-2를 85%로 수득하였다.Triphenylphosphinepalladium was added to 2-neck in Sub 1-1 dissolved in oxodichlorobenzene, and the mixture was refluxed and stirred for 24 hours. Thereafter, the mixture was heated to room temperature, concentrated and separated by silica gel column chromatography to obtain Sub 1-2 as 85%.
Sub 1-3 합성법Sub 1-3 Synthesis
250 ml 2구 플라스크에 Sub 1-2와 Ar-Br을 넣은 다음, Pd2(dba)3, (t-bu)3, t-BuONa, toluene을 넣은 다음 환류시키면서 교반한다. 물과 MC를 넣고 추출한 다음, MgSO4로 건조하여 MC/Hexane(3:7)로 실리카겔 컬럼 크로마토 그래피로 분리한 후 Hexane으로 재결정하고 필터하여 Sub 1-3을 얻었다.Add Sub 1-2 and Ar-Br to a 250 ml two-necked flask, add Pd 2 (dba) 3 , (t-bu) 3 , t-BuONa, toluene and stir while refluxing. Water and MC were added, extracted, dried over MgSO 4 , separated by silica gel column chromatography with MC / Hexane (3: 7), recrystallized with Hexane and filtered to obtain Sub 1-3.
Ar-Br의 예시는 다음과 같으나, 반드시 이에 한정되는 것은 아니다.Examples of Ar-Br are as follows, but are not necessarily limited thereto.
Figure PCTKR2012001191-appb-I000049
Figure PCTKR2012001191-appb-I000049
[표 6]TABLE 6
Figure PCTKR2012001191-appb-I000050
Figure PCTKR2012001191-appb-I000050
Sub 1 합성법Sub 1 Synthesis
100 ml 2구 플라스크에 Sub 1-3과 NBS를 MC에 녹여 넣고 상온에서 5시간 교반한 다음 소듐바이카보네이트가 녹아있는 물과 MC로 추출하여 농축한 다음 헥산으로 세정하여 Sub 1을 98% 수율로 얻었다.Dissolve 1-3 and NBS in MC in a 100 ml two-necked flask, stir at room temperature for 5 hours, extract with sodium bicarbonate and MC and concentrate, wash with hexane, and wash Sub 1 in 98% yield. Got it.
[실시예 7]Example 7
Sub 2 합성법 예시 :Example of Sub 2 synthesis:
둥근바닥플라스크에 브롬화합물 (1당량), 아민화합물 (1당량), Pd2(dba)3 (0.06~0.1 mmol), PPh3 (0.2당량), NaOt-Bu (6당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 2를 얻었다.Bromine compound (1 equiv), amine compound (1 equiv), Pd 2 (dba) 3 (0.06 ~ 0.1 mmol), PPh 3 (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5) mL / 1 mmol) and then proceed with the reaction at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain the product Sub 2.
Sub 2의 예시는 아래와 같으나, 이에 한정되는 것은 아니다.An example of Sub 2 is as follows, but is not limited thereto.
Figure PCTKR2012001191-appb-I000051
Figure PCTKR2012001191-appb-I000051
Figure PCTKR2012001191-appb-I000052
Figure PCTKR2012001191-appb-I000052
Figure PCTKR2012001191-appb-I000053
Figure PCTKR2012001191-appb-I000053
L은 구체적으로 단일결합; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기; 및 2가의 치환 또는 비치환된 지방족 탄화수소로 구성된 군에서 선택될 수 있다. 예컨대, 2가 작용기인 페닐렌, 비페닐렌, 나프틸렌, 피리딘일렌, 피리미딘일렌, 피라진일렌, 피페리딘일렌, 피페라진일렌, 피롤리덴일렌, 피롤렌, 플루오렌일렌 등으로 이루어진 군에서 선택될 수 있으며, 합성방법은 동일하다. L is specifically a single bond; C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy and amino groups Ren group; C 2 -C 60 hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group and an amino group Ring groups; And divalent substituted or unsubstituted aliphatic hydrocarbons. For example, a group consisting of divalent functional groups such as phenylene, biphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazinylene, piperidinylene, piperazinylene, pyrrolidenylene, pyrrolene, fluoreneylene and the like The synthesis method is the same.
Sub 2-1 내지 2-32의 화합물에 대한 질량분석 결과는 표 7과 같았다.Mass spectrometry results for the compounds of Sub 2-1 to 2-32 were as shown in Table 7.
[표 7]TABLE 7
Figure PCTKR2012001191-appb-I000054
Figure PCTKR2012001191-appb-I000054
최종 화합물 합성 예시 :Example of final compound synthesis:
둥근바닥플라스크에 Sub 1 화합물을 (1당량), Sub 2 화합물을 (1.1당량), Pd(PPh3)4 (0.03~0.05당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. To the round bottom flask, Sub 1 compound (1 equivalent), Sub 2 compound (1.1 equivalent), Pd (PPh 3 ) 4 (0.03 to 0.05 equivalent), NaOH (3 equivalent), THF (3 mL / 1 mmol), Add water (1.5 mL / 1 mmol).
그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature.
시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 얻었다.And extract with methylene chloride and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was purified by silicagel column and recrystallized to obtain a product.
[실시예 8]Example 8
Product 1-1 합성 예시 Product 1-1 Synthesis Example
Figure PCTKR2012001191-appb-I000055
Figure PCTKR2012001191-appb-I000055
둥근바닥플라스크에 2-bromo-4-phenyl-4H-thieno[3,2-b]indole (6.6g, 20mmol)), diphenylboramidic acid (5.1g, 24mmol), Pd(PPh3)4 (0.03~0.05당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 5.7g (수율: 68%)을 얻었다.2-bromo-4-phenyl-4H-thieno [3,2-b] indole (6.6g, 20mmol)), diphenylboramidic acid (5.1g, 24mmol), Pd (PPh 3 ) 4 (0.03 ~ 0.05) Equivalent), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol) are added. After that, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 5.7g (yield: 68%).
[실시예 9]Example 9
Product 2-29 합성 예시 Product 2-29 Synthesis Example
Figure PCTKR2012001191-appb-I000056
Figure PCTKR2012001191-appb-I000056
둥근바닥플라스크에 2-bromo-4-phenyl-4H-thieno[3,2-b]indole (6.6g, 20mmol)), 4-(biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)phenylboronic acid (11.6g, 24mmol), Pd(PPh3)4 (0.03~0.05당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 9.0g (수율: 66%)을 얻었다.2-bromo-4-phenyl-4H-thieno [3,2-b] indole (6.6 g, 20 mmol)), 4- (biphenyl-4-yl (9,9-dimethyl-9H-fluoren-) in a round bottom flask 2-yl) amino) phenylboronic acid (11.6g, 24mmol), Pd (PPh 3 ) 4 (0.03-0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol ). After that, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 9.0g (yield: 66%).
[실시예 10]Example 10
Product 3-28 합성 예시 Product 3-28 Synthesis Example
Figure PCTKR2012001191-appb-I000057
Figure PCTKR2012001191-appb-I000057
둥근바닥플라스크에 2-bromo-4-phenyl-4H-thieno[3,2-b]indole (6.6g, 20mmol)), 4'-(dibiphenyl-4-ylamino)biphenyl-4-ylboronic acid (12.4g, 24mmol), Pd(PPh3)4 (0.03~0.05당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 9.7g (수율: 67%)을 얻었다.2-bromo-4-phenyl-4H-thieno [3,2-b] indole (6.6 g, 20 mmol)), 4 '-(dibiphenyl-4-ylamino) biphenyl-4-ylboronic acid (12.4 g) in a round bottom flask , 24 mmol), Pd (PPh3) 4 (0.03-0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), and water (1.5 mL / 1 mmol) are added. After that, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO 4, concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 9.7g (yield: 67%).
[실시예 11]Example 11
Product 4-21 합성 예시 Product 4-21 Synthesis Example
Figure PCTKR2012001191-appb-I000058
Figure PCTKR2012001191-appb-I000058
둥근바닥플라스크에 2-bromo-4-phenyl-4H-thieno[3,2-b]indole (6.6g, 20mmol)), 5-((9,9-dimethyl-9H-fluoren-2-yl)(naphthalen-2-yl)amino)thiophen-2-ylboronic acid (11.1g, 24mmol), Pd(PPh3)4 (0.03~0.05당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. 그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 8.6g (수율: 65%)을 얻었다.In a round bottom flask, 2-bromo-4-phenyl-4H-thieno [3,2-b] indole (6.6 g, 20 mmol)), 5-((9,9-dimethyl-9H-fluoren-2-yl) ( naphthalen-2-yl) amino) thiophen-2-ylboronic acid (11.1g, 24mmol), Pd (PPh 3 ) 4 (0.03 ~ 0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol) is added. After that, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 8.6g (yield: 65%).
[표 8]TABLE 8
Figure PCTKR2012001191-appb-I000059
Figure PCTKR2012001191-appb-I000059
Figure PCTKR2012001191-appb-I000060
Figure PCTKR2012001191-appb-I000060
Figure PCTKR2012001191-appb-I000061
Figure PCTKR2012001191-appb-I000061
Figure PCTKR2012001191-appb-I000062
Figure PCTKR2012001191-appb-I000062
Figure PCTKR2012001191-appb-I000063
Figure PCTKR2012001191-appb-I000063
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
비교 compare 실험예Experimental Example 1 One
합성을 통해 얻은 본 발명의 화합물을 정공 수송층으로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 정공 주입층으로서 4,4’,4”-트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민 (이하 2T-NATA로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. 이어서, 정공 수송 화합물로서 본 발명의 화합물을 30 nm의 두께로 진공증착하여 정공 수송층을 형성하였다. 정공 수송층을 형성한 후 상부에 45nm 두께의 BD-052X(Idemitus사)가 7% 도핑된 발광층 (이때, BD-052X는 청색 형광 도펀트이고, 발광 호스트 물질로는 9,10-다이(나프탈렌-2-안트라센(AND))을 사용하였다. 정공 저지층으로 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 의 두께로 진공 증착하고, 이어서 전자 주입층으로 트리스(8-퀴놀리놀) 알루미늄 (이하 Alq3로 약칭함)을 40 nm의 두께로 성막하였다. 이 후, 할로젠화 알칼리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 사용함으로써 유기 전계 발광소자를 제조하였다.An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a hole transport layer. First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter referred to as 2T-NATA) as a hole injection layer on the ITO layer (anode) formed on the glass substrate The film was vacuum deposited to form a thickness of 10 nm. Subsequently, the compound of the present invention was vacuum deposited to a thickness of 30 nm as the hole transport compound to form a hole transport layer. After forming the hole transporting layer, a light emitting layer 7% doped with BD-052X (Idemitus Co., Ltd.) having a thickness of 45 nm (where BD-052X is a blue fluorescent dopant, and 9,10-die (naphthalene-2) is used as a light emitting host material. Anthracene (AND) was used as (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (abbreviated as BAlq) as the hole blocking layer. Vacuum deposition was carried out to a thickness of 10 nm, and then tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq3) was deposited to a thickness of 40 nm with an electron injection layer. Thereafter, LiF, an alkali metal halide, was deposited at a thickness of 0.2 nm, and then Al was deposited at a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic EL device.
Figure PCTKR2012001191-appb-I000064
Figure PCTKR2012001191-appb-I000064
전술한 화합물들과 비교예1을 정공수송층 물질로 사용하여 제작한 유기전계발광소자의 성능들(구동전압, 전류밀도, 밝기, 효율, 수명, 색좌표)을 비교하면 아래 표 9와 같다. Comparing the above-described compounds and the performance (driving voltage, current density, brightness, efficiency, lifespan, color coordinates) of the organic light emitting device manufactured using Comparative Example 1 as a hole transport layer material as shown in Table 9 below.
[표 9]TABLE 9
Figure PCTKR2012001191-appb-I000065
Figure PCTKR2012001191-appb-I000065
Figure PCTKR2012001191-appb-I000066
Figure PCTKR2012001191-appb-I000066
Figure PCTKR2012001191-appb-I000067
Figure PCTKR2012001191-appb-I000067
Figure PCTKR2012001191-appb-I000068
Figure PCTKR2012001191-appb-I000068
Figure PCTKR2012001191-appb-I000069
Figure PCTKR2012001191-appb-I000069
Figure PCTKR2012001191-appb-I000070
Figure PCTKR2012001191-appb-I000070
Figure PCTKR2012001191-appb-I000071
Figure PCTKR2012001191-appb-I000071
비교 compare 실험예Experimental Example 2 2
합성을 통해 얻은 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 구리프탈로사이아닌(이하 CuPc로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. 이어서, 이 막 상에 정공수송 화합물로서 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 -NPD로 약기함)을 30 nm 두께로 진공증착하여 홀 수송층을 형성하였다. 홀 수송층을 형성한 후, 이 홀 수송층 상부에 본 발명에 따른 화합물을 인광 호스트 재료로서 증착하여 발광층을 성막한 후, 인광 발광성의 Ir 금속 착체 도펀트로서 트리스(2-페닐피리딘)이리듐(이하 I r(ppy)3로 약기함)을 첨가하였다. 이때 발광층 중에 있어서의 Ir(ppy)3의 농도는 5중량%로 하였다. 홀 저지층으로 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자주입층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약칭함)을 40 nm 두께로 성막하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 하는 유기전계 발광소자를 제조하였다.An organic light emitting diode was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material of a light emitting layer. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 30 nm as a hole transporting compound on the membrane to form a hole transport layer. Formed. After the hole transport layer was formed, the compound according to the present invention was deposited on the hole transport layer as a phosphorescent host material to form a light emitting layer, and then tris (2-phenylpyridine) iridium (hereinafter, I r) was used as a phosphorescent Ir metal complex dopant. (abbreviated to (ppy) 3)). At this time, the concentration of Ir (ppy) 3 in the light emitting layer was 5% by weight. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and electron injection was performed. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited into the layer to a thickness of 40 nm. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to manufacture an organic light emitting device using the Al / LiF as a cathode.
Figure PCTKR2012001191-appb-I000072
Figure PCTKR2012001191-appb-I000072
전술한 화합물들과 비교예 2를 발광 호스트 물질로 사용하여 제작한 유기전계발광소자의 성능들(구동전압, 전류밀도, 밝기, 효율, 수명, 색좌표)를 비교하면 아래 표 10과 같다. Comparing the above-described compounds and the performance (driving voltage, current density, brightness, efficiency, lifetime, color coordinates) of the organic light emitting device manufactured using Comparative Example 2 as a light emitting host material is shown in Table 10 below.
[표 10]TABLE 10
Figure PCTKR2012001191-appb-I000073
Figure PCTKR2012001191-appb-I000073
상기 표들의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 발광 호스트, 정공 수송재료로 사용되어 낮은 구동전압, 색순도, 높은 발광효율 및 수명을 현저히 개선시킬 수 있다. As can be seen from the results of the tables, the organic light emitting device using the organic light emitting device material of the present invention can be used as a light emitting host, a hole transporting material can significantly improve the low driving voltage, color purity, high luminous efficiency and lifespan. have.
본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
한편, 화학식 1로 표시되는 화합물들의 각 치환기들은 광범위한 관계로, 대표적인 화합물들의 합성예를 예시적으로 설명하였으나, 합성예로 예시적으로 설명하지 않은 화학식 1로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다.On the other hand, each of the substituents of the compounds represented by the formula (1) has a broad relationship, exemplarily described the synthesis examples of the representative compounds, the compounds represented by the formula (1) not illustrated by way of example as a synthesis example Can be configured.
또한, 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기발광소자를 비롯한 유기전기소자의 제조시 사용되는 정공주입층 물질, 정공수송층 물질, 발광층 물질, 및 전자 수송층 물질에 사용되는 치환기를 상기 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 제조할 수 있다.Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.
본 발명에 따른 화합물은 치환기의 종류 및 성질에 따라 유기전기발광소자에서 다양한 용도로 사용될 수 있다.The compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.
본 발명의 화합물은 코어와 치환체에 의해 조절이 자유롭기 때문에 인광 또는 형광 발광층의 호스트 이외의 다양한 층으로 작용할 수 있다.The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
본 발명의 유기전기소자는 전술한 화합물들을 이용하여 한층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기전기소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.
본 발명의 화합물들을 유기전기발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.When the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
한편 본 발명의 화합물은 용액 공정(soluble process)에 사용될 수 있다. 다시 말해 상기 화합물을 용액 공정(soluble process)에 의해 후술할 유기전기소자의 유기물층을 형성할 수 있다. 즉 상기 화합물을 유기물층으로 사용할 때 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
본 발명의 화합물들이 사용될 수 있는 유기전기소자는 예를 들어, 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 등이 있다.Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
본 발명의 화합물들이 적용될 수 있는 유기전기소자 중 일예로 유기전기발광소자(OLED)에 대하여 설명하나, 본 발명은 이에 제한되지 않고 다양한 유기전기소자에 위에서 설명한 화합물들이 적용될 수 있다.As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
본 발명의 다른 실시예는 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층 중 1층 이상이 본 발명의 화합물들을 포함하는 유기전기발광소자를 제공한다.Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전기발광소자의 예를 도시한 것이다.1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
본 발명의 다른 실시예에 따른 유기전기발광소자는, 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층 중 1층 이상을 본 발명의 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 통상의 제조 방법 및 재료를 이용하여 당 기술 분야에 알려져 있는 구조로 제조될 수 있다.The organic electroluminescent device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.
본 발명에 다른 실시예에 따른 유기전기발광소자의 구조는 도 1 내지 6에 예시되어 있으나, 이들 구조에만 한정된 것은 아니다. 이때, 도면번호 101은 기판, 102는 양극, 103은 정공주입층(HIL), 104는 정공수송층(HTL), 105는 발광층(EML), 106은 전자주입층(EIL), 107은 전자수송층(ETL), 108은 음극을 나타낸다. The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.
미도시하였지만, 이러한 유기전기발광소자는 정공의 이동을 저지하는 정공저지층(HBL), 전자의 이동을 저지하는 전자저지층(EBL), 발광을 돕거나 보조하는 발광보조층 및 보호층이 더 위치할 수도 있다. 보호층의 경우 최상위층에서 유기물층을 보호하거나 음극을 보호하도록 형성될 수 있다.Although not shown, the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
이때, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물층 중 하나 이상에 포함될 수 있다.In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
구체적으로, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 정공저지층, 전자저지층, 발광보조층 및 보호층 중 하나 이상을 대신하여 사용되거나 이들과 함께 층을 형성하여 사용될 수도 있다. 물론 유기물층 중 한층에만 사용되는 것이 아니라 두층 이상에 사용될 수 있다.Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.
특히, 본 발명의 화합물에 따라서 정공주입 재료, 정공수송 재료, 전자주입 재료, 전자수송 재료, 발광 재료 및 패시베이션(케핑) 재료로 사용될 수 있고, 특히 단독으로 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다.In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
예컨대, 본 발명의 다른 실시예에 따른 유기전기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.For example, the organic electroluminescent device according to another embodiment of the present invention is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.
이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기전기소자를 만들 수도 있다. 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.In addition, the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
본 발명의 다른 실시예에 따른 유기전기발광소자는 위에서 설명한 화합물을 스핀 코팅(spin coating)이나 잉크젯(ink jet) 공정과 같은 용액 공정(soluble process)에 사용될 수도 있다.The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
기판은 유기전기발광소자의 지지체이며, 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다.The substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.
기판 위에는 양극이 위치된다. 이러한 양극은 그 위에 위치되는 정공주입층으로 정공을 주입한다. 양극 물질로는 통상 유기물층으로 정공주입이 원활할 수 있도록 일함수가 큰 물질일 수 있다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐주석 산화물(ITO), 인듐아연산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
양극 위에는 정공주입층이 위치된다. 이러한 정공주입층의 물질로 요구되는 조건은 양극으로부터의 정공주입 효율이 높으며, 주입된 정공을 효율적으로 수송할 수 있어야 한다. 이를 위해서는 이온화 포텐셜이 작고 가시광선에 대한 투명성이 높으며, 정공에 대한 안정성이 우수해야 한다.The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
정공주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입받을 수 있는 물질로서, 정공주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이일 수 있다. 정공주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴 헥사아자트리페닐렌, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공주입층 위에는 정공수송층이 위치된다. 이러한 정공수송층은 정공주입층으로부터 정공을 전달받아 그 위에 위치되는 유기발광층으로 수송하는 역할을 하며, 높은 정공 이동도와 정공에 대한 안정성 및 전자를 막아주는 역할를 한다. 이러한 일반적 요구 이외에 차체 표시용으로 응용할 경우 소자에 대한 내열성이 요구되며, 유리 전이 온도(Tg)가 70 ℃ 이상의 값을 갖는 재료일 수 있다.The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
이와 같은 조건을 만족하는 물질들로는 NPD(혹은 NPB라 함), 스피로-아릴아민계화합물, 페릴렌-아릴아민계화합물, 아자시클로헵타트리엔화합물, 비스(디페닐비닐페닐)안트라센, 실리콘게르마늄옥사이드화합물, 실리콘계아릴아민화합물 등이 될 수 있다.Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compound, a silicon-based arylamine compound, and the like.
정공수송층 위에는 유기발광층이 위치된다. 이러한 유기발광층는 양극과 음극으로부터 각각 주입된 정공과 전자가 재결합하여 발광을 하는 층이며, 양자효율이 높은 물질로 이루어져 있다. 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자효율이 좋은 물질일 수 있다.The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.
이와 같은 조건을 만족하는 물질 또는 화합물로는 녹색의 경우 Alq3가, 청색의 경우 Balq(8-hydroxyquinoline beryllium salt), DPVBi(4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl) 계열, 스피로(Spiro) 물질, 스피로-DPVBi(Spiro-4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl), LiPBO(2-(2-benzoxazoyl)-phenollithium salt), 비스(디페닐비닐페닐비닐)벤젠, 알루미늄-퀴놀린 금속착체, 이미다졸, 티아졸 및 옥사졸의 금속착체 등이 있으며, 청색 발광 효율을 높이기 위해 페릴렌, 및 BczVBi(3,3'[(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(9-ethyl)-9H-carbazole; DSA(distrylamine)류)를 소량 도핑하여 사용할 수 있다. 적색의 경우는 녹색 발광 물질에 DCJTB([2-(1,1-dimethylethyl)-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo(ij)quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene]-propanedinitrile)와 같은 물질을 소량 도핑하여 사용할 수 있다. Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.
잉크젯프린팅, 롤코팅, 스핀코팅 등의 공정을 사용하여 발광층을 형성할 경우에, 폴리페닐렌비닐렌(PPV) 계통의 고분자나 폴리 플루오렌(poly fluorene) 등의 고분자를 유기발광층에 사용할 수 있다.When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .
유기발광층 위에는 전자수송층이 위치된다. 이러한 전자수송층은 그 위에 위치되는 음극으로부터 전자주입 효율이 높고 주입된 전자를 효율적으로 수송할 수 있는 물질이 필요하다. 이를 위해서는 전자 친화력과 전자 이동속도가 크고 전자에 대한 안정성이 우수한 물질로 이루어져야 한다. The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
이와 같은 조건을 충족시키는 전자수송 물질로는 구체적인 예로 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
전자수송층 위에는 전자주입층이 적층된다. 전자주입층은 Balq, Alq3,Be(bq)2, Zn(BTZ)2, Zn(phq)2, PBD, spiro-PBD, TPBI, Tf-6P 등과 같은 금속착제화합물, imidazole ring 을 갖는 aromatic 화합물이나 boron화합물 등을 포함하는 저분자 물질을 이용하여 제작할 수 있다. 이때, 전자주입층은 100Å ~ 300Å의 두께 범위에서 형성될 수 있다.The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.
전자주입층 위에는 음극이 위치된다. 이러한 음극은 전자를 주입하는 역할을 한다. 음극으로 사용하는 재료는 양극에 사용된 재료를 이용하는 것이 가능하며, 효율적인 전자주입을 위해서는 일 함수가 낮은 금속일 수 있다. 특히 주석, 마그네슘, 인듐, 칼슘, 나트륨, 리튬, 알루미늄, 은 등의 적당한 금속, 또는 그들의 적절한 합금이 사용될 수 있다. 또한 100 ㎛ 이하 두께의 리튬플루오라이드와 알루미늄, 산화리튬과 알루미늄, 스트론튬산화물과 알루미늄 등의 2 층 구조의 전극도 사용될 수 있다.The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.
전술하였듯이, 본 발명의 화합물에 따라서 적색, 녹색, 청색, 흰색 등의 모든 칼라의 형광과 인광소자에 적합한 정공주입 재료, 정공수송 재료, 발광 재료, 전자수송 재료 및 전자주입 재료로 사용할 수 있으며, 다양한 색의 호스트 또는 도판트 물질로 사용될 수 있다.As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
본 발명에 따른 유기전기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
한편 본 발명은, 위에서 설명한 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 구동하는 제어부를 포함하는 단말을 포함한다. 이 단말은 현재 또는 장래의 유무선 통신단말을 의미한다. 이상에서 전술한 본 발명에 따른 단말은 휴대폰 등의 이동 통신 단말기일 수 있으며, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 단말을 포함한다.Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명 하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments.
본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2011년 02월 24일 한국에 출원한 특허출원번호 제 10-2011-0016267 호 및 2012년 02월 07일 한국에 출원한 특허출원번호 제 10-2012-0012490 호에 대해 미국 특허법 119(a)조(35 U.S.C § 119(a))에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. This patent application is filed with the Patent Application No. 10-2011-0016267 filed in Korea on February 24, 2011 and the patent application No. 10-2012-0012490 filed in Korea on February 7, 2012. (a) Claims priority under section 35 USC § 119 (a), all of which are hereby incorporated by reference in this patent application. In addition, if this patent application claims priority to a country other than the United States for the same reason, all its contents are incorporated into this patent application by reference.

Claims (14)

  1. 하기 화학식 1 또는 화학식 2로 표시되는 화합물. A compound represented by the following formula (1) or (2).
    [화학식 1] [Formula 1]
    상기 화학식에서,In the above formula,
    (1) A 는
    Figure PCTKR2012001191-appb-I000075
    이고, B는
    Figure PCTKR2012001191-appb-I000076
    이며,    (1) A is
    Figure PCTKR2012001191-appb-I000075
    And B is
    Figure PCTKR2012001191-appb-I000076
    Is,
    (2) L은 단일결합; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 니트로기, 니트릴기, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기; 및 2가의 치환 또는 비치환된 지방족 탄화수소로 구성된 군에서 선택되며,(2) L is a single bond; C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy and amino groups Ren group; C 2 -C 60 hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group and an amino group Ring groups; And divalent substituted or unsubstituted aliphatic hydrocarbons,
    (3) n은 1 내지 7의 정수이고,(3) n is an integer of 1 to 7,
    (4) Ar1 내지 Ar3, R1 내지 R6은 서로 같거나 상이하고, 각각 독립적으로 (4) Ar 1 to Ar 3 , R 1 to R 6 are the same as or different from each other, and each independently
    수소; 할로겐; 치환 또는 비치환된 지방족 탄화 수소기;Hydrogen; halogen; Substituted or unsubstituted aliphatic hydrocarbon group;
    수소, 중수소, 할로겐기, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~ C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1~ C60의 알킬 티오펜기, C6 ~ C60의 아릴 티오펜기, C2 ~ C60의 알케닐기, C2 ~ C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 치환 또는 비치환된 C2 ~ C60의 헤테로고리기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환된 C6 ~ C60의 아릴기; Hydrogen, deuterium, halogen group, C 1 ~ C 60 alkyl group, C 1 ~ C 60 alkoxy group, C 1 ~ C 60 alkylamine group, C 1 ~ C 60 arylamine group, C 1 ~ C 60 Alkyl thiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ~ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C 2 ~ C 60 heterocyclic group;
    수소, 중수소, 할로겐, CN, NO2, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1 ~ C60의 알킬티오기, C2 ~ C60의 알케닐기, C2 ~C60의 알키닐기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C3 ~ C60의 시클로알킬기, C7 ~ C60의 아릴알킬기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 C2 ~ C60의 헤테로고리기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 아세틸렌기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환되고 O, N, S, Si, P 중 적어도 하나를 포함하는 C2 ~C60의 헤테로고리기; Hydrogen, deuterium, halogen, CN, NO 2 , C 1 to C 60 alkyl group, C 1 to C 60 alkoxy group, C 1 to C 60 alkylamine group, C 1 to C 60 arylamine group, C 1 - an alkylthio group of C 60, C 2 ~ C 60 alkenyl group, C 2 - C 60 alkynyl group, a C 6 ~ C 60 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 60 of the aryl group, C 3 ~ C 60 cycloalkyl group, C 7 ~ C 60 arylalkyl group, C 8 ~ C 60 aryl alkenyl group, substituted or unsubstituted C 2 ~ C 60 heterocyclic group, substituted or unsubstituted silane group, substitution Or unsubstituted or substituted with at least one group selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and an acetylene group, C 2 ~ C 60 containing at least one of O, N, S, Si, P Heterocyclic group of;
    C6 ~ C60의 방향족 고리와 C4 ~ C60의 지방족 고리의 축합 고리기; 및Condensed ring groups of C 6 -C 60 aromatic rings and C 4 -C 60 aliphatic rings; And
    아릴아민기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C20의 아릴기, C7 ~ C20의 아릴알킬기, C8 ~ C20의 아릴알케닐기, C2 ~ C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환된 C2 ~ C20의 알케닐기;로 구성된 군에서 선택되며,Arylamine group, C 6 ~ C 60 aryl group, C 6 ~ C 20 aryl group substituted with deuterium, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 2 ~ C 20 It is selected from the group consisting of C 2 ~ C 20 alkenyl group unsubstituted or substituted with one or more substituents in the group consisting of a heterocyclic group, a nitrile group and an acetylene group of
    (5) X는 NR10, O, S, P, Si(R11)(R12), C(R13)(R14) 중 하나이며, (5) X is one of NR 10 , O, S, P, Si (R 11 ) (R 12 ), C (R 13 ) (R 14 ),
    여기서 R10 내지 R14는 서로 같거나 상이하고, 각각 독립적으로Wherein R 10 to R 14 are the same as or different from each other, and each independently
    수소원자; 할로겐 원자; 치환 또는 비치환된 C1~C20의 알킬기; Hydrogen atom; Halogen atom; Substituted or unsubstituted C1-C20 Alkyl group;
    수소, 중수소, 할로겐기, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~ C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1~ C60의 알킬티오펜기, C6 ~ C60의 아릴 티오펜기, C2 ~ C60의 알케닐기, C2 ~ C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C8 ~ C60의 아릴알케닐기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기, 및 치환 또는 비치환된 C2 ~ C60의 헤테로고리기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환된 C6 ~ C60의 아릴기; Hydrogen, deuterium, halogen group, C 1 ~ C 60 alkyl group, C 1 ~ C 60 alkoxy group, C 1 ~ C 60 alkylamine group, C 1 ~ C 60 arylamine group, C 1 ~ C 60 Alkylthiophene group, C 6 -C 60 aryl thiophene group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 3 -C 60 cycloalkyl group, C 6 -C 60 aryl A group, a C 6 to C 60 aryl group substituted with deuterium, a C 8 to C 60 arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C 6 ~ C 60 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C 2 ~ C 60 heterocyclic group;
    수소, 중수소, 할로겐, CN, NO2, C1 ~ C60의 알킬기, C1 ~ C60의 알콕시기, C1 ~C60의 알킬아민기, C1 ~ C60의 아릴아민기, C1 ~ C60의 알킬티오기, C2 ~ C60의 알케닐기, C2 ~C60의 알키닐기, C3 ~ C60의 시클로알킬기, C6 ~ C60의 아릴기, 중수소로 치환된 C6 ~ C60의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, 치환 또는 비치환된 C2 ~ C60의 헤테로고리기, 아세틸렌기, 치환 또는 비치환된 실란기, 치환 또는 비치환된 붕소기, 치환 또는 비치환된 게르마늄기로 이루어진 군으로부터 선택된 하나 이상의 기로 치환 또는 비치환되고 O, N, S, Si, P 중 적어도 하나를 이종 원자로 포함하는 C2 ~C60의 헤테로고리기; 및Hydrogen, deuterium, halogen, CN, NO 2 , C 1 to C 60 alkyl group, C 1 to C 60 alkoxy group, C 1 to C 60 alkylamine group, C 1 to C 60 arylamine group, C 1 ~ C import of 60 alkylthio, C 2 ~ C 60 alkenyl group, C 2 ~ C 60 alkynyl group, C 3 ~ C 60 cycloalkyl group, C 6 ~ C 60 of the aryl group, a C 6 substituted with deuterium ~ C 60 aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, substituted or unsubstituted C 2 ~ C 60 heterocyclic group, acetylene group, substituted or unsubstituted silane C 2 to C substituted or unsubstituted with one or more groups selected from the group consisting of a group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and containing at least one of O, N, S, Si, and P as hetero atoms. 60 heterocyclic group; And
    C6 ~ C60의 방향족 고리와 C4 ~ C60의 지방족 고리의 축합고리기;로 이루어진 군에서 선택되며,It is selected from the group consisting of a condensed ring group of C 6 ~ C 60 aromatic ring and C 4 ~ C 60 Aliphatic ring,
    (6) Ar1 내지 Ar3 및 R1 내지 R6은 각각 인접한 기와 결합하여 치환 또는 비치환된 포화 또는 불포화 고리를 형성할 수 있다.(6) Ar 1 to Ar 3 and R 1 to R 6 may be bonded to adjacent groups, respectively, to form a substituted or unsubstituted saturated or unsaturated ring.
  2. 제 1항에 있어서,The method of claim 1,
    상기 Ar1 내지 Ar3 및 R1 내지 R6은 각각 인접한 기와 결합하여 치환 또는 비치환된 포화 또는 불포화 고리를 형성하는 것을 특징으로 하는 화합물.Ar 1 to Ar 3 and R 1 to R 6 are each combined with an adjacent group to form a substituted or unsubstituted saturated or unsaturated ring.
  3. 제 1항에 있어서,The method of claim 1,
    상기 L은 상기 Ar1, R1 내지 R6 중 적어도 하나의 위치에 결합되는 것을 특징으로 하는 화합물.Wherein L is bonded to at least one of Ar 1 , R 1 to R 6 .
  4. 제 1항에 있어서,The method of claim 1,
    상기 L은 하기 화학식으로 구성된 그룹으로부터 선택되는 것을 특징으로 하는 화합물.Wherein L is selected from the group consisting of:
    Figure PCTKR2012001191-appb-I000077
    Figure PCTKR2012001191-appb-I000077
  5. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1)은 하기 화학식 (2)로 표시되는 것을 특징으로 하는 화합물.Formula (1) is a compound, characterized in that represented by the following formula (2).
    [화학식 2]          [Formula 2]
    Figure PCTKR2012001191-appb-I000078
    Figure PCTKR2012001191-appb-I000078
    상기 화학식 (2)에서, Ar1 내지 Ar3, R1 내지 R6, X, L 및 n은 화학식 (1)에서 정의된 것과 동일하다.In the above formula (2), Ar 1 to Ar 3 , R 1 to R 6 , X, L and n are the same as defined in the formula (1).
  6. 제 5항에 있어서,The method of claim 5,
    상기 화학식 (2)는 하기 화학식 (3) 내지 화학식 (6) 중 하나로 표시되는 것을 특징으로 하는 화합물.Formula (2) is a compound, characterized in that represented by one of the following formula (3) to formula (6).
    Figure PCTKR2012001191-appb-I000079
    Figure PCTKR2012001191-appb-I000079
    상기 화학식 (3) 내지 화학식 (6)에서, Ar1 내지 Ar3, R1 내지 R6, X는 화학식 (1)에서 정의된 것과 동일하다.In the above formulas (3) to (6), Ar 1 to Ar 3 , R 1 to R 6 , X are the same as defined in the formula (1).
  7. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1) 은 하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.Formula (1) is a compound, characterized in that represented by one of the following formula.
    Figure PCTKR2012001191-appb-I000080
    Figure PCTKR2012001191-appb-I000080
    Figure PCTKR2012001191-appb-I000081
    Figure PCTKR2012001191-appb-I000081
    Figure PCTKR2012001191-appb-I000082
    Figure PCTKR2012001191-appb-I000082
    Figure PCTKR2012001191-appb-I000083
    Figure PCTKR2012001191-appb-I000083
  8. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1)은 하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.Formula (1) is a compound, characterized in that represented by one of the following formula.
    Figure PCTKR2012001191-appb-I000084
    Figure PCTKR2012001191-appb-I000084
    Figure PCTKR2012001191-appb-I000085
    Figure PCTKR2012001191-appb-I000085
    Figure PCTKR2012001191-appb-I000086
    Figure PCTKR2012001191-appb-I000086
    Figure PCTKR2012001191-appb-I000087
    Figure PCTKR2012001191-appb-I000087
    Figure PCTKR2012001191-appb-I000088
    Figure PCTKR2012001191-appb-I000088
    Figure PCTKR2012001191-appb-I000089
    Figure PCTKR2012001191-appb-I000089
    Figure PCTKR2012001191-appb-I000090
    Figure PCTKR2012001191-appb-I000090
    Figure PCTKR2012001191-appb-I000091
    Figure PCTKR2012001191-appb-I000091
    Figure PCTKR2012001191-appb-I000092
    Figure PCTKR2012001191-appb-I000092
    Figure PCTKR2012001191-appb-I000093
    Figure PCTKR2012001191-appb-I000093
    Figure PCTKR2012001191-appb-I000094
    Figure PCTKR2012001191-appb-I000094
    Figure PCTKR2012001191-appb-I000095
    Figure PCTKR2012001191-appb-I000095
    Figure PCTKR2012001191-appb-I000096
    Figure PCTKR2012001191-appb-I000096
    Figure PCTKR2012001191-appb-I000097
    Figure PCTKR2012001191-appb-I000097
    Figure PCTKR2012001191-appb-I000098
    Figure PCTKR2012001191-appb-I000098
  9. 제 1항의 화합물을 포함하는 1층 이상의 유기물층을 포함하는 유기전자소자.An organic electronic device comprising at least one organic material layer comprising the compound of claim 1.
  10. 제 9항에 있어서,The method of claim 9,
    상기 유기전기소자는 순차적으로 적층된 제 1 전극, 상기 1층 이상의 유기물층 및 제2 전극을 포함하는 것을 특징으로 하는 유기전기소자.The organic electric device comprises an organic electrode comprising a first electrode, the organic material layer and the second electrode of one or more layers sequentially stacked.
  11. 제 9항에 있어서,The method of claim 9,
    상기 화합물을 용액공정(soluble process)에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자.And forming the compound into the organic material layer by a solution process.
  12. 제 9항에 있어서,The method of claim 9,
    상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 하나인 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electric element, characterized in that one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  13. 제 9항의 유기전기소자를 포함하는 디스플레이장치와;A display device comprising the organic electric element of claim 9;
    상기 디스플레이장치를 구동하는 제어부를 포함하는 전자장치.And a controller for driving the display device.
  14. 제 13항에 있어서,The method of claim 13,
    상기 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 중 적어도 하나인 것을 특징으로 하는 전자장치.The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic TFT).
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CN113121361A (en) * 2021-03-31 2021-07-16 吉林奥来德光电材料股份有限公司 Hole transport material with phenanthrene diarylamine structure and preparation method and application thereof
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