WO2012128509A2 - Composé et élément électrique organique qui utilise ledit composé, et dispositif électronique associé - Google Patents

Composé et élément électrique organique qui utilise ledit composé, et dispositif électronique associé Download PDF

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WO2012128509A2
WO2012128509A2 PCT/KR2012/001905 KR2012001905W WO2012128509A2 WO 2012128509 A2 WO2012128509 A2 WO 2012128509A2 KR 2012001905 W KR2012001905 W KR 2012001905W WO 2012128509 A2 WO2012128509 A2 WO 2012128509A2
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organic
indolyl
compound
aryl
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WO2012128509A3 (fr
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박정환
김대성
백장열
문성윤
정화순
김원삼
변지훈
최연희
이범성
최대혁
김동하
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덕산하이메탈(주)
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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    • 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
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    • 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
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • Y02E10/549—Organic PV cells

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 a 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.
  • the present invention provides a compound represented by the following formula.
  • the present invention provides an organic electric device and an electronic device including the compound represented by the above formula.
  • the present invention is a novel compound, which is useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc. Provides useful effects as a transport material.
  • the present invention provides an effect of increasing the efficiency of the organic electronic device, lowering the driving voltage, increasing the life and stability.
  • 1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
  • the present invention is a compound represented by the following formula (1) or (2).
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C One Through C 50 Alkyl group; C 6 ⁇ C 60 aryl group; It may be a heteroaryl group of C 2 ⁇ C 50 containing at least one hetero atom, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), but is not limited thereto.
  • n and m may be an integer of 1 to 4.
  • R 1 , R 2 , R 3 and R 4 may be bonded to adjacent groups to form a saturated or unsaturated ring.
  • R 2 and R 3 , R 2 and R 4 , R 3 and R 4 may combine with each other to form a saturated or unsaturated ring.
  • L is a single bond; Halogen group, C 1 ⁇ C 20 alkyl group, C 2 ⁇ C 20 alkenyl group, C 1 ⁇ C 20 alkoxy group, C 6 ⁇ C 20 aryl group, C 7 ⁇ C 20 arylalkyl group, C 8 ⁇ C 6 ⁇ C 60 arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of C 20 arylalkenyl group, C 2 ⁇ C 20 heterocyclic group, nitrile group and acetylene group; A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 Or an unsubstituted or substituted with one or more substituents in the group consisting of arylalkyl group of -C 20 , C 8 -
  • Ar 1 and Ar 2 are each independently C 1 ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl group, C 1 ⁇ C 20 Alkoxy group, C 6 ⁇ C 20 Aryl group, C 7 ⁇ C 20 C 1 ⁇ C 50 Alkyl group unsubstituted or substituted with a substituent selected from the group consisting of an arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 2 ⁇ C 20 hetero ring group, a nitrile group and an acetylene group; Halogen, amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 1 ⁇ C 20 alkoxy group, C 1 ⁇ C 20 alkylamine group, C 1 ⁇ C 20 alkylthiophene group, C 6 C 20 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20
  • aryl group, heteroaryl group of Ar 1 , Ar 2 may be represented as follows, but is not limited thereto.
  • the hetero ring group is a heterocyclic group containing O, N or S as a hetero atom, carbon number is not particularly limited, but may be 2-60 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzthiazole group, benzcarbazole group, benzthiophene group, dibenzothiophene group, benzfuranyl group, dibenzofura Although there exist a nil group etc., it is not limited to these.
  • the substituents may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring or ring, for example, an aliphatic, aromatic, or heteroaromatic monocyclic or polycyclic ring.
  • the present invention may include two or more structures of Formula 1 or 2.
  • the compound having the structural formula may be used in a solution process.
  • the compound may form an organic material layer of an organic electric device, which will be described later, by a soluble 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.
  • the compound represented by the formula (1) or (2) may be divided and represented by the formula (3) to the formula (6) according to the type of the substituents.
  • R 1 to R 4 and Ar 1 , Ar 2 , and L may be the same as those of Formulas 1 and 2 described above.
  • the compounds represented by Formulas 1 to 6 may each be one or more than one of the compounds represented by Formula 7.
  • the intermediate E synthesized in the above step was dissolved in anhydrous THF, and the temperature of the reaction was lowered to -78 ° C. After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour. Then, the temperature of the reaction was lowered to -78 °C, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate G (yield: 74%).
  • the intermediate G, 4-bromoaniline, Pd (PPh 3 ) 4 , and K 2 CO 3 synthesized in the above step were dissolved in THF and H 2 O, and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate I (yield: 62%).
  • the intermediate J and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 2 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 58%).
  • the intermediate J and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 3 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
  • the intermediate K and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 61 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
  • the intermediate K and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 62 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 49%).
  • the intermediate K and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 63 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 42%).
  • the intermediate L and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 88 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 81%).
  • the intermediate L and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 89 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 79%).
  • the intermediate L and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 90 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 77%).
  • the intermediate B synthesized in the above step under nitrogen was dissolved in a solvent of CH 2 Cl 2 , and then N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH 2 Cl 2 and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH 2 Cl 2 and methanol solvent to obtain the desired intermediate P (yield: 90%).
  • the intermediate Q and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 176 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 62%).
  • Synthesis of other compounds is substantially the same as the method for synthesizing compounds that specifically describes the preparation examples, except that some of the starting materials or intermediates are replaced with starting materials or intermediates of the corresponding compounds.
  • Synthesis of the chemicals 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, in the intermediate J, instead of phenyl at the N atom of the amine group, naphthyl or biphenyl group Synthesis method is substantially the same as that of Compound 1 except that Intermediate 3, which is substituted with an anthryl group, a carbazole group, a fluorene group, and the like are reacted.
  • Synthesis of chemicals 40, 43, 46, 49, 53, 55, 58 replaces the naphthyl group, biphenyl group, anthryl group, carbazole group, fluorene group, etc. instead of phenyl in N atom of amine group in intermediate J.
  • the method of synthesis is substantially the same as that of compound 1, except that the intermediate of the naphthyl group of the N atom of carbazole reacts with intermediate 3.
  • the compound which has the intrinsic property of the introduced substituent can be synthesize
  • the compound according to the present invention can be used for various purposes in the organic light emitting electronic 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 electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic material layer is formed using the above-described compounds.
  • 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.
  • the compound of the present invention can be used in a soluble process.
  • the compound may form an organic material layer of an 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 can 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 light emitting diode (OLED) will be described.
  • OLED organic light emitting diode
  • 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 light emitting display device to which the compound of the present invention can be applied.
  • the organic light emitting device except that at least one layer of 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 to include the compound of the present invention.
  • 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 to include the compound of the present invention.
  • 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.
  • the organic electroluminescent device includes a substrate 101, 201, 301, 401, 501, 601, an anode 102, 202, 302, 402, 502, 602, a hole injection layer 103, 203, 303, hole transport layer 104, 204, 304, 404, light emitting layer 105, 205, 305, 405, 505, 605, electron transport layer 106, 206, 406, 506, electron injection layer 107 2 to 6, at least one layer of the organic material layer except for the light emitting layer may be omitted.
  • the organic light emitting diode further includes a hole blocking layer (HBL) that blocks hole movement, an electron blocking layer (EBL) that blocks electrons from moving, 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 light emitting device is a metal having a 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 light emitting 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 light emitting device, and a silicon wafer, quartz or glass plate, metal plate, 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
  • an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene.
  • PPV polyphenylene vinylene
  • a polymer such as poly fluorene can be used for
  • 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 material containing a boron compound 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 light emitting device may be a top emission type, a bottom emission type or a double-sided emission type according to 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.
  • the compounds were synthesized according to the synthesis method described above, and the examples in which the compounds were applied to an organic material layer of an organic electroluminescent device, for example, an organic electroluminescent device, were compared with those of commonly used compounds.
  • a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited as a hole injection layer on the ITO layer (anode) formed on the organic substrate to form a thickness of 10 nm.
  • the inventive compound and the comparative example were vacuum deposited with a hole transport layer to a thickness of 20 nm. Vacuum deposition was carried out for comparative experiments.
  • BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant, and the host material was 9,10-di- (naphthalene-2-anthracene) (hereinafter abbreviated as ADN), and the doping concentration was fixed at 4%.
  • a comparative experiment was conducted. Subsequently, tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, which is an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic light emitting device by using Al / LiF as a cathode.
  • LiF which is an alkyl halide metal
  • the electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was 1000 cd / m 2.
  • the T95 lifetime was measured using a life measurement instrument manufactured by McScience Inc. at the reference luminance.
  • an organic electroluminescent device having the same structure was manufactured using the compound represented by the following formula instead of the compound of the present invention as the hole transport layer material.
  • the organic light emitting device using the organic light emitting device material of the present invention can not only improve color purity but also improve driving voltage significantly.
  • the driving voltage, luminous efficiency, emission color, and lifespan are not only higher than those of the comparative example, but also higher in color purity and improved in driving voltage. It confirmed that there was.

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Abstract

La présente invention concerne un composé, un élément électrique organique qui utilise ledit composé, et un dispositif électronique associé.
PCT/KR2012/001905 2011-03-21 2012-03-16 Composé et élément électrique organique qui utilise ledit composé, et dispositif électronique associé WO2012128509A2 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468245A (zh) * 2013-08-16 2013-12-25 石家庄诚志永华显示材料有限公司 一种具有载流子传输能力的oled材料及其制备方法和应用
CN103601668A (zh) * 2013-11-26 2014-02-26 大连联化化学有限公司 一种n-苯基-3-溴咔唑的制备方法
WO2016201513A1 (fr) * 2015-06-18 2016-12-22 Commonwealth Scientific And Industrial Research Organisation Matériau électroactif, compositions d'impression et procédés de fabrication de cellules solaires
CN107868038A (zh) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 一种含有9,9’‑螺二芴的有机化合物及其应用
CN107868031A (zh) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 一种以9,9’‑螺二芴为核心的有机化合物及其在有机电致发光器件上的应用
CN109134348A (zh) * 2018-09-30 2019-01-04 长春海谱润斯科技有限公司 一种咔唑类化合物及其有机发光器件
CN110835304A (zh) * 2018-08-17 2020-02-25 江苏三月光电科技有限公司 一种以螺芴烯结构为核心的化合物及其制备方法和其应用
CN111362866A (zh) * 2018-12-26 2020-07-03 江苏三月光电科技有限公司 一种由氮杂苯修饰的有机化合物及其应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013039073A1 (fr) * 2011-09-15 2013-03-21 出光興産株式会社 Dérivé d'amine aromatique et élément électroluminescent organique l'utilisant
KR101973030B1 (ko) * 2012-06-20 2019-04-30 덕산네오룩스 주식회사 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
KR102082668B1 (ko) * 2013-11-14 2020-02-28 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
KR102649050B1 (ko) * 2016-11-29 2024-03-18 엘지디스플레이 주식회사 유기 화합물과 이를 이용한 발광다이오드 및 유기발광다이오드 표시장치

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050221124A1 (en) * 2004-04-02 2005-10-06 Seok-Hwan Hwang Fluorene-based compound and organic electroluminescent display device using the same
KR20090112148A (ko) * 2008-04-23 2009-10-28 덕산하이메탈(주) 유기층에 플루오렌계 유도체를 포함하는 유기 전계발광소자
KR20090129799A (ko) * 2008-06-13 2009-12-17 덕산하이메탈(주) 신규한 카바졸 유도체 및 이를 포함하는 유기 전계발광소자
KR20100008947A (ko) * 2008-07-17 2010-01-27 덕산하이메탈(주) 플루오렌카바졸계 유도체 및 이를 포함하는유기전계발광소자

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101072812B1 (ko) * 2009-03-30 2011-10-14 덕산하이메탈(주) 카바졸과 플루오렌이 결합하여 고리를 형성하는 비대칭 구조를 갖는 화합물 및 이를 이용한 유기전자소자, 그 단말

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050221124A1 (en) * 2004-04-02 2005-10-06 Seok-Hwan Hwang Fluorene-based compound and organic electroluminescent display device using the same
KR20090112148A (ko) * 2008-04-23 2009-10-28 덕산하이메탈(주) 유기층에 플루오렌계 유도체를 포함하는 유기 전계발광소자
KR20090129799A (ko) * 2008-06-13 2009-12-17 덕산하이메탈(주) 신규한 카바졸 유도체 및 이를 포함하는 유기 전계발광소자
KR20100008947A (ko) * 2008-07-17 2010-01-27 덕산하이메탈(주) 플루오렌카바졸계 유도체 및 이를 포함하는유기전계발광소자

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OZLEM USLUER ET AL.: 'Fluorene-Carbazole Dendrimers : Synthesis, Thermal, Photophysical and Electroluminescent Device Properties' ADVANCED FUNCTIONAL MATERIAL vol. 20, no. 23, 2010, ISSN 1616-3028 pages 4152 - 4161 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468245A (zh) * 2013-08-16 2013-12-25 石家庄诚志永华显示材料有限公司 一种具有载流子传输能力的oled材料及其制备方法和应用
CN103601668A (zh) * 2013-11-26 2014-02-26 大连联化化学有限公司 一种n-苯基-3-溴咔唑的制备方法
WO2016201513A1 (fr) * 2015-06-18 2016-12-22 Commonwealth Scientific And Industrial Research Organisation Matériau électroactif, compositions d'impression et procédés de fabrication de cellules solaires
CN107868038A (zh) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 一种含有9,9’‑螺二芴的有机化合物及其应用
CN107868031A (zh) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 一种以9,9’‑螺二芴为核心的有机化合物及其在有机电致发光器件上的应用
CN110835304A (zh) * 2018-08-17 2020-02-25 江苏三月光电科技有限公司 一种以螺芴烯结构为核心的化合物及其制备方法和其应用
CN109134348A (zh) * 2018-09-30 2019-01-04 长春海谱润斯科技有限公司 一种咔唑类化合物及其有机发光器件
CN111362866A (zh) * 2018-12-26 2020-07-03 江苏三月光电科技有限公司 一种由氮杂苯修饰的有机化合物及其应用

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