WO2013094834A1 - Nouveau composé ayant une stabilité, et matière de transfert de charge et diode organique émettant de la lumière phosphorescente bleue le comprenant - Google Patents

Nouveau composé ayant une stabilité, et matière de transfert de charge et diode organique émettant de la lumière phosphorescente bleue le comprenant Download PDF

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WO2013094834A1
WO2013094834A1 PCT/KR2012/005204 KR2012005204W WO2013094834A1 WO 2013094834 A1 WO2013094834 A1 WO 2013094834A1 KR 2012005204 W KR2012005204 W KR 2012005204W WO 2013094834 A1 WO2013094834 A1 WO 2013094834A1
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compound
light emitting
substituted
carbazole
triphenylamine
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WO2013094834A9 (fr
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신동윤
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율촌화학 주식회사
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    • C—CHEMISTRY; METALLURGY
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L21/2658—Bombardment with radiation with high-energy radiation producing ion implantation of a molecular ion, e.g. decaborane
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • 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
    • 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
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the present invention relates to a novel compound having stability, a charge transporting material containing the same, and a blue phosphorescent organic light emitting device. More particularly, the present invention relates to a novel compound having stable stability and electrical stability such as a high glass transition temperature (Tg) A charge transporting material containing the same, and a blue phosphorescent organic light emitting device.
  • Tg glass transition temperature
  • OLEDs organic light emitting devices
  • PM passive matrix
  • Phosphorescent luminescence is a phenomenon in which electrons transition from ground states to excited states, followed by intersystem crossing to cause non-luminescent transition of singlet excitons to triplet excitons, And a light emitting mechanism.
  • This phosphorescence emission can not transfer to the ground state when the triplet exciton is transited, and the lifetime (luminescence time) of the phosphorescence is longer than that of fluorescence because the phosphorescence is transferred to the bottom state after the reversal of the electron spin proceeds. That is, the emission duration of fluorescence emission is only several nanoseconds, but in the case of phosphorescence emission, it corresponds to a relatively long time of several microseconds.
  • the phosphorescent organic light emitting device includes an anode made of an ITO transparent electrode; A hole transport layer (HTL) formed on the anode; An emission layer (EML) formed on the hole transport layer (HTL); An electron transport layer (ETL) formed on the emission layer (EML); And a cathode formed on the electron transport layer (ETL), which are successively laminated on the substrate through a method such as vapor deposition.
  • the light emitting layer (EML) includes a host as a charge transporting material and a dopant as a phosphorescent material.
  • the phosphorescent organic light emitting device having the above structure
  • holes are injected from the anode and electrons are injected from the cathode.
  • the injected holes and electrons are injected through the hole transport layer (HTL) and the electron transport layer (EML) to form luminescent excitons.
  • the formed luminescent excitons emit light while transitioning to the ground state.
  • Korean Patent Registration No. 10-0454500 discloses an organic light emitting element in which a buffer layer is formed between a hole transporting layer (HTL) and a light emitting layer (EML)
  • HTL hole transporting layer
  • EML light emitting layer
  • HTL hole transporting layer
  • EML light emitting layer
  • HTL hole transporting layer
  • EML light emitting layer
  • the OLEDs shown in the prior art documents 1 and 2 have a complicated manufacturing process and a large thickness due to a number of processes for forming each layer due to the multilayer structure having an excessively large number of layers. And is not suitable for blue characteristics, so that it is difficult to have high luminous efficiency and long life characteristics.
  • Korean Patent Laid-Open No. 10-2007-0091291 discloses an organic light-emitting device using a material containing a triarylamine group as a hole transport material.
  • Korean Patent Laid-Open No. 10-2011-0041952 discloses a carbazole compound represented by a specific formula.
  • the charge transport material In order to increase the luminous efficiency of the blue phosphorescent organic light emitting device (PHOLED), the charge transport material must maximize the injection of charges (holes and electrons) into the light emitting layer (EML). And this requires a wide energy band gap. In addition, triplet energy (ET) must be high. In addition, the charge transporting material should have excellent electrical properties such as charge mobility and excellent thermal stability such as glass transition temperature (Tg).
  • the hole transporting material particularly, the hole transporting material constituting the HTL is preferably TAPC (1,1-bis (4-bis (4-methylphenyl) .
  • the charge transporting materials used for conventional blue phosphorescence including TAPC have a low glass transition temperature (Tg) and a low stability of the compound, resulting in a short life span.
  • a novel high-molecular-weight compound having a high thermal stability such as a glass transition temperature (Tg) and a wide energy bandgap and having improved electrical properties such as charge mobility, , A charge transporting material containing the same, and a blue phosphorescent organic light emitting device (PhOLED).
  • Tg glass transition temperature
  • PhOLED blue phosphorescent organic light emitting device
  • the present invention provides a compound wherein an aromatic compound is substituted for a carborane.
  • the aromatic compound is selected from compounds having a phenyl group and a nitrogen atom according to a preferred embodiment.
  • the aromatic compound is preferably selected from a triphenylamine-based compound or a carbazole-based compound.
  • the aromatic compound may be substituted at the o-, m- or para- position of the carbene, preferably substituted at the para- position of the carbene.
  • the phenyl group of the aromatic compound preferably has one or more alkyl groups bonded thereto.
  • the present invention also provides a charge transport material comprising the compound according to the present invention and a blue phosphorescent organic light emitting device (PhOLED).
  • a charge transport material comprising the compound according to the present invention and a blue phosphorescent organic light emitting device (PhOLED).
  • the blue phosphorescent organic light emitting device includes a positive electrode; A hole transport layer (HTL) formed on the anode; And an emission layer (EML) formed on the hole transport layer (HTL); An electron transport layer (ETL) formed on the light emitting layer (EML); And a cathode formed on the electron transport layer (ETL), wherein at least one selected from the group consisting of the hole transport layer (HTL), the emission layer (EML) and the electron transport layer (ETL) includes the compound according to the present invention.
  • an aromatic compound preferably a triphenylamine-based compound or a carbazole-based compound
  • a carborane has a high glass transition temperature (Tg), thereby having excellent thermal stability.
  • electrical characteristics such as charge mobility are excellent.
  • Tg glass transition temperature
  • PhOLED blue phosphorescent organic light emitting device
  • it is electrically stable and has long-life characteristics in the blue phosphorescent organic light emitting device (PhOLED).
  • FIG. 1 and FIG. 2 are cyclic voltammetry (CV) curves showing the electrochemical stability evaluation results of compounds according to an embodiment of the present invention.
  • the charge transporting material used for the blue phosphorescent organic light emitting device must have a high triplet energy (ET) and a wide energy band gap in order to realize high efficiency blue phosphorescence.
  • physical properties such as charge mobility (charge mobility) and the like should be excellent and thermal stability such as glass transition temperature (Tg) should be excellent.
  • Tg glass transition temperature
  • it should have electrical stability and long life characteristics.
  • the compound provided in the present invention has a structure in which an aromatic compound is substituted for a carborane. Specifically, it has a structure in which an aromatic compound is substituted for a carborane having a three-dimensional structure represented by B 10 C 2 H 2 . At this time, one or two aromatic compounds may be substituted for H of carboran.
  • the aromatic compound is not limited as long as it has one or two or more phenyl groups in the molecule.
  • the phenyl group of the aromatic compound is substituted and bonded to the H site of the carboran.
  • the aromatic compound is selected from compounds having at least one phenyl group and at least one nitrogen (N) atom.
  • the aromatic compound may be selected from a triphenylamine-based compound or carbazole-based compound having a phenyl group and nitrogen (N), which has good charge mobility.
  • a triphenylamine-based compound or a carbazole-based compound is substituted for an aromatic compound in a carborane, it is preferable in terms of electric characteristics such as charge mobility as well as thermal properties such as a glass transition temperature (Tg).
  • the triphenylamine-based compound is not limited as long as it has three phenyl groups and at least one nitrogen (N) in the molecule.
  • the triphenylamine-based compound includes, for example, triphenylamine having three phenyl groups and at least one nitrogen (N) in the molecule, and any other compound may be bonded to the triphenylamine.
  • one or more alkyl, aryl (a compound having at least one phenyl group) and a heterocyclic compound may be bonded to the phenyl group of triphenylamine.
  • the carbazole-based compound is not limited as long as it has at least one carbazole structure in the molecule.
  • the carbazole-based compound is not particularly limited as long as it has a carbazole in which two 6-atom phenyl groups (benzene rings) are bonded to both sides of a five-membered ring containing nitrogen (N) .
  • N nitrogen
  • one or more alkyl, aryl (a compound having at least one phenyl group) and a heterocyclic compound may be bonded to the carbazole.
  • the aromatic compound has a phenyl group, and the phenyl group is bound to at least one alkyl group (C n H 2n + 1 - where n is not limited, for example from 1 to 20) It is good to have.
  • the alkyl group is bonded to the phenyl group of the aromatic compound, the electrochemical stability and the like are advantageous.
  • the aromatic compound when the aromatic compound is selected from a triphenylamine-based compound, at least one of the three phenyl groups of the triphenylamine-based compound preferably has at least one alkyl group bonded thereto.
  • the aromatic compound when the aromatic compound is selected from carbazole-based compounds, it is preferable that at least one of the two phenyl groups of the carbazole-based compound has at least one alkyl group bonded thereto.
  • the compound provided in the present invention has a structure in which two aromatic compounds are substituted. That is, it is preferable that two aromatic compounds as described above are substituted for carboranes.
  • the compound provided by the present invention is selected from compounds represented by the following general formula (1) or (2).
  • CB is carboran.
  • R 1 , R 2 , R 3 and R 4 may be the same or different and are each hydrogen (H) or an alkyl group.
  • the alkyl group is not limited. That is, the number of carbon atoms of the alkyl group is not limited.
  • the alkyl group may have, for example, a C1 to C20 carbon number.
  • the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the propyl group includes an n-propyl group and an iso-propyl group
  • the butyl group is an n-butyl group. group, an iso-butyl group and a tertiary-butyl group. It is preferable that at least one selected from R 1 , R 2 , R 3 and R 4 in the above formulas (1) and (2) is an alkyl group.
  • the two aromatic compounds When two aromatic compounds are substituted for carboranes, the two aromatic compounds may be substituted at the ortho (o-), meta (m-) or para (p-) position of the carboran.
  • the aromatic compound is preferably substituted at the m-position or the p-position of carboran, more preferably at the p-position.
  • Tg glass transition temperature
  • the compound according to the present invention has a structure in which an aromatic compound (preferably a triphenylamine-based compound or carbazole-based compound) is substituted for carboranes.
  • an aromatic compound preferably a triphenylamine-based compound or carbazole-based compound
  • specific examples of the compound according to the present invention are illustrated by the structural formulas.
  • carboran (-B 10 C 2 -) is represented by a molecular model.
  • R 5 is an alkyl group.
  • the compounds according to the present invention can be selected from among the groups listed in the following formulas (3) and (4).
  • the aromatic compound exemplifies a structure selected from a triphenylamine-based compound or a carbazole-based compound, and may be selected from the group listed in the following Chemical Formula 4, among which the alkyl group (R 5 ) It is good.
  • the alkyl group (R 5 ) is bonded to the phenyl group in the formula (4), but one to four alkyl groups (R 5 ) may be bonded to the phenyl group.
  • the compounds according to the invention may also be selected from the group of compounds represented by the following formulas (3) and (4), preferably from compounds in which the aromatic compound is bonded at the p-position of the carboran.
  • the compounds according to the present invention can be synthesized (produced) in various ways.
  • a carbene when a carbene is substituted with a triphenylamine-based compound, it is synthesized by, for example, synthesizing triphenylamine substituted with Br (bromine) and then reacting the carbene (R 1 , R 2 , R 3 and R 4 in Formula (1) may be H).
  • alkyltriphenylamine is synthesized, followed by substitution reaction of carboran (o-, m-, or p-) in the presence of a catalyst and a solvent to synthesize (R 1 , R 2 , R 3 and R 4 are alkyl groups).
  • a carbazole (o-, m-, or p-) substitution reaction is carried out with a carbazole (or a carbazole in which an alkyl group is bonded) in the presence of a catalyst and a solvent to synthesize (R 1 , R 2 , R 3 and R 4 are H or an alkyl group).
  • the compound according to the present invention is a compound having a specific structure in which an aromatic compound (preferably a triphenylamine-based compound or a carbazole compound) is substituted for carboranes, which has high triple energy (ET) And has a wide energy bandgap.
  • an aromatic compound preferably a triphenylamine-based compound or a carbazole compound
  • ET triple energy
  • the compound according to the present invention is a compound having a specific structure in which an aromatic compound (preferably a triphenylamine-based compound or a carbazole compound) is substituted for carboranes, which has high triple energy (ET) And has a wide energy bandgap.
  • thermal stability such as glass transition temperature (Tg) and electrical properties such as charge mobility are superior to those of TAPC and carbazole compounds conventionally used.
  • the compound according to the present invention is suitable for use in products requiring thermal stability and electrical characteristics (such as charge transport properties), for example, organic light emitting devices (OLEDs), more specifically blue phosphorescent organic light emitting devices It is applied as a charge carrier and realizes excellent luminous efficiency.
  • the compound according to the present invention has high electrochemical stability, so that it has long life characteristics in a device such as a blue phosphorescent organic light emitting device (PhOLED).
  • the charge transporting material according to the present invention includes the compound according to the present invention.
  • the charge transport material according to the present invention is usefully used, for example, as a charge (electron and electron) transport material of an organic light emitting device (OLED), specifically, a blue phosphorescent organic light emitting device (PhOLED) It is very useful as a sieve.
  • OLED organic light emitting device
  • PhOLED blue phosphorescent organic light emitting device
  • the blue phosphorescent organic light emitting device (PhOLED) according to the present invention includes the compound according to the present invention.
  • the blue phosphorescent organic light emitting device (PhOLED) according to the present invention may have a plurality of organic thin film layers as usual, and at least one of the plurality of organic thin film layers may transmit the compound according to the present invention to the charge transport material .
  • the blue phosphorescent organic light-emitting device comprises an anode; A hole transport layer (HTL) formed on the anode; A light emitting layer (EML) formed on the hole transport layer (HTL); An electron transport layer (ETL) formed on the light emitting layer (EML); And a cathode formed on the electron transport layer (ETL).
  • the blue phosphorescent organic light emitting device (PhOLED) according to the present invention may include a hole injection layer (HIT) formed between the anode and the hole transport layer (HTL), as occasion demands; And an electron injection layer (EIL) formed between the electron transport layer (ETL) and the cathode.
  • the blue phosphorescent organic light emitting device (PhOLED) according to the present invention may include a substrate for supporting the respective layers.
  • At this time, at least one selected from the HTL, the EML, and the ETL may include the compound according to the present invention.
  • at least the hole transport layer (HTL) comprises the compound according to the present invention.
  • the substrate is not particularly limited as long as it has a supporting force, and can be selected from, for example, a glass substrate or a polymer substrate. Further, the substrate may be selected from a polymer substrate in consideration of flexibility, and may be made of a polymer including, for example, one or more resins selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polycarbonate A film can be used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • a film can be used.
  • the anode is not particularly limited and may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tungsten oxide (WO), tin oxide (SnO), zinc oxide (ZnO) Metal oxides such as aluminum-oxide (ZAO); Metal nitrides such as titanium nitride; Metals such as gold, platinum, silver, copper, aluminum, nickel, cobalt, lead, molybdenum, tungsten, tantalum and niobium; An alloy of such a metal or an alloy of copper iodide; And conductive polymers such as polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, poly (3-methylthiophene), and polyphenylene sulfide; And the like.
  • the anode may be selected from transparent electrodes selected from ITO, IZO and WO, for example.
  • the hole transport layer (HTL) may include the compound according to the present invention as described above. Further, the hole transport layer (HTL) may further include conventionally used hole transport materials in addition to the compounds according to the present invention.
  • the light emitting layer may be composed of a single layer or a multilayer, including a host for charge transport and a dopant for phosphorescence characteristics.
  • the host may be conventional or may contain the compound according to the present invention.
  • the host of the light emitting layer may be, for example, 4,4'-N, N-dicarbazolebiphenyl (CBP), 1,3-N, N-dicarbazolebenzene (mCP) Can be used.
  • the host material may be selected from the group consisting of (4,4'-bis (2,2-diphenyl-ethen-1-yl) diphenyl (DPVBi), bis (styryl) amine Quinolinolato) (aluminum (III) (BAlq), 3 (2-methyl-8-quinolinolato) (4-dimethylamino) 4- (4-ethylphenyl) -1,2,4-triazole (p-EtTAZ), 3- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,2 ', 7,7'-tetrakis (P-TTA), 5,5-bis (dimetiethylboryl) -2,2-bithy
  • the dopant of the light emitting layer may be at least one selected from commonly used FIr6 and FIrpic, and may be DCM1 (4-dicyanomethylene-2-methyl-6- (para-dimethylaminostyryl) -4H-pyran), dicyanomethylene) -2-methyl-6- (1,1,7) -tetramethylene- 9-enyl) -4H-pyran), dicyanomethylene) -2-tertiarybutyl-6- (1,1,7,7-tetramethylduluridyl- ) -4H-pyran), dicyanomethylene) -2-isopropyl-6- (1,1,7,7-tetramethylduluridyl-9-enyl) -4H- And Rubrene, and the like.
  • the electron transport layer (ETL) may be a conventional one or may include the compound according to the present invention.
  • the electron transport layer (ETL) is conventional and may be selected from, for example, aryl-substituted oxadiazole, aryl-substituted triazole, aryl-substituted phenanthroline, benzoxazole and benzisazole compounds, Specific examples thereof include 4-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl (BAlq), 1,3- -Oxadiazole (OXD-7), 3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4- triazole (TAZ), and tris (8- quinolinato) aluminum (III) (Alq3), and the like.
  • the compounds according to the present invention may be mixed in the above listed materials.
  • HIL hole injection layer
  • EIL electron injection layer
  • HIL hole injection layer
  • EIL electron injection layer
  • these include, for example, 4,4'-bis ⁇ N- (1-naphthyl) -N-phenyl-amino ⁇ biphenyl (? -NPD), PEDOT / PSS, copper phthalocyanine , 4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), and 4,4' -Triphenylamine (2-TNATA), and the like.
  • the negative electrode is not limited, and a conventional one can be used.
  • the cathode can be selected from metal.
  • the negative electrode may include one or more alloys selected from Al, Ca, Mg and Ag, for example, and an alloy containing Al or Al may be coated with LiF.
  • the thicknesses of the respective layers constituting the blue phosphorescent organic light emitting device (PhOLED) in the present invention are not limited.
  • the layers may be formed by vacuum deposition such as sputtering, drying after liquid coating, firing after coating, and the like, and the formation method thereof is not limited.
  • a compound in which a carbazole compound was substituted at the o-position of carboran was synthesized (prepared) by the following procedure.
  • the final product according to the present example 1 synthesized as described above is a compound in which a carbazole compound is substituted at the o-position, as shown in the following chemical formula 5, which was confirmed by 1 H-NMR analysis.
  • a compound in which a carbazole compound was substituted at the m-position of carboran was synthesized (prepared) by the following procedure.
  • K 2 CO 3 potassium carbonate
  • palladium tripotassium phosphate were added dropwise to the carbazole and stirred. Then, dicarbazoyl ethylene was separated by column chromatography.
  • the final product according to Example 2 synthesized as described above is a compound in which a carbazole compound is substituted at the m-position, as shown in Formula 6 below, which was confirmed by 1 H-NMR analysis.
  • the final product according to Example 3 synthesized as described above is a compound in which a carbazole compound is substituted at the p-position, as shown in the following Chemical Formula 7, which was confirmed by 1 H-NMR analysis.
  • triphenyl amine substituted with Br was dissolved in tetrahydrofuran (THF) solvent, and the solution was maintained at -78 ° C. Next, the temperature was lowered, n-butyllithium (n-BuLi) was added, the temperature of the refluxing solution was maintained for 30 minutes, trimethoxyborate was added and reacted. After removing moisture through anhydrous magnesium sulfate, the solvent was removed. Then, triphenylamine boronic acid produced by column chromatography was isolated.
  • THF tetrahydrofuran
  • Triphenylamine 4-boronic acid was charged with p-carborane, Pd (PPh 3 ) 4 (Tetrakis (triphenylphosphine) palladium) and K 2 CO 3 (DME) and distilled water were added dropwise thereto, followed by stirring at 140 ⁇ ⁇ for 12 hours. The stirred solution was dehydrated through anhydrous magnesium sulfate, and the solvent was removed. Next, the final product was isolated using column chromatography.
  • the final product according to the present example 4 synthesized as above was a compound in which triphenylamine was substituted at the p-position, as shown in the following chemical formula 8, which was confirmed by 1 H-NMR analysis.
  • the final product according to the present example 5 synthesized as described above is a compound in which triphenylamine is substituted at the p-position and a methyl group (Me) is bonded to the phenyl group of the triphenylamine, This was confirmed by 1 H-NMR analysis.
  • Me is a methyl group (CH 3 -).
  • a carbazole compound represented by the following formula (11) was used as a specimen according to Comparative Example 2.
  • the glass transition temperature (Tg) and melting temperature (Tm) were evaluated as thermal properties.
  • the triplet energy (ET) and the energy band gap were evaluated using a laser measuring instrument (1 ns pulsed nitrogen laser, manufactured by Photon Technology International, model name GL-3300) And Digital Oscilloscope (product of LeCroy, model LC 572A).
  • the thermal properties (Tg, Tm) were evaluated using a Pysis Diamond DSC instrument from Perkin-Elmer.
  • the characteristics were different depending on the substitution position of the carbazole. That is, it was found that the case where the substituent carbazole is bonded at the m-position with respect to the o-position of carboran exhibits good characteristics. And showed the best characteristics when substituted at the p-position. In particular, it was found that the glass transition temperature (Tg), when substituted at the p-position, had a high thermal property of 10 ° C or higher than that at the o-position or the m-position.
  • Tg glass transition temperature
  • FIG. Fig. 1 is the CV curve of the compound according to Example 4
  • Fig. 2 is the CV curve of the compound according to Example 5.
  • a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), and an electron transport layer (ETL) were formed on the ITO film by a conventional deposition method. Thereby forming a negative electrode. (CBP) and a dopant (FIr6) were used at a molar ratio of 9: 1, which are commonly used for the hole injecting layer (HIL) and the light emitting layer (EML), respectively.
  • CBP hole injecting layer
  • EML electron transport layer
  • ETL electron transport layer
  • the electron transport layer (ETL) and the cathode were laminated to each other by using glass / anode / HIL (NPD) / HTL / EML (CBP + FIr6) / ETL (SiTAZ) / cathode using SiTAZ and LiF / Was prepared.
  • Example 1 used the compound according to Example 1
  • Example 2 used the compound according to Example 2 above.
  • Working Example 3 the compound according to Example 3 was used.
  • PhOLED was prepared in the same manner as above except that HTL was used in a different manner. Specifically, the compound (TAPC) according to Comparative Example 1 was used for Comparative Sample 1, and the compound (carbazole) according to Comparative Example 2 was used for Comparative Sample 2.
  • the minimum driving voltage (V ON ) causing the current density and the current density at 12 V were evaluated for PhOLED according to each of the test pieces (1 to 3) and the comparative test pieces (1 and 2) manufactured as described above. Further, device characteristics such as light emission luminance cd / A, light emission efficiency (lm / W) and color coordinates (CIE) were evaluated.
  • PhOLED according to the embodiment of the present invention has high current density as well as excellent device characteristics such as light emission luminance (Cd / A) and luminous efficiency (lm / W), as compared with conventional comparative samples . Further, in the case of the test piece 3 using the compound in which the aromatic compound (carbazole-based) was substituted at the p-position of carboran, it was found that the device was driven at a low voltage of 4.5 V with excellent luminescence characteristics.
  • PhOLED an element using the compound according to Example 5 in which triphenylamine (Me) was bonded to a hole transporting layer (HTL), and a device using HTL as a hole transporting layer
  • HTL hole transporting layer
  • the lifetime was measured by measuring the lifetime of the PhOLED with DC-power supply (ED-200E) and luminance meter for optical and electrical characteristics. At this time, the measurement of the lifetime is called half-life at half of the initial luminance, and the lifetime is defined as the half-life.
  • the device specimen according to the present invention has a lifetime characteristic of at least 2 times, which is a half life period of 871 hours for the device using the compound according to Example 5 and 428 hours for the device according to the comparative specimen 1 could know.
  • the compound (charge transport material) according to the present invention has a high triplet energy (ET) and a wide energy bandgap. And excellent electrical properties such as hole mobility, and particularly excellent thermal stability such as glass transition temperature (Tg). In addition, it has electrochemical stability as well as thermal stability, and it has a long life characteristic. In addition, it can be seen that PhOLED employing it has excellent luminescence characteristics.
  • a charge transporting material and a blue phosphorescent organic light emitting device having a long life characteristic including a novel compound having improved thermal stability and electric characteristics are provided.

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Abstract

La présente invention concerne un nouveau composé, et une matière de transfert de charge et une diode émettant de la lumière organique phosphorescente bleue le comprenant (PhOLED). La présente invention concerne un composé dans lequel un composé aromatique remplace le carborane, et la matière de transfert de charge et la PhOLED bleue comprenant le composé. Le composé aromatique est choisi de préférence parmi un composé triphénylamine ou un composé carbazole et est substitué à une position p du carborane. Dans le nouveau composé selon la présente invention, le composé aromatique remplace le carborane, et ainsi a des caractéristiques électriques supérieures comprenant une stabilité thermique élevée, telle qu'une température de transition vitreuse, une large bande interdite d'énergie et une mobilité de charges, permettant ainsi d'améliorer une caractéristique d'émission de lumière d'une diode et de fournir une longue durée de vie en ayant une stabilité électrique.
PCT/KR2012/005204 2011-12-19 2012-06-29 Nouveau composé ayant une stabilité, et matière de transfert de charge et diode organique émettant de la lumière phosphorescente bleue le comprenant WO2013094834A1 (fr)

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