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WO2013128818A1 - Composé ayant une structure cyclique du triphénylène et un groupe pyridylique substitué, et élément électroluminescent organique - Google Patents

Composé ayant une structure cyclique du triphénylène et un groupe pyridylique substitué, et élément électroluminescent organique Download PDF

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WO2013128818A1
WO2013128818A1 PCT/JP2013/000787 JP2013000787W WO2013128818A1 WO 2013128818 A1 WO2013128818 A1 WO 2013128818A1 JP 2013000787 W JP2013000787 W JP 2013000787W WO 2013128818 A1 WO2013128818 A1 WO 2013128818A1
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substituted
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group
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安達　千波矢
和法 富樫
雄太 相良
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Kyushu University NUC
Hodogaya Chemical Co Ltd
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Kyushu University NUC
Hodogaya Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K50/16—Electron transporting 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers

Definitions

  • the present invention relates to a compound suitable for an organic electroluminescence element (hereinafter abbreviated as an organic EL element) which is a self-luminous element suitable for various display devices and the element, and more specifically, a pyridyl having a substituent.
  • an organic EL element an organic electroluminescence element
  • the present invention relates to a compound having a group and a triphenylene ring structure, and an organic EL device using the compound.
  • organic EL elements are self-luminous elements, they have been actively researched because they are brighter and more visible than liquid crystal elements and are capable of clear display.
  • Non-Patent Document 1 To date, many improvements have been made for practical application of organic EL devices, and various roles have been further subdivided, and sequentially on the substrate, anode, hole injection layer, hole transport layer, light emitting layer, electron transport High efficiency and durability are achieved by an electroluminescent element provided with a layer, an electron injection layer, and a cathode (see, for example, Non-Patent Document 1).
  • Non-Patent Document 2 the use of triplet excitons has been attempted for the purpose of further improving the luminous efficiency, and the use of phosphorescent emitters has been studied (for example, see Non-Patent Document 2).
  • the light emitting layer can also be prepared by doping a charge transporting compound generally called a host material with a phosphor or a phosphorescent light emitter.
  • a charge transporting compound generally called a host material with a phosphor or a phosphorescent light emitter.
  • the light injected from both electrodes is recombined in the light emitting layer to obtain light emission.
  • the hole moving speed is faster than the electron moving speed, some of the holes pass through the light emitting layer. There is a problem of efficiency reduction due to passing through. Therefore, an electron transport material having a high electron moving speed is demanded.
  • Tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3 ), which is a typical luminescent material, is generally used as an electron transport material, but has a slow electron mobility and a work function of 5. Since it is 6 eV, it cannot be said that the hole blocking performance is sufficient.
  • a method for preventing a part of holes from passing through the light emitting layer and improving the probability of charge recombination in the light emitting layer is to insert a hole blocking layer.
  • a hole blocking material triazole derivatives (for example, refer to Patent Document 3), bathocuproine (hereinafter abbreviated as BCP), mixed ligand complexes of aluminum [aluminum (III) bis (2-methyl-8) -Quinolinato) -4-phenylphenolate (hereinafter abbreviated as BAlq)] (for example, see Non-Patent Document 2).
  • TAZ 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole
  • TAZ has a large work function of 6.6 eV and high hole blocking ability
  • an electron transporting hole blocking layer laminated on the cathode side of a fluorescent light emitting layer or phosphorescent light emitting layer produced by vacuum deposition or coating contributes to high efficiency of the organic EL element (see, for example, Non-Patent Document 3).
  • BCP also has a high work function of 6.7 eV and a high hole blocking ability, but its glass transition point (Tg) is as low as 83 ° C., so that the stability of the thin film is poor and it functions sufficiently as a hole blocking layer. I can't say that. Therefore, it has been proposed to use BAlq as a hole blocking layer as a measure for extending the lifetime of phosphorescent light emitting devices. In this device, although the life extension is improved, since the work function of BAlq is as small as 5.8 eV, the holes are not efficiently confined in the light emitting layer, and the efficiency is reduced as compared with the device using BCP. Seen, not enough.
  • JP-A-8-048656 Japanese Patent No. 3194657 Japanese Patent No. 2734341 International Publication No. 2003/060956
  • An object of the present invention is to provide an organic compound having characteristics excellent in electron injection / transport performance as a material for a low power consumption organic EL element, and further using this compound, a low power consumption organic EL element Is to provide.
  • the physical properties that the organic compound to be provided by the present invention should have include (1) good electron injection properties, (2) fast electron transfer speed, and (3) high molecular orientation. And (4) excellent heat resistance.
  • the physical characteristics that the organic EL element to be provided by the present invention should have include (1) high power efficiency, (2) low light emission starting voltage, and (3) low practical driving voltage. I can give you something.
  • the present inventors have high flatness, that is, good intermolecular packing in a thin film state can be expected, and the presence of abundant ⁇ electrons results in good electron transport properties.
  • the present invention is a compound having a pyridyl group having a substituent represented by the general formula (1) or (2) and a triphenylene ring structure.
  • R 1 to R 10 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • R 1 and A 2 may be the same or different and represent a monovalent group represented by the following structural formula (B).
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • 1 to 6 linear or branched alkyl groups substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • V, W, X, Y and Z represent a carbon atom or a nitrogen atom, and V, W, X, Y and Z are any one of 0 to 3 nitrogen atoms. In this case, the nitrogen atom is R 14 to R 18 are not substituted.
  • R 1 to R 9 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • R 1 to R 9 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • a 1 , A 2 , and A 3 may be the same or different and each represents a monovalent group represented by the structural formula (B).
  • organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, at least one layer of the organic layer is represented by the general formula (1) or the general formula (2).
  • An organic EL device comprising a pyridyl group having a group and a compound having a triphenylene ring structure.
  • Specific examples of the “alkyl group” in the “shaped alkyl group” include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, n-hexyl group and the like.
  • a linear or branched alkyl group having 1 to 6 carbon atoms having a substituent represented by R 1 to R 18 in the general formula (1), the general formula (2), or the structural formula (B)
  • substituent specifically, a deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 6 carbon atoms
  • substituted or unsubstituted aromatic heterocyclic group represented by R 11 to R 18
  • a substituted or unsubstituted pyrimidyl group or a substituted or unsubstituted phenyl group is preferable, and the electron injection property is improved. Can be expected.
  • Specific examples of the “substituent” in the “polycyclic aromatic group” include a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a nitro group, a straight chain having 1 to 6 carbon atoms or Dialkyl substituted with a branched alkyl group, a cyclopentyl group, a cyclohexyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms Amino group, phenyl group, biphenylyl group, terphenylyl group, tetrakisphenyl group, sty
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom) 1 to 6 linear or branched alkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • R 11 to R 14 , R 16 and R 18 may be the same or different and each has a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group or substituent.
  • R 11 to R 15 and R 17 may be the same or different and each may have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group or substituent).
  • R 11 to R 13 , R 15 and R 17 may be the same or different and each has a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group or substituent.
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • 1 to 6 linear or branched alkyl groups substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • V, W, X, Y and Z represent a carbon atom or a nitrogen atom, and V, W, X, Y and Z are any one of 0 to 3 nitrogen atoms. In this case, the nitrogen atom is R 14 to R 18 are not substituted.
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • 1 to 6 linear or branched alkyl groups substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • V, W, X, Y and Z represent a carbon atom or a nitrogen atom, and V, W, X, Y and Z are any one of 0 to 3 nitrogen atoms. In this case, the nitrogen atom is R 14 to R 18 are not substituted.
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • 1 to 6 linear or branched alkyl groups substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • V, W, X, Y and Z represent a carbon atom or a nitrogen atom, and V, W, X, Y and Z are any one of 0 to 3 nitrogen atoms. In this case, the nitrogen atom is R 14 to R 18 are not substituted.
  • R 11 to R 18 may be the same or different and each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or an optionally substituted carbon atom
  • 1 to 6 linear or branched alkyl groups substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, or substituted or unsubstituted condensed polycyclic aromatic groups.
  • V, W, X, Y and Z represent a carbon atom or a nitrogen atom, and V, W, X, Y and Z are any one of 0 to 3 nitrogen atoms. In this case, the nitrogen atom is R 14 to R 18 are not substituted.
  • the compound represented by the general formula (1) or the general formula (2) of the present invention which has a pyridyl group having a substituent and a triphenylene ring structure, is a novel compound, and moves electrons faster than conventional electron transport materials. Thus, a stable thin film state can be maintained, the luminous efficiency is improved, and the drive voltage is lowered.
  • the compound having a pyridyl group having a substituent and a triphenylene ring structure represented by the general formula (1) or the general formula (2) of the present invention is a constituent material of an electron injection layer and / or an electron transport layer of an organic EL device.
  • the compound having a pyridyl group having a substituent and a triphenylene ring structure represented by the general formula (1) or the general formula (2) of the present invention can also be used as a constituent material of a light emitting layer of an organic EL element.
  • the material of the present invention which has excellent electron transport properties and a wide band gap, is used as a host material for a light emitting layer, and a phosphor or phosphorescent light emitter called a dopant is supported to form a light emitting layer. By using it, the drive voltage is lowered, and an organic EL element with improved luminous efficiency can be realized.
  • the organic EL device of the present invention uses a compound having a pyridyl group having a substituent and a triphenylene ring structure, in which the electron movement is faster than the conventional electron transport material and the thin film state is stable, it is highly efficient and highly durable. It became possible to realize sex.
  • the compound having a pyridyl group having a substituent and a triphenylene ring structure of the present invention has a fast electron movement and a stable thin film state, it is a constituent material of an electron injection layer, an electron transport layer, or a light emitting layer of an organic EL device.
  • An organic EL device manufactured using a compound having a substituted pyridyl group and a triphenylene ring structure can improve the light emission efficiency and drive voltage, and can improve durability.
  • FIG. 2 is a 1 H-NMR chart of the compound of Example 2 of the present invention (Compound 4).
  • FIG. FIG. 5 is a diagram showing EL device configurations of Examples 5 to 6 and Comparative Example 1 of the present invention.
  • the compound having a pyridyl group having a substituent and a triphenylene ring structure according to the present invention is a novel compound, and these compounds can be synthesized, for example, as follows.
  • the corresponding boronate ester form is synthesized by subjecting the corresponding triphenylene compound dihalide to boronic esterification with bis (pinacolato) diboron or the like (see, for example, Non-Patent Document 5), and further, the corresponding boron.
  • a compound having a pyridyl group having a substituent and a triphenylene ring structure by performing a cross-coupling reaction such as Suzuki coupling between an acid ester and a halogenopyridine having various substituents (see, for example, Non-Patent Document 6) Can be synthesized.
  • boronic acid ester forms of pyridine having various substituents are synthesized by subjecting halogenopyridines having various substituents to boronic acid esterification with bis (pinacolato) diboron or the like.
  • a compound having a pyridyl group having a substituent and a triphenylene ring structure can be synthesized by performing a cross-coupling reaction such as Suzuki coupling between a boronic acid ester of pyridine having a pyridine group and a dihalide of a corresponding triphenylene compound. .
  • melting point is an index of vapor deposition
  • glass transition point (Tg) is an index of stability in a thin film state
  • work function is an index of hole blocking ability
  • Tg Melting point and glass transition point (Tg) were measured with a high sensitivity differential scanning calorimeter (Bruker AXS, DSC3100S) using powder.
  • the work function was measured using a photoelectron spectrometer (AC-3, manufactured by Riken Keiki Co., Ltd.) in the atmosphere after forming a 100 nm thin film on the ITO substrate.
  • an anode, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode are sequentially formed on the substrate, and the anode and the hole transport layer Examples include those having a hole injection layer between them, those having an electron injection layer between the electron transport layer and the cathode, and those having an electron blocking layer between the light emitting layer and the hole transport layer.
  • several organic layers can be omitted.
  • a structure having an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode sequentially on a substrate can be used. .
  • the light emitting layer, the hole transport layer, and the electron transport layer may have a structure in which two or more layers are laminated.
  • an electrode material having a large work function such as ITO or gold is used.
  • a hole injection layer of the organic EL device of the present invention in addition to a porphyrin compound typified by copper phthalocyanine, a starburst type triphenylamine derivative, three or more triphenylamine structures in the molecule, single bond or heteroatom
  • triphenylamine trimers and tetramers such as arylamine compounds having a structure linked by a divalent group not containing an acceptor, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials Can do.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (hereinafter abbreviated as TPD) or N, N′-diphenyl-N , N′-di ( ⁇ -naphthyl) -benzidine (hereinafter abbreviated as NPD)
  • TPD N, N′-diphenyl-N , N′-di ( ⁇ -naphthyl) -benzidine
  • NPD benzidine derivatives such as N, N, N ′, N′-tetrabiphenylylbenzidine, 1,1-bis [(di-4 -Tolylamino) phenyl] cyclohexane
  • TAPC 1,1-bis [(di-4 -Tolylamino) phenyl] cyclohexane
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS poly (styrene sulfonate)
  • a material that is usually used for the layer is further P-doped with trisbromophenylamine hexachloroantimony or the like, or a TPD structure having a partial structure. Molecular compounds and the like can be used.
  • TCTA 4,4 ′, 4 ′′ -tri (N-carbazolyl) triphenylamine
  • TCTA 9,9-bis [4- (carbazole- 9-yl) phenyl] fluorene
  • mCP 1,3-bis (carbazol-9-yl) benzene
  • Ad 2,2-bis (4-carbazol-9-ylphenyl) adamantane
  • Carbazole derivatives such as 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene
  • a compound having an electron blocking action such as a compound having a triarylamine structure can be used.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • various metal complexes and anthracene derivatives in addition to metal complexes of quinolinol derivatives including Alq 3 Bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like can be used.
  • the light-emitting layer may be composed of a host material and a dopant material, and in addition to the light-emitting material, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used as the host material.
  • a dopant material quinacridone, coumarin, rubrene, perylene, and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • a phosphorescent light emitting material can be used as the light emitting material.
  • a phosphorescent emitter of a metal complex such as iridium or platinum can be used.
  • Green phosphorescent emitters such as Ir (ppy) 3
  • blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters
  • Btp 2 Ir (acac) are used as the host material.
  • carbazole derivatives such as 4,4′-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP), TCTA, mCP, and the like can be used.
  • UGH2 p-bis (triphenylsilyl) benzene
  • TPBI 2,2 ′, 2 ′′-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole
  • the phosphorescent light-emitting material into the host material by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light-emitting layer.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • phenanthroline derivatives such as bathocuproin (hereinafter abbreviated as BCP), and quinolinol such as BAlq
  • BCP bathocuproin
  • quinolinol such as BAlq
  • various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having a hole blocking action can be used. These materials may also serve as the material for the electron transport layer.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • the electron transport layer of the organic EL device of the present invention in addition to the substituted bipyridyl group and the compound having a triphenylene ring structure of the present invention, in addition to metal complexes of quinolinol derivatives including Alq 3 and BAlq, various metal complexes, Triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like can be used.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • an alkali metal salt such as lithium fluoride and cesium fluoride
  • an alkaline earth such as magnesium fluoride
  • metal oxides such as metal salts and aluminum oxide can be used, this can be omitted in the preferred selection of the electron transport layer and the cathode.
  • a material usually used for the layer and further doped with a metal such as cesium can be used.
  • an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as the electrode material.
  • the crude product was purified by column chromatography (carrier: silica gel, eluent: n-hexane) and white powder of 3,3 ′′ -bis (trimethylsilyl) -1,1 ′: 2 ′, 1 ′′ -terphenyl 23.3 g (84% yield) was obtained.
  • Chloroform 200 ml, n-hexane 600 ml, and silica gel 36.6 g were added to the crude product, followed by adsorption purification, followed by washing with chloroform to obtain 5.5 g of light yellow powder of 2,7-dibromotriphenylene (yield 46%).
  • Example 3 About the compound of this invention, melting
  • the glass transition point of the compound of the present invention was not observed. This indicates that the thin film state is stable in the compound of the present invention.
  • Example 4 Using the compound of the present invention, a 50 nm-thick deposited film was formed on an ITO substrate, and the work function was measured with an atmospheric photoelectron spectrometer (AC-3 type, manufactured by Riken Keiki Co., Ltd.). Work Function Compound of Invention Example 1 6.10 eV Compound of Example 2 of the present invention 6.20 eV
  • the compound of the present invention has a value deeper than the work function 5.4 eV of a general hole transport material such as NPD or TPD, and has a large hole blocking ability.
  • the organic EL element has a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and an electron injection layer 6 on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2.
  • the cathode (silver electrode) 7 was deposited in this order.
  • the glass substrate 1 on which ITO having a thickness of 100 nm was formed was washed with an organic solvent, and then the surface was washed by UV ozone treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less. Subsequently, NPD was formed as a hole transport layer 3 so as to cover the transparent anode 2 so as to have a film thickness of 50 nm at a deposition rate of 2 ⁇ / s. On this hole transport layer 3, Alq 3 was formed as the light emitting layer 4 so as to have a film thickness of 20 nm at a deposition rate of 2 ⁇ / s.
  • the compound of Example 1 of the present invention (Compound 3) was formed as an electron transport layer 5 so as to have a film thickness of 30 nm at a deposition rate of 2 ⁇ / s.
  • a magnesium silver alloy was formed as the electron injection layer 6 so as to have a film thickness of 100 nm at a deposition rate of 3.3 ⁇ / s.
  • silver was deposited to a thickness of 10 nm to form the cathode 7.
  • the characteristic measurement was performed at normal temperature in air
  • Example 6 An organic EL device was produced under the same conditions as in Example 5 by replacing the material of the electron transport layer 5 in Example 5 with the compound of Example 2 of the present invention (Compound 4). About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • Example 1 For comparison, instead of the material of the electron transport layer 5 in Example 5 to Alq 3, to produce an organic EL element under the same conditions as in Example 5. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • the driving voltage at a current density of 10 mA / cm 2 is 4.20 V in Example 5 and Example 6 as large as 5.70 V in Comparative Example 1 using Alq 3. The voltage was lowered. Furthermore, all of luminance, light emission efficiency, and power efficiency at a current density of 10 mA / cm 2 were greatly improved.
  • the organic EL device using the pyridyl group having a substituent of the present invention and the compound having a triphenylene ring structure is a device using Alq 3 used as a general electron transport material. It was found that a large improvement in power efficiency and a significant reduction in practical driving voltage can be achieved as compared with the above.
  • the organic EL device using the pyridyl group having a substituent and the compound having a triphenylene ring structure according to the present invention has a remarkable decrease in driving voltage, so that the compound having the substituted pyridyl group and the triphenylene ring structure according to the present invention can be used.
  • the speed of electron transfer is predicted to be higher in each stage than Alq 3 which is a general electron transport material.
  • the compound having a substituent having a pyridyl group and a triphenylene ring structure of the present invention is excellent as a compound for an organic EL device because it has good electron injection / transport performance and a stable thin film state.
  • an organic EL element using the compound, high efficiency can be obtained, practical driving voltage can be lowered, and durability can be improved. For example, it has become possible to develop home appliances and lighting.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne un composé organique qui a d'excellentes caractéristiques de performance d'injection/de transport d'électrons et qui sert de matériau pour un élément organique électroluminescent à faible consommation de puissance et un élément organique électroluminescent à faible consommation d'énergie utilisant ce composé. Le composé ayant une structure cyclique de triphénylène et un groupe pyridyle avec un groupe substituant représenté par la formule générale (1) ou (2), et un élément électroluminescent organique ayant deux électrodes et une ou plusieurs couches organiques disposées en sandwich entre elles, l'élément électroluminescent organique étant caractérisé en ce que ledit composé est utilisé comme matériau de constitution pour une ou plusieurs couches organiques.
PCT/JP2013/000787 2012-02-28 2013-02-14 Composé ayant une structure cyclique du triphénylène et un groupe pyridylique substitué, et élément électroluminescent organique Ceased WO2013128818A1 (fr)

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JP2017191661A (ja) * 2016-04-11 2017-10-19 出光興産株式会社 有機エレクトロルミネッセンス素子
JP2019091748A (ja) * 2017-11-13 2019-06-13 東ソー株式会社 ジナフトテトラフェニレン化合物を含む有機エレクトロルミネッセンス素子

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