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WO2003065770A1 - Dispositif d'electroluminescence organique - Google Patents

Dispositif d'electroluminescence organique Download PDF

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WO2003065770A1
WO2003065770A1 PCT/JP2003/000870 JP0300870W WO03065770A1 WO 2003065770 A1 WO2003065770 A1 WO 2003065770A1 JP 0300870 W JP0300870 W JP 0300870W WO 03065770 A1 WO03065770 A1 WO 03065770A1
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group
emitting layer
polymer
light
layer
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PCT/JP2003/000870
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Japanese (ja)
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Toshihiro Ohnishi
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Sumitomo Chemical Company, Limited
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    • 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
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • 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
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds

Definitions

  • the present invention relates to an organic electroluminescent device having a hole injection layer and a light emitting layer (hereinafter sometimes referred to as an organic EL device).
  • Organic EL devices are devices that use low-molecular or high-molecular organic compounds as light-emitting materials. Compared with conventional inorganic electroluminescent devices, they emit light of many colors in addition to low-voltage driving and high brightness. Various studies have been conducted because of the characteristics that it can be obtained.
  • a light-emitting layer alone or a hole-transporting layer or an electron-transporting layer laminated on the light-emitting layer is used between electrodes.
  • it is adjacent to the anode. It is common to use a hole injection layer.
  • Materials used for the hole injection layer include copper phthalocyanine and aromatic amine oligomers formed by vacuum deposition, and conductive polymers formed by coating.
  • Japanese Patent Application Laid-Open No. 2000-91081 discloses Discloses an element in which a hole injection layer contains a polythiophene derivative (polyethylenedioxythiophene), which is a conductive polymer, and polystyrenesulfonic acid.
  • Japanese Patent Application Laid-Open No. 9-54979 discloses a device in which the hole injection layer contains polyaniline, which is a conductive high molecule, and camphorsulfonic acid.
  • An object of the present invention is to provide a long-life organic EL device having a hole injection layer and a light-emitting layer, and a hole injection material that can be used for the organic EL device and the like.
  • a long-life organic EL device can be obtained by including a super-strong acid in the hole-injecting layer, leading to the present invention.
  • the present invention relates to an organic electroluminescent device having a hole injection layer and a light emitting layer between an electrode comprising an anode and a cathode, wherein the hole injection layer contains a super strong acid.
  • the hole injection layer is a layer provided adjacent to the anode and has a function of improving the efficiency of hole injection from the anode.
  • the hole injection layer of the organic EL device of the present invention contains a super strong acid as an essential component.
  • the super-strong acid means an acid substantially stronger than 100% sulfuric acid (Revised 4th edition, Basic Handbook of Chemistry (II), p. 324, edited by The Chemical Society of Japan (Maruzen Co., Ltd.)).
  • the super-strong acid examples include low-molecular-weight materials in which one OH group of sulfuric acid is substituted with a negative group, such as C 1 S0 3 H, FS 3 H, CF 3 S 3 H, and C 2 F 5 S 0 3 H, C 4 F 9 S_ ⁇ 3 H, C 6 F 1 3 S_ ⁇ 3 H, a compound of hydrogen atoms of toluenesulfonic acid and Kanfu earth sulfonate was substituted with a fluorine atom.
  • the super-strong acid of the low molecular weight material also includes a mixture of the above and ruyl acid such as antimony pentafluoride and tantalum pentafluoride.
  • a polymer material a polymer having a super-strong acid group represented by one or more of the following general formulas (P-1), (P-2), (P-3) and CP-4) in a side chain is used. Molecules.
  • G is an alkylene group in which part or all of hydrogen is substituted with fluorine, an aralkylene group in which part or all of hydrogen is substituted with fluorine, or an arylene group in which part or all of hydrogen is substituted with fluorine.
  • G is an alkylene group in which part or all of hydrogen is substituted with fluorine, an aralkylene group in which part or all of hydrogen is substituted with fluorine, or an arylene group in which part or all of hydrogen is substituted with fluorine.
  • E is an alkyl group in which part or all of hydrogen is substituted with fluorine, an aralkyl group in which part or all of hydrogen is substituted with fluorine, or part or all of hydrogen is fluorine.
  • typical examples of these include hydrogen ions, sodium ions, alkali metal ions such as lithium ions, and the like. When used as a mixture with a hole injection material, hydrogen ions are preferred.
  • the alkylene group in G usually has about 1 to 6 carbon atoms
  • the aralkylene group usually has about 7 to 12 carbon atoms
  • the arylene group usually has about 6 to 10 carbon atoms.
  • G is preferably an alkylene group in which all of the hydrogens have been substituted with fluorine, an aralkylene group in which all of the hydrogens have been substituted with fluorine, or an arylene group in which all of the hydrogens have been substituted with fluorine.
  • G include, for example, a difluoromethylene group, a tetrafluoroethylene group, a propylene group having a hexafluoro group, a benzylene group having a hexafluoro group, a tetrafluorophenylene group, and a hexafluoronaphthylene group.
  • the alkyl group in E usually has about 1 to 6 carbon atoms
  • the aralkyl group usually has about 7 to 12 carbon atoms
  • the aryl group usually has about 6 to 10 carbon atoms.
  • E is preferably an alkyl group in which all of the hydrogen has been substituted with fluorine, an aralkyl group in which all of the hydrogen has been substituted with fluorine, or an aryl group in which all of the hydrogen has been substituted with fluorine.
  • E include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a heptafluorobenzyl group, a pentafluorophenyl group, a heptafluoronaphthyl group, and the like.
  • the main chain of the polymer is not particularly limited as long as it has a superacid group represented by -1), (P-2), (P-3) and 0P-4) in the side chain.
  • the main chain and the super-strong acid group of the polymer may be directly or an alkylene group having 1 to 20 carbon atoms, an alkylenedioxy group having 1 to 20 carbon atoms, — ⁇ —, —S—, _C ⁇ _, -S ⁇ 2 —, and a group consisting of repeating of the same or different ones thereof may be used, or a part of superacid group may be incorporated in the main chain.
  • the polymer may have a substituent in addition to the super-strong acid group as a side chain, for example, an alkyl group having 1 to 6 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, and a propyl group.
  • an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group
  • an aryl group such as an aralkyl group having 7 to 12 carbon atoms such as a benzyl group, a phenyl group, a naphthyl group, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • It may have a plurality of substituents, in which case they may be different. Among them, those substituted with a fluorine atom are preferably used.
  • Nafion registered trademark
  • 0P-5 a registered trademark
  • a polymer material is preferable, and a polymer containing a repeating structural unit represented by the above general formula (P-5) such as Naphion (registered trademark) is more preferable.
  • the polymerization degree of the super strong acid of the polymer material is preferably 5 or more, and 10 to 1
  • the proportion of the repeating structural unit having a super strong acid group is usually 1 mol% or more and 100 mol% or less, preferably 10 mol% or more and 100 mol% or less of the total of all the repeating structural units.
  • the hole injection layer of the organic EL device of the present invention contains a material (hole injection material) capable of imparting a function of improving hole injection efficiency (hole injection property), in addition to the super strong acid. Let it.
  • the hole injecting material examples include a material of the anode, a work function of [for example, a transparent electrode (indium tin oxide)] and a work function of the light emitting material used in the light emitting layer and the hole transporting material used in the hole transport layer.
  • a material of the anode a work function of [for example, a transparent electrode (indium tin oxide)] and a work function of the light emitting material used in the light emitting layer and the hole transporting material used in the hole transport layer.
  • Examples of the low-molecular-weight hole injection material include a pyrazoline derivative, an arylamine derivative, a stilbene derivative, and a triphenylenediamine derivative.
  • a hole transporting material described in Japanese Patent Application Laid-Open No. H10-203,878 can be suitably used.
  • Examples of the polymer-based hole injection material include a polymer having an aromatic amine group, a polymer having a carbazole group, and a conductive polymer.
  • polymer having an aromatic amine group and the polymer having a carbazole group include polyvinyl carbazole and its derivatives, and a polymer compound having an aromatic amine group in a main chain or a side chain.
  • the conductive polymer examples include polymers of thiophene and its derivatives (eg, poly-1-alkylthiophene, polyethylenedioxythiophene), polymers of pyrrole and its derivatives (eg, polypyrrolyl), and aniline and its derivatives.
  • Derivative polymer for example, polyaniline
  • polyphenylenevinylene and its derivatives polychenylenevinylene and its derivatives
  • polyacetylene and its derivatives polyphenylene and its derivatives
  • polyfluorene and its derivatives polyisothionaphthene and its derivatives Is exemplified.
  • polymers of thiophene and its derivatives preferred are polymers of thiophene and its derivatives, polymers of pyrrole and its derivatives, and polymers of polyaniline and its derivatives, and more preferred are those of aniline and its derivatives. It is a polymer of thiophene and its derivatives.
  • a polymer-based hole injection material is preferable, and a conductive polymer is more preferable.
  • the hole-injectable composition containing a super-strong acid of the present invention is a composition containing a super-strong acid and having a hole-injection property, and further containing a hole-injection material in addition to the super-strong acid.
  • Examples include those containing a super strong acid having a hole injecting property, such as a conductive polymer having a super strong acid group.
  • the hole injectable composition can be used for a hole injection layer such as an organic electroluminescence device.
  • the hole injectable composition is usually used as a thin film having a thickness of 1 nm to 30 nm in the hole injection layer.
  • the content of the super strong acid is preferably 0.1% by weight or more of the whole components constituting the hole injection layer, more preferably 0.5% by weight to 90% by weight, It is more preferably from 5% to 60% by weight, particularly preferably from 5% to 50% by weight, most preferably from 15% to 30% by weight.
  • the effect of the present invention tends to be reduced, and if it is too large, the hole injection ability tends to be insufficient.
  • the super strong acid has a hole injecting property like the above-mentioned conductive polymer having a super strong acid group
  • it is preferably 0.1% by weight to 100% by weight of the whole components constituting the hole injecting layer. More preferably, it is 10% by weight to 100% by weight.
  • the content of the hole injecting material may be appropriately determined with respect to the whole components constituting the hole injecting layer, and a preferable range is from 0.5% by weight to 98% by weight. It is from 5% by weight to 80% by weight, more preferably from 1% by weight to 60% by weight, and particularly preferably from 2% by weight to 40% by weight.
  • the hole injection layer may contain an acid which is as acidic as 100% sulfuric acid or an acid which is weaker than 100% sulfuric acid (acid weaker than super strong acid).
  • acids weaker than superacids include low molecular sulfonic acids such as toluenesulfonic acid and camphorsulfonic acid; high molecular sulfonic acids such as polystyrenesulfonic acid and polyvinylsulfonic acid; and inorganic acids such as sulfuric acid.
  • low molecular sulfonic acids such as toluenesulfonic acid and camphorsulfonic acid
  • high molecular sulfonic acids such as polystyrenesulfonic acid and polyvinylsulfonic acid
  • inorganic acids such as sulfuric acid.
  • high molecular sulfonic acids are preferable, and polystyrene sulfonic acid and polyvinyl sulfonic acid are more preferable.
  • the electric conductivity measured by mixing all the materials constituting the hole injection layer is preferably 10 17 S / cm or more and 10 3 S / cm or less. to small, 10- 5 S / cm or more 10 2 SZcm less it is more favorable preferred, more preferably 10_ 5 SZcm least 10 1 SZcm below.
  • the electric conductivity is generally adjusted by the amount of superacid, an acid weaker than superacid, and the like.
  • the hole injecting layer contains a material other than a super strong acid such as a hole injecting material or an acid weaker than the super strong acid
  • a material other than a super strong acid such as a hole injecting material or an acid weaker than the super strong acid
  • a conductive polymer when used as a hole injection material, a method of producing a conductive polymer by mixing a raw material monomer with a super strong acid in advance and polymerizing it; And a method of mixing a super strong acid or a solution thereof.
  • the material other than the super strong acid is a material insoluble in water, it can be mixed by bringing the aqueous solution of the super strong acid into contact with the material.
  • the light-emitting material contained in the light-emitting layer of the organic EL device of the present invention a low-molecular light-emitting material and a high-molecular light-emitting material can be used.
  • low-molecular light emitters include low-molecular fluorescent materials and singlet luminescent complexes.
  • Examples of the low-molecular fluorescent material include naphthalene or a derivative thereof, anthracene or a derivative thereof, perylene or a derivative thereof, polymethine-based, xanthen-based, coumarin-based, and cyanine-based dyes, and 8-hydroxyquinoline or the like.
  • a metal complex of a derivative, aromatic amine, tetraphenylcyclopentagen or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. Specifically, it is described in, for example, JP-A-57-51781 and JP-A-59-194393.
  • triplet luminescent complex examples include Ir (ppy) 3 having iridium as a central metal, PtOEP having platinum as a central metal: Eu (TTA) 3phen having europium as a central metal, and the like.
  • PtOEP Specifically, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (199 9), 75 (1), 4, Pro SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light- Emitting Materials and Devices IV), 119, J. Am. Cem. Soc, (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., ( 1998), 94 (1), 103, Syn.Met., (1999), 99 (2), 1361, Adv.Mater., (1999), 11 (10), 852
  • the polymer light-emitting material is not limited as long as it is a polymer that exhibits fluorescence (polymer fluorescent material) or a polymer that exhibits phosphorescence.
  • a polymer light-emitting material having a repeating unit represented by (2) is preferably used.
  • This molecular weight of the polymer light emitters et al has a number average molecular weight of 1 X 10 3 ⁇ 1 X 10 7 in terms of polystyrene, preferably 5X 10 3 ⁇ 1 X 10 7, more preferably
  • X 10 is a 4 ⁇ 5 X 10 6.
  • Alpha gamma iota a divalent group which have a Ariren group or a divalent heterocyclic group, or a metal complex structure. ⁇ is
  • R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. It is an integer of 0 to 2. When a plurality of R 2 and R 2 are present, they may be the same or different.
  • Ar 2 and Ar 3 each independently represent an arylene group or a divalent heterocyclic group.
  • R 3 represents an alkyl group, an aryl group, a monovalent heterocyclic group, a group represented by the following formula (3) or a group represented by the following formula (4).
  • m is an integer from 1 to 4. If the A r 3 Contact and R 3 is present in plural, it found that but it may also have Tsu different even Tsu same der.
  • R 3 is an aryl group or a monovalent heterocyclic group
  • the aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, and an aryl group.
  • Aryloxy group, aryl alkyl group, aryl alcohol It may have a substituent such as a xyl group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group.
  • Ar 4 is an arylene group or a divalent heterocyclic group.
  • R 4 represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, or a group represented by the following formula (4).
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.
  • p shows the integer of 0-2. When a plurality of R 5 and R 6 are present, they may be the same or different.
  • R 4 , R 5 and R 6 are an aryl group or a monovalent heterocyclic group
  • the aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, It may have a substituent such as a substituted amino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group and the like.
  • aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, It may have a substituent such as a substituted amino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group and
  • Ar 5 and Ar 6 are each independently an arylene group or a divalent heterocyclic group.
  • R 7 represents an alkyl group, aryl group or monovalent heterocyclic group.
  • R 8 represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.
  • q is an integer from 1 to 4.
  • R 7 and R 8 are an aryl group or a monovalent heterocyclic group
  • the aryl group, the monovalent heterocyclic group is an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, an aryl group, Aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, monovalent complex It may have a substituent such as a ring group.
  • R 2 , R 4 , R 5 , R 6 , and R 8 depend on the stability of the compound and the ease of production, but include an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, an aryloxy group, and an aryl group. It may be an alkyl group, an arylalkoxy group, an arylalkenyl group, or an arylalkynyl group.
  • ⁇ represents an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, a monovalent group. It may have a substituent such as a heterocyclic group.
  • the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.
  • the aromatic hydrocarbon includes those having a condensed aromatic polycyclic ring and those in which two or more independent benzene rings or condensed polycyclic rings are bonded directly or via a group such as vinylene.
  • the compound having a condensed aromatic polycyclic ring is preferably an aromatic compound in which the number of carbon atoms contained in the ring is usually about 6 to 60, and 2 to 5 benzene rings are condensed.
  • Specific examples include naphthene len, anthracene, phenanthrene, pyrene, perylene, naphthocene, pentacene, chrysene, coronene, and the like, with naphthalene and anthracene being preferred.
  • the compound preferably has at least one substituent.
  • Examples of a structure in which two or more independent benzene rings or condensed aromatic polycycles are bonded directly or via a group such as vinylene include a stilbene group and a distilbene group. Further, the benzene ring may have one or two groups selected from the group consisting of an alkoxy group, an aryl group substituted with an alkoxy group, an aryloxy group, and an arylalkoxy group.
  • a distilbene group is a group having an arylene group or a divalent heterocyclic group at the center, and having a vinylene group between two phenylene groups.
  • the arylene group examples include a phenylene group (for example, formulas 1 to 3 in the figure below), a naphthylene diphenyl group (formulas 4 to 13 in the figure below), and an anthracenylene group (formula in the figure below. 14-19), a biphenyl-2-yl group (formulas 20-25 in the following figure), a terphenyl-2-yl group (formulas 26-28 in the following figure), a condensed ring compound group (formulas 29-38 in the following figure), and the like.
  • a phenylene group, a biphenyl group, and a fluorene group are preferable.
  • the divalent heterocyclic group is an atomic group obtained by removing two hydrogen atoms from a heterocyclic compound.
  • a heterocyclic compound is a compound in which a single ring structure such as a 5-membered ring or a 6-membered ring contains not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring.
  • a single ring structure such as a 5-membered ring or a 6-membered ring contains not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring.
  • the condensed polycyclic heterocyclic compound is an organic compound having a cyclic structure in which two or more rings are condensed, in which not only carbon atoms but also oxygen, sulfur, nitrogen, A substance containing a hetero atom such as phosphorus or boron in the ring.
  • the number of carbon atoms contained in the ring is preferably about 6 to 60, and more preferably 6 to 30. Specific examples include quinoline, quinoxaline, acridine, phenanthamine, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, dibenzofuran, dibenzothiophene, and kylvazol. And sorbazole are preferred. From the viewpoint of solubility, the compound preferably has at least one substituent.
  • examples of the divalent heterocyclic group include the following.
  • Divalent heterocyclic groups containing nitrogen as hetero atoms pyridine-diyl group (Formulas 39-44 in the figure below), diazaphenylene group (Formulas 45-48 in the figure below), and quinolinedyl group (Formula 49 in the figure below) ⁇ 63), quinoxalinedyl group (Formulas 64 to 68 in the figure below), acridinediyl group (Formulas 69 to 72 in the figure below), bipyridyldiyl group (Formulas 73 to 75 in the figure below), and phenanthrolinedyl group (Formulas 76 to 76 78), etc.
  • a group with a fluorene structure containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom Formmulas 79 to 93 in the figure below).
  • the divalent group having a metal complex structure refers to a divalent group obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand.
  • the carbon number of the organic ligand of the metal complex having the organic ligand is usually about 4 to 60.
  • the organic ligand include 8-quinolinol and its derivatives, benzoquinolinol and its derivatives, 2-phenyl-pyridine and its derivatives, 2-phenyl-benzothiazol and its derivatives, and 2-phenyl Rubenzoxazole and its derivatives, porphyrin and its derivatives, and the like.
  • Examples of the central metal of the metal complex having an organic ligand include aluminum, zinc, beryllium, iridium, platinum, gold, europium, terbium, and the like.
  • Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a known phosphorescent material, and a so-called triplet luminescent complex.
  • Examples of the divalent group having a metal complex structure include the following (122 to 128).
  • R is each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a substituted amino group, a substituted silyl group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group And an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group and a cyano group.
  • one structural formula has a plurality of Rs, but they may be the same or different.
  • at least one of a plurality of Rs in one structural formula is other than a hydrogen atom, and that the shape of the repeating unit including a substituent has little symmetry. Is preferred.
  • one or more of R in one structural formula is a group containing a cyclic or branched alkyl group. A plurality of Rs may be linked to form a ring.
  • R when R is an alkyl group-containing substituent, the alkyl group may be linear, branched or cyclic, or a combination thereof.
  • the alkyl group is not linear, for example, an isoamyl group, hexyl group Echiru, 3,7-di-Mechiruokuchiru group, cyclohexyl group, 4 - including C x -C i 2 alkoxy Le alkyl cycloheteroalkyl are exemplified.
  • methyl group ⁇ methylene group of the alkyl group of the group containing the alkyl group may be replaced with a methyl group or methylene group substituted with a heteroatom or one or more fluorine atoms.
  • hetero atoms include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • R when R includes an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.
  • the alkyl group may be straight-chain, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl Groups such as pentyl, hexyl, octyl, 2-ethylhexyl, decyl, and 3,7-dimethyl A cyoctyl group is preferred.
  • the alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i —Butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, desiloxy, 3,7-dimethyloctyl And a phenyl group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.
  • the alkylthio group may be straight-chain, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methylthio, ethylthio, propylthio, i-propylthio, and butylthio groups I-butylthio, t-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethylo Examples thereof include a octylthio group and a laurylthio group, and a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethylo
  • the substituted silyl group is an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group is a silyl group substituted with one, two, or three groups selected from substituent groups. About 60.
  • trimethylsilyl group triethylsilyl group, tripropylsilyl group, tri_i-propylsilyl group, dimethyl-i-propylsilyl group, dimethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group , Lauryl dimethylsilyl group, phenyl C, ⁇ C, 2 alkyl silyl group, C, -C, 2 alkoxyphenyl- 2 alkylsilyl groups,.
  • the substituted amino group refers to an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group, and the number of carbon atoms is usually about 1 to 60. It is.
  • methylamino group dimethylamino group, ethylamino group, ethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t-butylamino group, Pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyloctylamino, laurylamino, cyclopentylamino Amino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, pyridyl group, ditrifluoromethylamin
  • the aryl group usually has about 6 to 60 carbon atoms.
  • the phenyl group and the (:!-Alkoxyphenyl group have 1 to 12 carbon atoms.
  • the aryloxy group usually has about 6 to 60 carbon atoms, and specifically includes a phenoxy group, a C! C alkoxyphenoxy group, a ( 12 -alkylphenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. etc. groups can be exemplified, 1-2 alkoxy phenoxyethanol group, C t-C, 2 alkylphenoxy group are preferable.
  • ⁇ reel alkyl group has a carbon number of usually 7 to about 60, specifically, phenyl - C [1-2 alkyl group, C, -C 12 alkoxy phenylalanine - ⁇ 12 ⁇ alkyl group, C, ⁇ C, 2 alkylphenyl—C i-C, 2 alkyl group, 1-naphthyl- (: 12 alkyl group, 2-naphthyl- ( 12 alkyl group, etc. are exemplified, and C i-C 12 alkoxyphenyl c, to c, 2 alkyl group, or two Arukirufue two Roux 1-2 alkyl group is preferred.
  • ⁇ reel alkoxy group has a carbon number of usually 7 to about 60, specifically, phenylene Lou C ⁇ -C 12 alkoxy group, - (- alkoxyphenyl-phenylalanine - 1-2 alkoxy group, C, -C , 2 alkylphenyl - -C, 2 alkoxy groups, 1 _ Na Fuchiru C, -C 12 alkoxy groups, 2-naphthyl - such as - (12 alkoxy groups and the like, - (: 12 alkoxy phenylalanine - (:! ⁇ (: societyAlkoxy group, ( ⁇ ⁇ (: 12 alkylphenyl (:. Alkoxy group is preferable.)
  • the arylamino group usually has about 6 to 60 carbon atoms, and includes a phenylamino group, a diphenylamino group, (:, to (
  • the aryl alkenyl group usually has about 8 to 60 carbon atoms.
  • the ⁇ reel alkynyl group has a carbon number of usually 8 to about 60, specifically, phenylene Lou C 2 -C 12 alkynyl group, ( ⁇ ⁇ (: 12 Arukokishifue two Lou C 2 -C 12 alkynyl groups, C [-C 12 Arukirufue two Lou C 2 -C 12 alkynyl group, 1 one-naphthyl - C 2 -C 12 alkynyl group, 2 one-naphthyl - such as C 2 -C I 2 alkynyl group and the like, ⁇ 1 ⁇ (: 12 alkoxyphenyl- (: 2 to 2 alkynyl groups, ⁇ 2 alkylphenyl C 2 to C 12 alkynyl groups are preferred.
  • the monovalent heterocyclic group the carbon number of usually 4 to about 60, specifically, Choi group, - (- 12 alkyl chain group, a pyrrolyl group, a furyl group, a pyridyl group, ⁇ 12 alkyl Preferred are a phenyl group, a phenyl group, a ⁇ ⁇ 12 alkyl phenyl group, a pyridyl group, and a ⁇ ⁇ ⁇ alkylpyridyl group.
  • a monovalent heterocyclic group is a heterocyclic compound obtained by removing one hydrogen atom from a heterocyclic compound. Refers to the remaining atomic groups.
  • substituents described above in the case of a substituent containing an alkyl chain, they may be linear, branched, or cyclic, or a combination thereof. If not linear, for example, isoamyl group, 2-Echiru hexyl group, 3,7-Jimechiruokuchiru group, cyclohexyl group, 4- ( ⁇ ⁇ 12 solubility alkylcycloalkyl such as cyclohexyl group and the like to. the light-emitting polymer solvent
  • a cyclic or branched alkyl chain is included.
  • the tips of two alkyl chains may be linked to form a ring.
  • some carbon atoms of the alkyl chain may be replaced by a group containing a hetero atom, and examples of the hetero atoms include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • substituents when an aryl group / heterocyclic group is included in a part thereof, they may further have one or more substituents.
  • K in the general formula (1) is an integer of 0 to 2, and is preferably 0 or 1.
  • M of the repeating unit represented by the general formula (2) is an integer from 1 to 4, and is preferably 1 or 2.
  • P in the general formula (3) is an integer of 0 to 2, and is preferably 0 or 1.
  • Q in the general formula (4) is an integer of 1 to 4, and is preferably 1 or 2.
  • R is exemplified by the same groups as described above.
  • the polymer light-emitting material containing at least one kind of the repeating unit represented by the general formula (1) and / or (2) contains a repeating unit other than the repeating unit represented by the general formula (1) or (2). You may go out.
  • the total of the repeating units represented by the formulas (1) and Z or the formula (2) is usually at least 50 mol% of all the repeating units.
  • Specific examples of the polymer light emitter containing one kind include, for example, WO 99/13692 published specification, WO 99/48160 published specification, GB 2340304 A, WO 00/53656 published specification, WO01Z19834 published specification, W ⁇ 00 Z 559 27 published specification, GB 2348316, WO 00/46321 published specification, WO 00/06665 published specification, W099Z54943 published specification, W ⁇ 99 Z 5 4385 published specification, US 5777070, WO 98/06773 Published specification, WO 97/05184 published specification, WO 00/35987 published specification, WO 00 53655 published specification, WO 01/34722 published specification, WO 99/245 26 published specification, WO 00/22027 published Description, WO 00/22026 published specification, W098Z 27136 published specification, US 573636, WO 98/21 262 published specification, US 5741921,
  • JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-8167, JP-A-10-324870, JP-A-10-114891, JP-A-9-1111233, JP-A-9-145478 and the like disclosed polyfluorene, derivatives and copolymers thereof, polyarylene, Examples thereof include derivatives and copolymers thereof, polyarylenevinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.
  • the light emitting layer of the organic EL device of the present invention is a polymer light emitting material
  • the light emitting layer further comprises a hole transporting material, an electron transporting material, a light emitting material other than the polymer light emitting material, (For example, a low molecular light emitter).
  • a method for producing a polymer light-emitting body such as a polymer light-emitting body including one type will be described.
  • a method described in JP-A-5-202355 can be used. That is, polymerization of a compound having an aldehyde group and a compound having a phosphonium base, or a compound having an aldehyde group and a phosphonium base by a Wittig reaction, and a compound having a vinyl group and a compound having a halogen group Of a compound having an aldehyde group and a compound having an alkylphosphonate group, or a compound having an aldehyde group and an alkylphosphonate group, or polymerization of a compound having a vinyl group and a halogen group by a Heck reaction.
  • the polymer light-emitting body does not have a vinylene group or a triple bond in the main chain
  • a method of polymerizing the corresponding monomer by a Suzuki coupling reaction for example, a method of polymerizing by a Grignard reaction, a method of Nii (0) how to polymerization by the catalyst, F eC 1 3 and a method of polymerization with an oxidizer, electrochemically methods oxidative polymerization or a method by decomposition of an intermediate polymer exemplified having a suitable leaving group, Is performed.
  • a compound having a plurality of reactive substituents which is a monomer, is dissolved in an organic solvent, if necessary, and is reacted using, for example, an alkali or a suitable catalyst at a temperature from the melting point of the organic solvent to the boiling point.
  • an alkali or a suitable catalyst for example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965.
  • Organic Reactions Vol. 27, pages 345-390, John Wiley & Sons, Inc., 1982, “Organic Synthesis” Syn theses)
  • the organic solvent varies depending on the compound used and the reaction, it is generally preferable that the solvent used be sufficiently deoxygenated and the reaction proceed in an inert atmosphere in order to suppress side reactions. In addition, it is preferable to similarly perform a dehydration treatment. However, this does not apply to the case of a two-phase reaction with water, such as the Su zuk i coupling reaction.
  • an alkali or a suitable catalyst is appropriately added. These may be selected according to the reaction used. It is preferable that the alkali or the catalyst be sufficiently soluble in the solvent used for the reaction.
  • the method of mixing the alkali or catalyst is reaction Add the alkali or catalyst solution slowly while stirring the solution under an inert atmosphere such as argon or nitrogen, or slowly add the reaction solution to the alkaline or catalyst solution. Is exemplified.
  • a polymer luminescent material When a polymer luminescent material is used for an organic EL device, its purity affects the performance of the device such as luminescence characteristics, so the monomer before polymerization is purified by a method such as distillation, sublimation purification, or recrystallization, and then polymerized. Is preferred. After the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification or fractionation by chromatography.
  • the organic EL device of the present invention has at least a hole injecting layer and a light emitting layer between an anode and a cathode, and the hole injecting layer contains a super strong acid.
  • the organic EL device of the present invention may have a hole transport layer or an electron transport layer in addition to the hole injection layer and the light emitting layer.
  • the hole transporting layer refers to a layer having a function of transporting holes
  • the electron transporting layer refers to a layer having a function of transporting electrons.
  • the electron transport layer and the hole transport layer are collectively called a charge transport layer.
  • the light-emitting layer, the hole transport layer, and the electron transport layer may be each independently used in two or more layers.
  • the hole transport layer and / or the electron transport layer may be two or more layers.
  • the organic EL device of the present invention in addition to a device having a hole injection layer in contact with the anode between electrodes composed of an anode and a cathode, and further having a light emitting layer (for example, a) below), for example, An EL element in which a hole transport layer is provided between the hole injection layer and the light emitting layer and adjacent to the light emitting layer (for example, b) below); An EL element provided with an electron transport layer adjacent thereto (for example, c) below); between the cathode and the light emitting layer, an electron transport layer provided adjacent to the light emitting layer; An EL device in which a hole transporting layer is provided adjacent to the light emitting layer (for example, d) below).
  • the thickness of the hole injection layer included in the organic EL device of the present invention is, for example, 1 nm to 300 nm, preferably 2 nm to 150 nm, and more preferably 10 nm to 100 nm. It is.
  • a method for forming the hole injection layer a method of forming a film from a solution or dispersion containing the above-described super strong acid and other materials as necessary, or a method of performing hole injection by performing electrochemical polymerization on the anode.
  • the formation of a layer is exemplified.
  • a method of doping with a super-strong acid after vapor deposition, or dispersing or dissolving a low-molecular-weight conjugate in a solution of a super-strong acid, and then applying the solution may be used.
  • Coating methods such as bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and ink jet printing can be used.
  • the thickness of the light emitting layer included in the organic EL device of the present invention may be different depending on the material used for the light emitting layer, and may be selected so that the driving voltage and the light emitting efficiency have appropriate values. It is necessary to have a thickness that does not cause pinholes. If the thickness is too large, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the light emitting layer is, for example, 1 nm to 1 nm, preferably 10 nm to 300 nm, and more preferably 20 nm to 150 nm.
  • the light-emitting layer can be formed, for example, by vacuum evaporation or film formation from a mixed solution with a polymer binder.
  • a film can be formed from a solution containing the light emitting material.
  • Solvents used for forming a luminescent material from a solution include those that dissolve a polymer light-emitting material or polymer binder having a repeating unit represented by general formulas (1) and Z or general formula (2).
  • chlorinated solvents such as chloroform, methylene chloride, and dichloroethane
  • ether solvents such as tetrahydrofuran
  • toluene, xylene, mesitylene, 1,2,3,4-tetramethylbenzene, n-- Aromatic solvents such as butylbenzene are more preferably used.
  • the optimal value of the thickness of the hole transport layer depends on the material used, and is selected so that the drive voltage and the luminous efficiency are appropriate.
  • the thickness should be at least such that pinholes do not occur. If the thickness is too large, the driving voltage of the device increases, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1, preferably 2 nm to 300 nm, and more preferably 5 nm to 200 nm.
  • the film thickness of the electron transporting layer may be different depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values. Good, but at least a thickness that does not generate pinholes is necessary. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 nm, preferably 2 nm to 300 nm, and more preferably 5 nm to 200 nm.
  • hole transporting material and the electron transporting material used in the organic EL device of the present invention known low molecular weight compounds and high molecular weight compounds can be used, but it is preferable to use high molecular weight compounds.
  • the hole-transporting material and the electron-transporting material include, as polymer compounds, WO099 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656 WO 01 Z 1983 4 published specification, WOO 0Z55927 published specification, GB 2348316, WO 0 0/46321 published specification, WO 00Z06665 published specification, WO 99/54 943 published specification, WO 99/54385 published specification, US 5777070, W 098/06773 published specification, WO 97 no 05184 published specification, WO 00/35987 published specification, WO00Z53655 published specification, WO 01/3472 2 published specification, W099Z24526 published specification, WO 00/22027 published specification WO 00/22026 published specification, WO 98/27136 published specification, US 573636, WO 98/21262 published specification, US 5741921, WO 97/09394 published specification, WO
  • hole transporting material of the polymer compound those described in the above-cited documents are more preferably used, but other polymer compounds such as polyvinyl carbazole or a derivative thereof, polysilane or Derivatives, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline or its derivatives, polythiophene or its derivatives, polypyrrole or its derivatives, or poly (2,5-Chenylenevinylene) or its derivatives are also used. It is possible.
  • Examples of the hole transporting material of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenylamine derivatives.
  • Examples of the electron transporting material of the high molecular weight compound include those described above. Also described Alternatively, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof may be used.
  • Examples of the low molecular weight compound electron-transporting materials include oxaziazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyano anthraquinodimethane or Examples thereof include a derivative thereof, a fluorenone derivative, diphenyldisocyanoethylene or a derivative thereof, a diphenoquinone derivative, and a metal of 8-hydroxyquinoline or a derivative thereof.
  • JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-209988, JP-A-37992, and 3-1 A hole transporting material, an electron transporting material, and the like described in Japanese Patent No. 52184 can be suitably used.
  • the hole transport layer and the electron transport layer are formed using a hole transport material and an electron transport material, respectively.
  • the hole-transporting material or the electron-transporting material is a low-molecular compound, it is exemplified by vacuum evaporation or film formation from a mixed solution with a polymer binder.
  • the solvent used in the solution is not particularly limited as long as the solvent can dissolve the material.
  • chlorinated solvents such as chloroform, methylene chloride and dichloroethane
  • aromatic compound solvents such as toluene, xylene, mesitylene, 1,2,3,4-tetramethylbenzene, n-butylbenzene, etc. Is preferably used.
  • the solvent used when forming the hole transport layer from a solution is not particularly limited as long as it dissolves the hole transport material and the polymer binder used as needed.
  • the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketones such as acetone and methyl ethyl ketone.
  • the solvent include ester solvents such as a solvent, ethyl acetate, butyl acetate, and ethyl cellosolve acetate. There is no particular limitation on the method of forming the electron transport layer.
  • a method of vacuum evaporation from powder or a method of forming a film from a solution or a molten state is used.
  • a method of forming a film from a solution or a molten state is exemplified.
  • a polymer binder may be used in combination.
  • the polymer binder to be mixed with the hole-transporting material or the electron-transporting material as required those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are preferably used.
  • the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, and poly (2,5-phenylenevinylene). Or a derivative thereof, polyacrylonitrile, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, or the like.
  • the organic EL device of the present invention may have a layer other than an anode, a cathode, a light emitting layer, a hole injection layer, a hole transport layer, and an electron transport layer.
  • Such a layer examples include an electron injection layer and an insulating layer having a thickness of 10 nm or less (a thin buffer layer provided at the interface between the charge transport layer and the light emitting layer to improve the adhesion of the interface and prevent mixing). ).
  • a layer provided adjacent to the cathode and having a function of improving the electron injection efficiency from the cathode and having an effect of lowering the driving voltage of the element is called an electron injection layer.
  • the order and number of layers to be stacked and the thickness of each layer can be appropriately used in consideration of luminous efficiency and device life.
  • the electron injection layer provided between the cathode and the light emitting layer or the electron transport layer, the work function of the cathode material and the electron affinity of the light emitting material contained in the light emitting layer or included in the electron transport layer
  • a layer containing a material having an electron affinity of an intermediate value with that of the electron transporting material is preferably used.
  • the layer is provided between the cathode and the light emitting layer and adjacent to the electrode.
  • the electric conductivity of the conductive polymer is 10 SZ Preferably cm to 1 0 is 3 SZ cm or less, in order to reduce the re one leakage current between light emitting pixels, more preferably at most 1 0- 5 SZ cm to 1 0 2 SZ cm, 1 0 _ 5 or SZ cm 1 0 1 SZ cm or less is more preferred.
  • the electrical conductivity of the conducting high content element to less 1 0- 5 SZ cm or 1 0 3 SZ cm, a suitable amount of ions are doped into the conducting polymer.
  • the type of ion to be doped is a cation, and examples thereof include a lithium ion, a sodium ion, a potassium ion, and a tetrabutylammonium ion.
  • the thickness of the electron injection layer is, for example, 1 nm to 150 nm, preferably 2 nm to 100 nm.
  • a method of forming a film from a solution is exemplified. It is only necessary to remove the solvent by drying after coating the solution, which is very advantageous in manufacturing.
  • the method for forming a film from a solution include spin coating, casting, microgravure coating, gravure coating, vacuum coating, roll coating, wire coating, dip coating, spray coating, and spray coating. Coating methods such as screen printing, flexographic printing, offset printing, and inkjet printing can be used.
  • An electron injection material that is dispersed in water or alcohol in the form of an emulsion can also be formed into a film by the same method as the solution.
  • a metal fluoride, a metal oxide, an organic insulating material, or the like is given, and a metal fluoride or a metal oxide such as an alkali metal or an alkaline earth metal is preferable. .
  • a vacuum evaporation method is illustrated as a method for forming the inorganic compound used for the insulating layer.
  • the substrate on which the organic EL device of the present invention is formed is not limited as long as it does not change when the electrodes and the layers of the device are formed, and examples thereof include glass, plastic, polymer films, and silicon substrates.
  • the opposite electrode is preferably transparent or translucent.
  • one of the anode and the cathode is transparent or translucent. Confuse.
  • the anode side is preferably transparent or translucent, but as the material of the anode, a conductive metal oxide, a translucent metal or the like is used.
  • a conductive glass such as NESA
  • ITO indium tin oxide
  • ITO indium tin oxide
  • Platinum, silver, copper, etc. are used, and IT ⁇ , indium zinc, oxide, and tin oxide are preferable.
  • an organic transparent conductive film such as polyaline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
  • the thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 zz rn, and preferably 20 nm to 1, More preferably, 50 ⁇ ⁇ ! 5500 nm.
  • Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • a material having a small work function is preferable.
  • metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc. , And alloys of two or more of them, or alloys of one or more of them with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, or tin, graph Aite or a graphite interlayer compound is used.
  • alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, etc. .
  • the cathode may have a laminated structure of two or more layers.
  • the thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, and is, for example, from 10 nm to 10 m, and preferably from 20 nm to 1 m. More preferably, it is 50 nm to 500 nm.
  • a vacuum evaporation method As a method for producing the cathode, a vacuum evaporation method, a sputtering method, a lamination method of thermocompression bonding of a metal thin film, and the like are used.
  • a protective layer for protecting the organic EL device may be provided.
  • a protective layer and Z or a protective cover it is preferable to attach a protective layer and Z or a protective cover to protect the device from the outside.
  • the protective layer polymer compounds, metal oxides, metal nitrides, metal nitrides, metal fluorides, metal borides, and the like can be used.
  • a glass plate, a plastic plate whose surface has been subjected to a low water permeability treatment, or the like can be used.
  • the production process can be performed.
  • a desiccant such as barium oxide or calcium oxide
  • the production process can be performed.
  • the organic EL device of the present invention can be used as a planar light source, a segment display, a dot matrix display, a backlight of a liquid crystal display, and the like.
  • a planar anode and a planar cathode may be arranged so as to overlap.
  • There are a method of emitting light a method of forming one or both of an anode and a cathode in a pattern.
  • both the anode and the cathode may be formed in a stripe shape and arranged orthogonally. How to apply different types of polymers with different emission colors By using a filter or a fluorescence conversion filter, partial color display and multi-color display can be achieved.
  • the dot matrix element may be passively driven or may be actively driven in combination with a thin film transistor using amorphous silicon / low temperature polysilicon.
  • These display elements can be used as display devices such as computers, televisions, mobile terminals, mobile phones, force navigation, and viewfinders of video cameras.
  • planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.
  • the average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using the pore form as a solvent.
  • the polystyrene reduced number average molecular weight of polymer compound 1 was 4.1 ⁇ 10 4 , and the weight average molecular weight was 1.2 ⁇ 10 5 .
  • the reaction was performed in an argon gas atmosphere. After the reaction, the solution was cooled and poured into a mixed solution of 25 ml of 25% aqueous ammonia, 150 ml of methanol and 150 ml of Z ion-exchanged water, and stirred for about 1 hour. Next, the formed precipitate was collected by filtration. After drying this precipitate, it was dissolved in toluene. The solution was filtered, after removal of the insoluble material, the solution was washed with IN HC 1 water and washed with 2% NH 3 water. After further washing with ion-exchanged water, the solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. The precipitate was dried under reduced pressure to obtain 1.6 g of a polymer (polymer compound 2).
  • the polystyrene equivalent weight average molecular weight of this polymer is 2.6 ⁇ 10 5
  • the number average molecular weight was 1.0 ⁇ 10 5 .
  • a dispersion solution of poly (ethylenedioxythiophene) Z polystyrene sulfonic acid (Bayer, Bay tron R P VP AI 4083) was placed on a glass substrate on which an ITO film with a thickness of 150 nm was attached by the sputtering method. ), A 5% solution of Nafion (registered trademark) (solution using a mixed solvent of lower alcohol and water manufactured by Aldrich) was added in a weight ratio of 95: 5, and mixed well. This mixed solution was formed into a film at 2000 rpm by spin coating. Then hot plate The above was dried at 200 ° C for 10 minutes.
  • the polymer compound 1 and the polymer conjugate 2 obtained above were mixed in a ratio of 3: 7, and dissolved in toluene. At this time, the solid content was adjusted to be about 1.5 wt%.
  • a film was formed at 2000 rpm by spin coating. After drying at 80 ° C for 1 hour under reduced pressure, about 4 nm of lithium fluoride, about 20 nm of calcium, and then about 50 nm of aluminum were deposited as a cathode to produce an organic EL device.
  • Contact vacuum such that, after reaching below 1 X 10- 4 P a, vapor deposition of a metal was initiated.
  • the device emitted blue light with a peak wavelength of 440 nm, and the light emission starting voltage at 1 cd / cm 2 was 3.IV.
  • the highest efficiency was 0.6 cdZA.
  • a device was prepared in the same manner as in Example 1, except that the mixing amount of Naphion (registered trademark) was changed to 90:10 by weight. This device emitted blue light with an emission peak of 44 Onm. The light-emission starting voltage at 1 cdZcm 2 was 3. IV. The highest efficiency was 0.68 cd / A.
  • a device was prepared in the same manner as in Example 1, except that the mixing amount of Naphion (registered trademark) was changed to 85:15 by weight. This device emitted blue light with an emission peak of 44 Onm. The light-emission starting voltage that resulted in 1 cdZcm 2 was 3. IV. The highest efficiency was 0.57 cd ZA.
  • Example 2 In the same manner as in Example 1 except that Nafion (registered trademark) was not added. A device was created. This device emitted blue light with an emission peak at 440 nm. The light-emission starting voltage at 1 cd / cm 2 was 3.2 V. The highest efficiency was 0.65 cd / A.
  • This organic EL element can be used as a liquid crystal or a curved or flat light source It can be preferably used for devices such as a dot matrix flat panel display.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un dispositif d'électroluminescence organique, caractérisé en ce qu'une couche d'injection à trou et une couche d'émission de lumière sont situées entres des électrodes composées d'une anode et d'une cathode, et en ce que la couche d'injection à trou contient un acide ultra-fort.
PCT/JP2003/000870 2002-01-31 2003-01-30 Dispositif d'electroluminescence organique WO2003065770A1 (fr)

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JP2002-23206 2002-01-31

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WO2003065770A1 true WO2003065770A1 (fr) 2003-08-07

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CN103339753A (zh) * 2011-01-26 2013-10-02 西门子公司 具有掺杂空穴导体层的有机半导体元件

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US9028932B2 (en) 2009-09-22 2015-05-12 Koninklijkle Philips N.V. Glass package for sealing a device, and system comprising glass package
JP5720671B2 (ja) * 2010-03-17 2015-05-20 コニカミノルタ株式会社 有機電子デバイスおよびその製造方法

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JPH1060425A (ja) * 1996-08-19 1998-03-03 Matsushita Electric Ind Co Ltd 有機エレクトロルミネセンス素子
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103339753A (zh) * 2011-01-26 2013-10-02 西门子公司 具有掺杂空穴导体层的有机半导体元件
US9263696B2 (en) 2011-01-26 2016-02-16 Siemens Aktiengesellschaft Organic semiconductor component comprising a doped hole conductor layer

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