WO2014024447A1 - Composé ayant une structure de noyau triphénylène et élément électroluminescent organique - Google Patents

Composé ayant une structure de noyau triphénylène et élément électroluminescent organique Download PDF

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WO2014024447A1
WO2014024447A1 PCT/JP2013/004684 JP2013004684W WO2014024447A1 WO 2014024447 A1 WO2014024447 A1 WO 2014024447A1 JP 2013004684 W JP2013004684 W JP 2013004684W WO 2014024447 A1 WO2014024447 A1 WO 2014024447A1
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group
compound
substituted
atom
light emitting
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安達　千波矢
和法 富樫
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保土谷化学工業株式会社
国立大学法人九州大学
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    • 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
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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Definitions

  • the present invention relates to a compound suitable for an organic electroluminescence element which is a self-luminous element suitable for various display devices and the element, and more specifically, a compound having a triphenylene ring structure, and an organic electroluminescence using the compound. It relates to an element.
  • organic electroluminescence elements are self-luminous elements, they have been actively researched because they are brighter and more visible than liquid crystal elements and can display clearly.
  • CBP 4,4′-di (N-carbazolyl) biphenyl
  • CBP has a low glass transition point (Tg) as low as 62 ° C. and strong crystallinity, so that it has poor stability in a thin film state. Therefore, satisfactory device characteristics have not been obtained in scenes where heat resistance is required, such as high luminance light emission.
  • the excited triplet level of the host compound is higher than the excited triplet level of the phosphorescent emitter. It has become clear that it must be high.
  • FIrpic which is a blue phosphorescent light emitting material represented by the following formula
  • the external quantum efficiency of the phosphorescent light emitting element remains at about 6%. This is because the excited triplet level of FIrpic is 2.67 eV, whereas the excited triplet level of CBP is as low as 2.57 eV, so that confinement of triplet excitons by FIrpic is insufficient with CBP. It was considered. This is demonstrated by the fact that the photoluminescence intensity of a thin film in which FIrpic is doped into CBP shows temperature dependence (see, for example, Non-Patent Document 3).
  • mCP 1,3-bis (carbazol-9-yl) benzene
  • Non-Patent Document 4 when a host compound having a higher excited triplet level is studied, when an iridium complex is doped into an electron transporting or bipolar transporting host compound, high luminous efficiency can be obtained (for example, Non-Patent Document 4).
  • An object of the present invention is to provide a host compound of a light emitting layer having a high excited triplet level and capable of completely confining triplet excitons of a phosphorescent emitter as a material for a highly efficient organic electroluminescence device. Furthermore, another object of the present invention is to provide a high-efficiency, high-brightness organic electroluminescence device using this compound.
  • the physical properties that the organic compound to be provided by the present invention should have include (1) high excitation triplet level, (2) bipolar transportability, and (3) stable thin film state. I can give you.
  • physical properties to be provided by the organic electroluminescence device to be provided by the present invention include (1) high luminous efficiency and (2) low practical driving voltage.
  • the present inventors designed a compound using the energy level as an index, paying attention to the possibility that the triphenylene ring, dibenzofuran ring and dibenzothiophene ring have a high excited triplet level.
  • the energy level of the compound was confirmed by actually synthesizing and actually measuring the work function, and a compound having a novel triphenylene ring structure having characteristics suitable for a phosphorescent light emitting device was found.
  • various organic electroluminescence devices were prototyped using the compound, and the characteristics of the devices were evaluated. As a result, the present invention was completed.
  • the present invention is a compound having a triphenylene ring structure represented by the general formula (1).
  • R 1 to R 6 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 a carbon atom which may have a substituent
  • 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
  • a 1 to A 6 may be the same or different and each represents a substituted or unsubstituted aromatic heterocyclic group.
  • this invention is a compound which has the triphenylene ring structure of the said 1) description represented by the following general formula (1 ').
  • R 1 to R 6 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 a carbon atom which may have a substituent
  • 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
  • a 1 to A 6 may be the same or different and each represents a substituted or unsubstituted aromatic heterocyclic group.
  • a 1 ⁇ A 6 are represented by a monovalent group represented by the following structural formula (B), being a compound having a triphenylene ring structure of the above 1), wherein .
  • R 7 to R 11 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 group, optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group , A substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, V, W, X, Y, Z represents a carbon atom or a nitrogen atom, and V, W, X, (It is assumed that one to three of Y and Z are nitrogen atoms, and the nitrogen atom in this case does not have a substituent of R 7 to R 11. )
  • this invention is a compound which has a triphenylene ring structure of said 3) description in which any one of V, W, X, Y, and Z is a nitrogen atom in the said structural formula (B).
  • this invention is a compound which has a triphenylene ring structure of said 3) description in which any two of V, W, X, Y, and Z are nitrogen atoms in the said structural formula (B).
  • this invention is a compound which has a triphenylene ring structure of said 3) description in which any three of V, W, X, Y, and Z are nitrogen atoms in the said structural formula (B).
  • the organic electroluminescence device having a pair of electrodes and at least one organic layer sandwiched therebetween, at least one of the organic layers has a triphenylene ring structure represented by the general formula (1). It is an organic electroluminescent element containing the compound which has.
  • the organic layer described above is a hole blocking layer
  • the compound having a triphenylene ring structure represented by the general formula (1) includes at least one constituent material in the hole blocking layer.
  • the organic layer described above is a light emitting layer, and the compound having a triphenylene ring structure represented by the general formula (1) is used as at least one constituent material in the light emitting layer.
  • the present invention is characterized in that the organic layer described above is a light emitting layer, and a compound having a triphenylene ring structure represented by the general formula (1) is used as a host material of the light emitting layer.
  • the present invention provides an organic electroluminescent device having a light emitting layer containing a phosphorescent light emitting material and at least one organic layer sandwiched between a pair of electrodes and represented by the general formula (1).
  • this invention is an organic electroluminescent element of said 11) description whose said phosphorescent luminescent material is a metal complex containing iridium or platinum.
  • this invention is an organic electroluminescent element of said 11) description whose above-mentioned phosphorescent luminescent material is a green luminescent material.
  • aromatic heterocyclic group in the “substituted or unsubstituted aromatic heterocyclic group” represented by A 1 to A 6 in the general formula (1) and general formula (1 ′), specifically, Pyridyl group, bipyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, isothiazolyl group, isoxazolyl group, quinolyl group, isoquinolyl group Quinoxalyl group, pteridinyl group, benzofuranyl group, benzothienyl group, indolyl group, isoindolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, carb
  • a 1 to A 6 in the general formula (1) and general formula (1 ′) are pyridyl group, bipyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, oxazolyl group.
  • substituted aromatic heterocyclic group represented by A 1 to A 6 in the general formula (1) and general formula (1 ′)
  • substituents include a deuterium atom and a fluorine atom. , Chlorine atom, cyano group, trifluoromethyl group, nitro group, linear or branched alkyl group having 1 to 6 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched group having 1 to 6 carbon atoms Alkyloxy group, dialkylamino group substituted by linear or branched alkyl group having 1 to 6 carbon atoms, phenyl group, biphenylyl group, terphenylyl group, tetrakisphenyl group, styryl group, naphthyl group, fluorenyl Group, phenanthryl group, indenyl group, pyrenyl group, pyridyl group, bipyridyl group
  • substituents may be further substituted by the above-exemplified substituents.
  • the “substituent” in the “substituted aromatic heterocyclic group” represented by A 1 to A 6 in the general formula (1) or general formula (1 ′) is the nitrogen-containing aromatic heterocyclic group exemplified above. Is preferred.
  • alkyl group in the “branched alkyl group”, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Examples thereof include an isopentyl group, a neopentyl group, and an n-hexyl group.
  • substituent specifically, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a nitro group, a cyclopentyl group, a cyclohexyl group, a straight chain having 1 to 6 carbon atoms Or a branched alkyloxy group, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, phenyl group, biphenylyl group, terphenylyl group, tetrakisphenyl group, styryl group, naphthyl group Fluorenyl group, phenanthryl group, indenyl group, pyr
  • aromatic hydrocarbon group “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group”
  • Substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group” or “substituted” represented by R 1 to R 11 in formula (1), formula (1 ′) and structural formula (B)
  • Specific examples of the “substituent” in the “condensed polycyclic aromatic group” include a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a nitro group, and a straight chain having 1 to 6 carbon atoms.
  • a branched alkyl group a cyclopentyl group, a cyclohexyl group, a linear or branched alkyloxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms
  • Dialkylamino phenyl, biphenylyl, terphenylyl, tetrakisphenyl, styryl, naphthyl, fluorenyl, phenanthryl, indenyl, pyrenyl, pyridyl Group, bipyridyl group, triazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, indolyl group, pyridoindolyl group, carbazolyl group, quinoxalyl group, pyrazolyl group, and these substituents can be further The substituents exemplified above may be substituted.
  • alkenyl group in the “linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” represented by R 7 to R 11 in the structural formula (B), Specific examples include vinyl group, allyl group, isopropenyl group, 2-butenyl group, isobutenyl group, 2-pentenyl group, isopentenyl group, 2-hexenyl group, 4-methyl-3-pentenyl group, and the like. And adjacent groups may be bonded to each other to form a ring.
  • the compound having a triphenylene ring structure represented by the general formula (1) or the general formula (1 ′) of the present invention is a novel compound, has an energy level suitable as a host compound of the light emitting layer, and has a triplet. Has excellent ability to confine excitons.
  • the compound having a triphenylene ring structure represented by the general formula (1) or general formula (1 ′) of the present invention is a light-emitting layer or a hole blocking layer of an organic electroluminescence element (hereinafter abbreviated as an organic EL element). It can be used as a constituent material of the layer.
  • an organic EL element organic electroluminescence element
  • the compound having a triphenylene ring structure of the present invention is useful as a compound for a hole blocking layer of an organic EL device or a host compound for a light emitting layer.
  • a compound for a hole blocking layer of an organic EL device or a host compound for a light emitting layer By producing an organic EL device using the compound, high efficiency, An organic EL element with a low driving voltage can be obtained.
  • FIG. 1 is a 1 H-NMR chart of the compound of Example 1 of the present invention (Compound 2).
  • FIG. 6 is a diagram showing EL element configurations of Example 4 and Comparative Example 1. 6 is a diagram showing an EL element configuration of Comparative Example 2.
  • FIG. 6 is a diagram showing an EL element configuration of Comparative Example 2.
  • the compound having a triphenylene ring structure of the present invention is a novel compound, and these compounds can be synthesized, for example, as follows.
  • a compound having a triphenylene ring structure is synthesized by performing a cross-coupling reaction such as Suzuki coupling between a boronic acid or boronic acid ester of an aromatic heterocyclic ring having various substituents and a halide of a corresponding triphenylene compound. be able to.
  • 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 energy level as a light-emitting host material.
  • 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 an atmospheric photoelectron spectrometer (AC-3 type, manufactured by Riken Keiki Co., Ltd.) by forming a 100 nm thin film on the ITO substrate.
  • an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, a cathode on the substrate sequentially, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, a cathode, Further, those having an electron injection layer between the electron transport layer and the cathode, and those having an exciton blocking layer on the anode side and / or the cathode side of the light emitting layer can be mentioned.
  • several organic layers can be omitted.
  • an anode, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode can be sequentially formed on the substrate.
  • Anode, hole transport layer, light emitting layer, electron transport layer, and cathode on the substrate sequentially.
  • 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 naphthalenediamine derivative, a starburst type triphenylamine derivative, a molecule having three or more triphenylamine structures, Triphenylamine trimers and tetramers such as arylamine compounds having a structure linked by a divalent group containing no bond or hetero atom, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymers Materials can 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.
  • N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (hereinafter referred to as “a”)
  • NPD N, N, N ′, N′-tetrabiphenylylbenzidine
  • Benzidine derivatives 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), various triphenylamine trimers and tetramers, and carbazole derivatives 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 coating type such as poly (3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT) / poly (styrene sulfonate) (hereinafter abbreviated as PSS) is used.
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS poly (styrene sulfonate)
  • These polymer materials can 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.
  • a material in which trisbromophenylamine hexachloroantimony is further P-doped to a material usually used in the layer, or a polymer having a TPD structure in its partial structure A compound or 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 such as metal complexes of quinolinol derivatives including tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3 ), anthracene derivatives, 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.
  • the host material is a compound having a triphenylene ring structure represented by the general formula (1) of the present invention, mCP, thiazole derivative, benzimidazole.
  • Derivatives polydialkylfluorene derivatives and the like can be used.
  • the dopant material quinacridone, coumarin, rubrene, anthracene, 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) and Ir (piq) 3 are used.
  • a carbazole derivative such as CBP, TCTA, or mCP can be used as a hole injecting / transporting host material.
  • p-bis (triphenylsilyl) benzene (hereinafter abbreviated as UGH2) or 2,2 ′, 2 ′′-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole) (hereinafter abbreviated as TPBI) and the like can be used.
  • UGH2 triphenylsilyl
  • TPBI 2,2 ′, 2 ′′-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole)
  • the doping of the phosphorescent light emitting material to the host material is preferably performed by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer.
  • thermally activated delayed fluorescent material As the thermally activated delayed fluorescent material, PIC-TRZ (see, for example, Non-Patent Document 1), compounds described in Japanese Patent Application No. 2012-088615, and the like can 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 element having a structure in which a light-emitting layer manufactured using a compound having a different work function as a host material is stacked adjacent to a light-emitting layer manufactured using the compound of the present invention can be manufactured (for example, non-patented). Reference 5).
  • phenanthroline derivatives such as bathocuproine (hereinafter abbreviated as BCP), aluminum (III)
  • BCP bathocuproine
  • BAlq metal complexes of quinolinol derivatives
  • oxazole derivatives such as bis (2-methyl-8-quinolinate) -4-phenylphenolate
  • BAlq metal complexes of quinolinol derivatives
  • oxazole derivatives such as bis (2-methyl-8-quinolinate) -4-phenylphenolate
  • triazole derivatives triazine derivatives
  • a compound 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.
  • various metal complexes triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline, in addition to metal complexes of quinolinol derivatives including Alq 3 and BAlq.
  • 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 metal salt such as magnesium fluoride
  • a metal oxide such as aluminum oxide
  • 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.
  • Example 2 About the compound of this invention, melting
  • Example 3 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 6.40 eV CBP 6.00eV
  • the compound of the present invention has a suitable energy level as compared with CBP generally used as a host compound in the light emitting layer.
  • the organic EL element has a hole transport layer 3, a light emitting layer 4, an electron transport layer 6, and an electron injection layer 7 on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2.
  • the cathode (aluminum electrode) 8 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, a compound (Tris-PCz) having the following structural formula was formed 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.
  • Example 1 For comparison, the material of the light-emitting layer 4 in Example 4 was changed from the compound of Example 1 (Compound 2) to CBP, and an organic EL device was produced under the same conditions as in Example 4. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • the organic EL element has a hole transport layer 3, a light emitting layer 4, a hole blocking layer 5, an electron transport layer on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2. 6, an electron injection layer 7 and a cathode (aluminum electrode) 8 were 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, as a hole transport layer 3 so as to cover the transparent anode 2, the compound of the structural formula (Tris-PCz) was formed to a film thickness of 50 nm at a deposition rate of 2 ⁇ / s.
  • BCP was formed as a hole blocking layer 5 so as to have a film thickness of 10 nm at a deposition rate of 2 ⁇ / s.
  • Alq 3 was formed as the electron transport layer 6 so as to have a film thickness of 30 nm at a deposition rate of 2 ⁇ / s.
  • lithium fluoride was formed as the electron injection layer 7 so as to have a film thickness of 1 nm at a deposition rate of 0.1 ⁇ / s. Finally, aluminum was deposited to a thickness of 100 nm to form the cathode 8. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • the maximum external quantum efficiency at a current density of 10 mA / cm 2 is 14.0% in Example 4 compared to 4.4% in Comparative Example 1 using CBP as the material of the light emitting layer. Increased efficiency. Furthermore, the maximum external quantum efficiency higher than 13.3% of the comparative example 2 which has the element structure which used CBP as a material of a light emitting layer, and added the hole-blocking layer using BCP was shown.
  • the organic EL device using the compound having a triphenylene ring structure of the present invention can achieve an improvement in external quantum efficiency as compared with CBP which is a general light-emitting host material. It was also found that the external quantum efficiency can be improved even when compared with an organic EL device having a device configuration in which a hole blocking layer using BCP, which is a general hole blocking layer material, is added.
  • the compound having a triphenylene ring structure of the present invention has a suitable energy level and has an ability to confine a suitable triplet energy.
  • the compound having a triphenylene ring structure of the present invention has a suitable energy level and has the ability to confine a suitable triplet energy, it can be used as a host compound and a hole blocking compound for a light-emitting layer. Are better. Moreover, the brightness

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

Abstract

L'invention concerne une matière destinée à être utilisée dans un élément électroluminescent organique à haut rendement, à savoir un composé hôte de couche d'émission de lumière qui a un niveau triplet excité élevé et est capable de sceller complètement des excitons triplets vis-à-vis d'un corps d'émission de lumière phosphorescente. Ledit composé a une structure de noyau triphénylène représentée par la formule générale (1). L'invention concerne également un élément électroluminescent organique à haut rendement, à luminance élevée, utilisant ledit composé. Ledit élément électroluminescent organique, qui a une paire d'électrodes et une ou plusieurs couches organiques prises en sandwich entre elles, est caractérisé en ce que le composé mentionné ci-dessus est utilisé comme matière constitutive pour au moins une couche organique.
PCT/JP2013/004684 2012-08-08 2013-08-02 Composé ayant une structure de noyau triphénylène et élément électroluminescent organique WO2014024447A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015029354A1 (fr) * 2013-08-27 2015-03-05 保土谷化学工業株式会社 Composé à structure cyclique triphénylène et élément électroluminescent organique
US10388888B2 (en) 2014-12-29 2019-08-20 University Court Of The University Of St Andrews Light emitting electrochemical cells and compounds
WO2022124365A1 (fr) * 2020-12-11 2022-06-16 日鉄ケミカル＆マテリアル株式会社 Dispositif électroluminescent organique
WO2022124366A1 (fr) * 2020-12-11 2022-06-16 日鉄ケミカル＆マテリアル株式会社 Élément électroluminescent organique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH118072A (ja) * 1996-12-09 1999-01-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2001094130A (ja) * 1999-09-21 2001-04-06 Fuji Photo Film Co Ltd 光電変換素子、太陽電池及び新規オリゴピロール化合物
JP2003045662A (ja) * 2001-08-01 2003-02-14 Konica Corp 有機エレクトロルミネッセンス素子及び表示装置
CN102532105A (zh) * 2010-12-17 2012-07-04 清华大学 一种含有吡啶基团的三亚苯类化合物及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH118072A (ja) * 1996-12-09 1999-01-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2001094130A (ja) * 1999-09-21 2001-04-06 Fuji Photo Film Co Ltd 光電変換素子、太陽電池及び新規オリゴピロール化合物
JP2003045662A (ja) * 2001-08-01 2003-02-14 Konica Corp 有機エレクトロルミネッセンス素子及び表示装置
CN102532105A (zh) * 2010-12-17 2012-07-04 清华大学 一种含有吡啶基团的三亚苯类化合物及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LUO,J. ET AL.: "Synthesis, physical properties and self-assembly of star-shaped oligothiophenes-substituted and fused triphenylenes", JOURNAL OF MATERIALS CHEMISTRY, vol. 20, no. 10, 2010, pages 1932 - 1941 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015029354A1 (fr) * 2013-08-27 2015-03-05 保土谷化学工業株式会社 Composé à structure cyclique triphénylène et élément électroluminescent organique
US10388888B2 (en) 2014-12-29 2019-08-20 University Court Of The University Of St Andrews Light emitting electrochemical cells and compounds
WO2022124365A1 (fr) * 2020-12-11 2022-06-16 日鉄ケミカル＆マテリアル株式会社 Dispositif électroluminescent organique
WO2022124366A1 (fr) * 2020-12-11 2022-06-16 日鉄ケミカル＆マテリアル株式会社 Élément électroluminescent organique

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