WO2017104325A1 - Élément électroluminescent organique, procédé de fabrication d'élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage et matériau d'élément électroluminescent organique - Google Patents

Élément électroluminescent organique, procédé de fabrication d'élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage et matériau d'élément électroluminescent organique Download PDF

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WO2017104325A1
WO2017104325A1 PCT/JP2016/083530 JP2016083530W WO2017104325A1 WO 2017104325 A1 WO2017104325 A1 WO 2017104325A1 JP 2016083530 W JP2016083530 W JP 2016083530W WO 2017104325 A1 WO2017104325 A1 WO 2017104325A1
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organic
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compound
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麻由香 加羽澤
則子 安川
大津　信也
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コニカミノルタ株式会社
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Priority to CN201680073453.4A priority Critical patent/CN108369995B/zh
Priority to KR1020187013567A priority patent/KR102081011B1/ko
Priority to JP2017556424A priority patent/JP6696512B2/ja
Publication of WO2017104325A1 publication Critical patent/WO2017104325A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to an organic electroluminescence element, a method for producing an organic electroluminescence element, a display device, a lighting device, and an organic electroluminescence element material.
  • the present invention is an organic compound having a small emission ratio of components longer than the emission maximum wavelength, high emission efficiency, low driving voltage, long emission lifetime, small voltage increase during driving, and excellent temporal stability.
  • the present invention relates to an electroluminescence element, a method for manufacturing the element, a display device and a lighting device including the element, and an organic electroluminescence element material used for the element.
  • organic electroluminescence element (hereinafter also referred to as “organic EL element”) is an all-film thin film type composed of an organic thin film layer (single layer portion or multilayer portion) containing an organic light-emitting substance between an anode and a cathode. It is a solid element.
  • the organic EL element When a voltage is applied to the organic EL element, electrons are injected from the cathode into the organic thin film layer and holes are injected from the anode, and these are recombined in the light emitting layer (organic light emitting substance-containing layer) to generate excitons.
  • the organic EL element is a light-emitting element using light emission (fluorescence / phosphorescence) from these excitons, and is a technology expected as a next-generation flat display and illumination.
  • the phosphorescence emission method is a method having a very high potential.
  • a method for controlling the position of the emission center is significantly different from that using fluorescence emission.
  • a multilayer stacked device including a hole transport layer located on the anode side of the light emitting layer and an electron transport layer located on the cathode side of the light emitting layer, etc. adjacent to the light emitting layer, or a phosphor layer on the light emitting layer.
  • iridium complex-based heavy metal complexes have been studied as materials exhibiting phosphorescence at room temperature.
  • tris (2-phenylpyridine) iridium complex is widely known, but sufficient device performance such as a light emission lifetime has not been obtained.
  • iridium complexes having phenylimidazole ligands or carbene ligands are known. With these ligands, the emission wavelength of the luminescent material has been shortened to achieve a blue color, and further, the emission efficiency and the emission lifetime have been greatly improved.
  • Phenyltriazole is known as a ligand that emits blue light (see, for example, Patent Document 1). Although these compounds can achieve a short wavelength of the emission maximum wavelength, the emission lifetime and emission efficiency are not sufficient values.
  • a metal complex having a triazole ligand in which a ring bonded to a metal atom with a carbon atom has a condensed ring structure is known (for example, see Patent Documents 2 and 3).
  • a metal complex having a triazole ligand in which a ring coordinated to a metal atom has an alkyl group adjacent to the coordination atom is known (see, for example, Patent Document 4). Although these compounds have achieved a certain improvement in the light emission lifetime, there is room for further improvement.
  • the present invention has been made in view of the above-described problems and situations, and its solution is a small emission ratio of components longer than the emission maximum wavelength, high emission efficiency, low drive voltage, and long emission lifetime.
  • An organic electroluminescence element having a small voltage rise during driving and excellent stability over time, a method for producing the element, a display device and a lighting device including the element, and an organic electroluminescence element material used for the element Is to provide.
  • a metal complex having a 1H-1,2,4-triazole derivative as a ligand is bonded to a metal atom with a carbon atom.
  • the y-value measured using the CIE coordinates is suppressed while suppressing long-wave light emission, so that there is no trade-off between the shortening of the light emission maximum wavelength and the light emission efficiency / light emission lifetime of the device.
  • An organic EL element can be provided.
  • the present inventors include a compound having a structure represented by the following general formula (1), so that the emission ratio of components longer than the emission maximum wavelength is small, and the luminous efficiency is high.
  • the present inventors have found that an organic electroluminescence device having a low driving voltage, a long life, a small voltage increase during driving, and an excellent stability over time can be provided.
  • the problems according to the present invention are solved by the following means.
  • An organic electroluminescent device comprising an organic layer sandwiched between at least one pair of an anode and a cathode,
  • the organic layer is composed of at least one layer including a light emitting layer, and at least one of the organic layers contains a compound having a structure represented by the following general formula (1).
  • R is an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxy group, and a mercapto group.
  • Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group.
  • Alkynyl group aromatic hydrocarbon group, heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxy Carbonyl, sulfamoyl, ureido, acyl, acyloxy, amide, cal Moyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkylphosphino group, arylphosphino group, alkylphosphoryl group Represents any group selected from an arylphosphoryl group, an alkylthiophosphoryl group, and an arylthiophosphoryl group.
  • X 1 -L 1 -X 2 represents a bidentate ligand, and X 1 and X 2 each independently represents a carbon atom, a nitrogen atom or an oxygen atom.
  • L 1 represents an atomic group that forms a bidentate ligand together with X 1 and X 2 .
  • m represents an integer of 1 to 3
  • n represents an integer of 0 to 2
  • m + n is 3.
  • at least two of adjacent R 1 to R 4 are condensed to represent any one of the following general formulas (2) to (4). )
  • Y 1 to Y 4 each independently represents O, S, or N—R ′, and Y 5 or Y 6 represents CR ′′ or N.
  • each of the plurality of Rx independently represents R 1 to R 4 in the general formula (1); Represents an equivalent group, and * represents a bonding position with the structure represented by the general formula (1).
  • R, Ar, R 1 to R 4 , Y 1 , Z 1 to Z 4 , X 1 , X 2 , L 1 , m and n are the same as those in the general formula (1).
  • And (2) are the same as R, Ar, R 1 to R 4 , Y 1 , Z 1 to Z 4 , X 1 , X 2 , L 1 , m and n.
  • R represents an alkyl group or a cyano group.
  • Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a substituent at the 2-position, according to any one of items 1 to 4
  • the organic electroluminescent element of description is not limited to:
  • n 0, The organic electroluminescent element as described in any one of 1st term
  • the said light emitting layer contains the compound which has a structure represented by the said General formula (1), The organic electroluminescent element as described in any one of Claim 1-6 characterized by the above-mentioned.
  • the organic electroluminescent element manufacturing method characterized by forming the layer containing the compound which has a structure represented by the said General formula (1) among the said organic layers with a wet process.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 8.
  • An illuminating device comprising the organic electroluminescence element according to any one of items 1 to 8.
  • An organic electroluminescence device material comprising a compound having a structure represented by the following general formula (1).
  • R is an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxy group, and a mercapto group.
  • Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group.
  • Alkynyl group aromatic hydrocarbon group, heterocyclic group, aromatic heterocyclic group, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxy Carbonyl, sulfamoyl, ureido, acyl, acyloxy, amide, cal Moyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkylphosphino group, arylphosphino group, alkylphosphoryl group Represents any group selected from an arylphosphoryl group, an alkylthiophosphoryl group, and an arylthiophosphoryl group.
  • X 1 -L 1 -X 2 represents a bidentate ligand, and X 1 and X 2 each independently represents a carbon atom, a nitrogen atom or an oxygen atom.
  • L 1 represents an atomic group that forms a bidentate ligand together with X 1 and X 2 .
  • m represents an integer of 1 to 3
  • n represents an integer of 0 to 2
  • m + n is 3.
  • at least two of adjacent R 1 to R 4 are condensed to represent any one of the following general formulas (2) to (4). )
  • Y 1 ⁇ Y 4 are .R each independently, O, 'represent, Y 5 or Y 6 is that CR' S or N-R represents a 'or N 'Represents any group selected from an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, and R''represents a hydrogen atom, an alkyl group, a cycloalkyl group, Z 1 to Z 8 represent any group selected from an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, an arylsilyl group and an arylphosphoryl group.
  • each of the plurality of Rx independently represents R 1 to R 4 in the general formula (1); Represents an equivalent group, and * represents a bonding position with the structure represented by the general formula (1).
  • an organic electroluminescence device having a small light emission ratio of a component longer than the light emission maximum wavelength, high light emission efficiency, low drive voltage, and long light emission lifetime, a small voltage increase during drive, and excellent stability over time.
  • a luminescence element and an organic electroluminescence element material used for the element can be provided.
  • a lighting device and a display device including the element can be provided.
  • a ring bonded to a metal atom with a carbon atom has a condensed ring structure, and a ring coordinated to a metal atom has a specific substitution at a position adjacent to the coordinate atom. It is a metal complex having a 1H-1,2,4-triazole derivative having a group as a ligand.
  • a ring bonded to a metal atom with a carbon atom has a condensed ring structure containing a heteroatom, so that an effect of suppressing light emission of components longer than the emission maximum wavelength can be seen.
  • the present inventors further suppress the aggregation by allowing the ring coordinated to the metal atom to have a specific substituent (R in the general formula (1) of the present invention) adjacent to the coordination atom. Furthermore, it was found that the effect of suppressing light emission of a component longer than the light emission maximum wavelength appears more remarkably by suppressing the vibration of the ligand.
  • the compound having the structure represented by the general formula (1) not only has an effect of suppressing light emission of components longer than the emission maximum wavelength, but also has high luminous efficiency, low driving voltage, and long life.
  • FIG. 2 is a schematic diagram of a passive matrix type full-color display device according to display unit A of FIG. Schematic of lighting device Cross section of the lighting device
  • Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device
  • Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device
  • Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device
  • the organic electroluminescence device of the present invention is an organic electroluminescence device comprising an organic layer sandwiched between at least one pair of an anode and a cathode, wherein the organic layer comprises at least one layer including a light emitting layer, Among them, at least one layer contains a compound having a structure represented by the general formula (1).
  • the structure represented by the general formula (1) is preferably a structure represented by any one of the general formulas (5) to (10).
  • at least two of the adjacent R 1 ⁇ R 4 preferably represents a structure of the general formula condensed (3) or (4).
  • R preferably represents an alkyl group or a cyano group.
  • Ar preferably represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a substituent at the 2-position.
  • n preferably represents 0.
  • the said light emitting layer contains the compound which has a structure represented by the said General formula (1).
  • the light emitting layer contains at least two kinds of the compound of the general formula (1) and a compound having a HOMO level of ⁇ 5.4 eV or less.
  • the compound having the structure represented by the general formula (1) according to the present invention has a deep HOMO level as compared with a conventional metal complex having a 4H-1,2,4-triazole derivative as a ligand. , When used together with a deep compound having a HOMO level of ⁇ 5.4 eV or less, the movement of electric charges becomes smooth, which leads to further improvement in light emission efficiency and driving voltage.
  • the manufacturing method of the organic electroluminescent element of this invention is a manufacturing method of the organic electroluminescent element which manufactures the said organic electroluminescent element, Comprising: The structure represented by the said General formula (1) among the said organic layers is provided. A layer containing a compound having the above is formed by a wet process. As a result, an organic electroluminescence device having a small emission ratio of components longer than the emission maximum wavelength, high luminous efficiency, low driving voltage, long emission lifetime, small voltage increase during driving, and excellent stability over time Can be manufactured.
  • the display device and the illumination device of the present invention are characterized by including the organic electroluminescence element.
  • the organic electroluminescence device material of the present invention is characterized by containing a compound having a structure represented by the general formula (1).
  • the organic electroluminescence element material By using the organic electroluminescence element material, the light emission ratio of components longer than the light emission maximum wavelength is small, high light emission efficiency, low drive voltage, long light emission lifetime, small voltage rise during driving, stable over time It is possible to obtain an organic electroluminescent element excellent in the above.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the organic electroluminescence device of the present invention is an organic electroluminescence device comprising an organic layer sandwiched between at least one pair of an anode and a cathode, wherein the organic layer comprises at least one layer including a light emitting layer, Among them, at least one layer contains a compound having a structure represented by the general formula (1).
  • General formula (1) will be described later.
  • Anode / light emitting layer / cathode (2) Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( 7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) luminescent layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode Among the above, the configuration of (7) is preferable. Although used,
  • the light emitting layer according to the present invention is composed of a single layer or a plurality of layers, and when it is composed of a plurality of layers, a non-light emitting intermediate layer may be provided between the light emitting layers.
  • a hole blocking layer also referred to as a hole blocking layer
  • an electron injection layer also referred to as a cathode buffer layer
  • An electron blocking layer also referred to as an electron barrier layer
  • a hole injection layer also referred to as an anode buffer layer
  • the electron transport layer used in the present invention is a layer having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer may be composed of a plurality of layers.
  • the hole transport layer used in the present invention is a layer having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer may be composed of a plurality of layers.
  • the layer excluding the anode and the cathode is referred to as an “organic layer”.
  • the organic EL element of the present invention may be a so-called tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • tandem structure As typical element configurations of the tandem structure, for example, the following configurations can be given.
  • Anode / first light emitting unit / second light emitting unit / third light emitting unit / cathode Anode / first light emitting unit / intermediate layer / second light emitting unit / intermediate layer / third light emitting unit / cathode
  • the first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. Further, the two light emitting units may be the same, and the remaining one may be different.
  • the third light emitting unit may not be provided, and on the other hand, a light emitting unit or an intermediate layer may be further provided between the third light emitting unit and the cathode.
  • the plurality of light emitting units may be directly stacked or may be stacked via an intermediate layer.
  • the intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and electrons are provided in an adjacent layer on the anode side and holes are provided in an adjacent layer on the cathode side. Any known material and structure can be used as long as the layer has a function of supplying.
  • Examples of materials used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiO x , VO x , CuI, InN, GaN, Conductive inorganic compound layers such as CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 and Al, two-layer films such as Au / Bi 2 O 3 , SnO 2 / Ag / SnO 2 , ZnO / Multi-layer film such as Ag / ZnO, Bi 2 O 3 / Au / Bi 2 O 3 , TiO 2 / TiN / TiO 2 , TiO 2 / ZrN / TiO 2 , fullerenes such as C 60 , conductivity such as oligothiophene Examples include organic material layers, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, metal porphy
  • Preferred examples of the structure within the light emitting unit include those obtained by removing the anode and the cathode from the structures (1) to (7) mentioned in the above representative element structures, but the present invention is not limited to these. Not.
  • tandem organic EL element examples include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734. Specification, U.S. Pat. No. 6,337,492, International Publication No.
  • the light emitting layer according to the present invention is a layer that emits light when excitons generated by recombination of electrons and holes injected from the cathode or the electron transport layer or the anode or the hole transport layer are deactivated.
  • the portion to be formed may be in the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the stability of the emission color against the driving current and the uniformity of the film, preventing unnecessary application of high voltage during light emission. It is preferably adjusted in the range of 2 nm to 5 ⁇ m, more preferably adjusted in the range of 2 to 200 nm, particularly preferably in the range of 5 to 100 nm.
  • a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, Examples thereof include an inkjet method, a printing method, a spray coating method, a curtain coating method, an LB method (Langmuir-Blodgett method) and the like.
  • the light emitting layer is a layer formed through a wet process. By forming the layer by a wet process, damage to the light emitting layer due to heat can be reduced as compared with the vacuum deposition method.
  • the light emitting layer of the organic EL device of the present invention contains a light emitting dopant and a host compound, and at least one light emitting dopant has a structure represented by the general formula (1) described above.
  • a complex preferably a phosphorescent organometallic complex having a structure represented by any one of the general formulas (5) to (10).
  • Luminescent dopant As the luminescent dopant, fluorescent dopants (also referred to as fluorescent compounds) and phosphorescent dopants (also referred to as phosphorescent dopants, phosphorescent compounds, phosphorescent compounds, etc.) can be used. .
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), although the phosphorescence quantum yield is defined to be a compound of 0.01 or more at 25 ° C., the preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. It ’s fine.
  • phosphorescent dopants There are two types of emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. It is an energy transfer type to obtain light emission from a phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
  • a phosphorescent organometallic complex having a structure represented by the general formula (1) described below is preferably used as the phosphorescent dopant.
  • the phosphorescent organometallic complex having the structure represented by the general formula (1) As the phosphorescent dopant in the embodiment of the present invention, a phosphorescent organometallic complex having a structure represented by the general formula (1) described below is preferably used.
  • R 1 to R 4 are each independently a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a (t) butyl group, a pentyl group, a hexyl group, Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, benzyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group ( For example, propargyl group, etc.), aromatic hydrocarbon group (also called aryl group, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthy
  • alkoxy group eg methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group etc.
  • cycloalkoxy group eg cyclopentyloxy
  • Group cyclohexyloxy group, etc.
  • aryloxy group eg, phenoxy group, naphthyloxy group, etc.
  • alkylthio group eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.
  • a cycloalkylthio group eg, cyclopentylthio group, cyclohexylthio group, etc.
  • Examples include the alkyl group of R in the general formula (1), halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfinyl group, sulfonyl group, nitro group, cyano group, hydroxy group, mercapto The same applies to the group. Furthermore, the specific examples in parentheses in the aromatic hydrocarbon group or aromatic heterocyclic group in the above substituent are the same in the aromatic hydrocarbon group or aromatic heterocyclic group of Ar in the general formula (1). .
  • R 1 to R 4 represent the above substituent, an alkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an aryloxy group, an arylthio group, an amino group, a cyano group It is preferably any of them, particularly preferably an aromatic hydrocarbon group, an aromatic heterocyclic group, a halogen atom or a cyano group, more preferably a halogen atom or a cyano group.
  • R is an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxy group, and a mercapto group. Represents any group selected. These groups may be further substituted with the above substituents.
  • R is preferably any one of an alkyl group, a halogen atom, and a cyano group.
  • R is an alkyl group or a cyano group from the viewpoint of more effectively suppressing emission of a component having a wavelength longer than the emission maximum wavelength.
  • an alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. These groups may be further substituted with the above substituents, or they may be condensed with each other to further form a ring.
  • Ar is preferably substituted by the above substituent, and in particular, substituted by any one of an alkyl group, a cycloalkyl group, a halogen atom, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group. In particular, it is preferably substituted by an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • the ortho position is substituted with respect to the bonding position with the 1H-1,2,4-triazole ring of the general formula (1) (the ring represented by Ar is 1H-1,2,4- It has a substituent at the position adjacent to the bonding position with the triazole ring) from the viewpoint of shortening the emission wavelength, and is particularly preferably substituted by an alkyl group.
  • X 1 -L 1 -X 2 represents a bidentate ligand, and X 1 and X 2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L 1 represents an atomic group that forms a bidentate ligand together with X 1 and X 2 .
  • bidentate ligand represented by X 1 -L 1 -X 2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, picolinic acid However, it is not limited to these.
  • the bidentate ligand represented by X 1 -L 1 -X 2 is preferably phenylpyrazole or phenyltriazole, particularly preferably phenyltriazole.
  • n represents an integer of 1 to 3
  • n represents an integer of 0 to 2
  • m + n is 3.
  • n is preferably 0 or 1, and particularly preferably 0 from the viewpoint of more effectively suppressing light emission of a component longer than the light emission maximum wavelength.
  • At least two of the adjacent R 1 to R 4 are condensed to represent any one of the general formulas (2) to (4).
  • Y 1 to Y 4 each independently represent O, S, or N—R ′, and Y 5 or Y 6 represents CR ′′ or N.
  • Y 1 or Y 4 is particularly preferably NR ′, Y 2 or Y 3 is preferably O or NR ′, and particularly preferably NR ′.
  • Y 5 is preferably CR ′′, and Y 6 is preferably N.
  • R ′ represents any group selected from an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, and an aromatic heterocyclic group. These groups may be further substituted with the above substituents, or they may be condensed with each other to further form a ring.
  • R ′ is preferably any group selected from an aromatic hydrocarbon group, a heterocyclic group, and an aromatic heterocyclic group, and particularly preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • R ′′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, or a cyano group.
  • R ′′ is preferably any group selected from a hydrogen atom, an aromatic hydrocarbon group, and an aromatic heterocyclic group.
  • Z 1 to Z 8 each independently represent C—Rx or N, and the plurality of Rx may be the same or different.
  • Z 1 to Z 8 are preferably C—Rx.
  • the plurality of Rx each independently represents a group equivalent to R 1 to R 4 in the general formula (1). These groups may be further substituted with the above substituents, or they may be condensed with each other to further form a ring.
  • Rx is selected from an alkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, and a cyano group.
  • any group selected from an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a halogen atom, and a cyano group is preferable.
  • the compound having the structure represented by the general formula (1) may be contained in an organic layer other than the light emitting layer.
  • R, Ar, R 1 to R 4 , Y 1 , Z 1 to Z 4 , X 1 , X 2 , L 1 , m and n are the same as those in the general formula (1).
  • (2) are synonymous with R, Ar, R 1 to R 4 , Y 1 , Z 1 to Z 4 , X 1 , X 2 , L 1 , m and n.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, and fluorescein dyes. Examples include dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, and compounds having high fluorescence quantum yields typified by laser dyes.
  • luminescent dopant using delayed fluorescence include, for example, compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Is not limited to these.
  • the light-emitting dopant according to the present invention may be used in combination with a plurality of types of compounds. Combinations of phosphorescent dopants having different structures, phosphorescent dopants and fluorescence A combination of dopants may be used. Known phosphorescent dopants and fluorescent dopants can be used.
  • the host compound (hereinafter also referred to as a light-emitting host) has a mass ratio in the layer of 20% or more among the compounds contained in the light-emitting layer, and a room temperature (25 ° C. ) Is defined as a compound having a phosphorescence quantum yield of phosphorescence of less than 0.1.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • the light-emitting host that can be used in the present invention is not particularly limited, and compounds conventionally used in organic EL devices can be used.
  • a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.
  • a conventionally known light emitting host may be used alone, or a plurality of types may be used in combination.
  • the movement of charges can be adjusted, and the organic EL element can be made highly efficient.
  • it becomes possible to mix different light emission by using multiple types of the metal complex of this invention used as the said phosphorescence dopant, and / or a conventionally well-known compound, and, thereby, arbitrary luminescent colors can be obtained.
  • the light emitting host used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emitting host). It is also possible to use one or a plurality of such compounds.
  • Light-emitting hosts include Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 Gazette, 2002-338579 gazette, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette.
  • the compound having the structure represented by the general formula (1) according to the present invention has a deep HOMO level
  • a host compound having a HOMO level of ⁇ 5.4 eV or less is used. It is preferable. Thereby, the movement of electric charges becomes smooth, which leads to further improvement in light emission efficiency and driving voltage.
  • the electron transport layer is made of a material having a function of transporting electrons and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the total thickness of the electron transport layer used in the present invention is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • the organic EL element when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer interferes with the light extracted after being reflected by the electrode from which the light is extracted and the electrode located at the counter electrode. It is known to wake up. When light is reflected by the cathode, this interference effect can be efficiently utilized by appropriately adjusting the thickness of the electron transport layer between several nanometers and several micrometers. On the other hand, when the layer thickness of the electron transport layer is increased, the voltage is likely to increase. Therefore, particularly when the layer thickness is large, the electron mobility of the electron transport layer is preferably 10 ⁇ 5 cm 2 / Vs or more. .
  • the material used for the electron transport layer may have any of an electron injection property or a transport property, and a hole barrier property. Any one can be selected and used.
  • nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, etc.), dibenzofuran derivatives, And dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene, etc.)
  • a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand such as tris (8-quinolinol) aluminum (Alq3), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7- Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
  • a metal complex in which the central metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • Distyrylpyrazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type-Si and n-type-SiC can be used as electron-transport materials as well as hole-injection layers and hole-transport layers. Can do.
  • a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can be used.
  • an electron transport layer may be doped with a doping material as a guest material to form an electron transport layer having a high n property (electron rich).
  • the doping material include n-type dopants such as metal complexes and metal compounds such as metal halides.
  • Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.
  • More preferable electron transport materials in the present invention include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having the function of an electron transport layer in a broad sense, and is preferably made of a material having a function of transporting electrons and a small ability to transport holes. By blocking the holes, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer used for this invention as needed.
  • the hole blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the cathode side of the light emitting layer.
  • the layer thickness of the hole blocking layer used in the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the material used for the hole blocking layer As the material used for the hole blocking layer, the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.
  • the electron injection layer (also referred to as “cathode buffer layer”) used in the present invention is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. 2 and Chapter 2 “Electrode Materials” (pages 123 to 166) of “The Forefront of Industrialization” (published by NTT Corporation on November 30, 1998).
  • the electron injection layer may be provided as necessary, and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
  • the electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 0.1 to 5 nm, depending on the material. Further, it may be a non-uniform film in which constituent materials are present intermittently.
  • JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like Specific examples of materials preferably used for the electron injection layer are as follows. , Metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compounds typified by magnesium fluoride, calcium fluoride, etc., oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by lithium 8-hydroxyquinolate (Liq), and the like. Further, the above-described electron transport material can also be used. Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.
  • the hole transport layer is made of a material having a function of transporting holes, and may have a function of transmitting holes injected from the anode to the light emitting layer.
  • the total thickness of the hole transport layer used in the present invention is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • a material used for the hole transport layer may have any of a hole injection property or a transport property, and an electron barrier property. Any one can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives , Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polyvinyl carbazole, polymer materials or oligomers with aromatic amines introduced into the main chain or side chain, polysilane, conductive And polymer (for example, PEDOT / PSS, aniline copolymer, polyaniline, polythiophene, etc.).
  • PEDOT / PSS aniline copolymer, poly
  • triarylamine derivatives examples include benzidine type typified by ⁇ -NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), starburst type typified by MTDATA, Examples include compounds having fluorene or anthracene in the triarylamine-linked core.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
  • a hole transport layer having a high p property doped with impurities can also be used.
  • examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • JP-A-11-251067 J. Org. Huang et. al.
  • a so-called p-type hole transport material or an inorganic compound such as p-type-Si, p-type-SiC, or the like as described in a book (Appl. Phys. Lett., 80 (2002), p. 139) is used. You can also.
  • ortho-metalated organometallic complexes having Ir or Pt as a central metal as typified by Ir (ppy) 3 are also preferably used.
  • the above-mentioned materials can be used as the hole transport material, a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain.
  • the polymer materials or oligomers used are preferably used.
  • Patent Application Publication No. 2008/0106190 U.S. Patent Application Publication No. 2008/0018221, International Publication No. 2012/115034, Special Table No. 2003-519432 JP, JP 2006 135145 JP, is US Patent Application No. 13/585981 Pat like.
  • the hole transport material may be used alone or in combination of two or more.
  • the electron blocking layer is a layer having a function of a hole transport layer in a broad sense, and is preferably made of a material having a function of transporting holes and a small ability to transport electrons, while transporting holes. By blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned above can be used as an electron blocking layer used for this invention as needed.
  • the electron blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the anode side of the light emitting layer.
  • the layer thickness of the electron blocking layer used in the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer is preferably used, and the material used for the host compound is also preferably used for the electron blocking layer.
  • the hole injection layer (also referred to as “anode buffer layer”) used in the present invention is a layer provided between the anode and the light emitting layer in order to lower the driving voltage or improve the light emission luminance. It is described in detail in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Elements and the Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the hole injection layer may be provided as necessary, and may exist between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
  • the details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc.
  • materials used for the hole injection layer include: Examples thereof include materials used for the hole transport layer described above.
  • phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432 and JP-A-2006-135145, etc.
  • Preferred are conductive polymers such as polyaniline (emeraldine) and polythiophene, orthometalated complexes represented by tris (2-phenylpyridine) iridium complex, and triarylamine derivatives.
  • the materials used for the hole injection layer described above may be used alone or in combination of two or more.
  • the organic layer in the present invention described above may further contain other additive compounds.
  • the additive compound include halogen elements such as bromine, iodine, and chlorine, halogenated compounds, alkali metals such as Pd, Ca, and Na, alkaline earth metals, transition metal compounds, complexes, and salts.
  • the content of the additive compound can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 50 ppm or less, based on the total mass% of the contained layer. . However, it is not within this range depending on the purpose of improving the transportability of electrons and holes, the purpose of making the energy transfer of excitons advantageous.
  • ⁇ Method for forming organic layer> A method for forming an organic layer (hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) used in the present invention will be described.
  • the formation method of the organic layer used in the present invention is not particularly limited, and a conventionally known formation method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • a layer formed by a process is preferable. That is, it is preferable to produce an organic EL element by a wet process.
  • By producing the organic EL element by a wet process it is possible to obtain an effect such that a homogeneous film (coating film) is easily obtained and pinholes are hardly generated.
  • membrane (coating film) here is a thing of the state dried after application
  • Examples of the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the organic EL material of the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesitylene, Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • fatty acid esters such as ethyl acetate
  • halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesitylene
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons
  • a dispersion method it can be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • a different film forming method may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature ⁇ 50 to 300 ° C., layer thickness 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic layer according to the present invention it is preferable to consistently produce from the hole injection layer to the cathode by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.
  • anode As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • a conductive transparent material such as a metal such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
  • a thin film may be formed by a method such as vapor deposition or sputtering using these electrode materials, and a pattern having a desired shape may be formed by a photolithography method, or pattern accuracy is not much required. If not (about 100 ⁇ m or more), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
  • wet film forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • cathode As the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, aluminum, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this from the viewpoint of durability against electron injection and oxidation for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
  • the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Appel (
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992. , And a relative humidity (90 ⁇ 2)%) of 1 ⁇ 10 ⁇ 2 g / (m 2 ⁇ 24 h) or less is preferable. Further, it is measured by a method in accordance with JIS K 7126-1987.
  • a high gas barrier film having an oxygen permeability of 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • oxygen permeability 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less
  • water vapor permeability 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the material for forming the gas barrier film may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, and the like can be used.
  • the method for forming the gas barrier film is not particularly limited.
  • the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
  • external extraction quantum efficiency (%) number of photons emitted to the outside of the organic EL element / number of electrons flowed to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using the phosphor may be used in combination.
  • sealing means used for sealing the organic EL element of the present invention include a method of bonding a sealing member, an electrode, and a support substrate with an adhesive.
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be concave or flat. Moreover, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and a method according to JIS K 7129-1992.
  • the measured water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)%) is preferably that of 1 ⁇ 10 -3 g / (m 2 / 24h) or less.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable.
  • a desiccant may be dispersed in the adhesive.
  • Application of the adhesive to the sealing portion may use a commercially available dispenser, or may be printed like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • a material for forming the film any material may be used as long as it has a function of suppressing infiltration of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma
  • a combination method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside. Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a protective film or a protective plate may be provided outside the sealing film or the sealing film on the side facing the support substrate with the organic layer interposed therebetween.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • An organic electroluminescent element emits light inside a layer having a refractive index higher than that of air (with a refractive index of about 1.6 to 2.1), and about 15% to 20% of light generated in the light emitting layer. It is generally said that only light can be extracted. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the element, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light undergoes total reflection between the light, the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the side surface direction of the element.
  • a technique for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the transparent substrate and the air interface (for example, US Pat. No. 4,774,435), A method for improving efficiency by providing light condensing property (for example, Japanese Patent Laid-Open No. 63-134795), a method for forming a reflective surface on the side surface of an element (for example, Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • by combining these means it is possible to obtain an element having higher luminance or durability.
  • the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium has a feature that the effect of improving the light extraction efficiency is high.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction, such as first-order diffraction or second-order diffraction.
  • the light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (inside a transparent substrate or transparent electrode). , Trying to extract light out.
  • the introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any layer or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention is processed in a microlens array-like structure on the light extraction side of the support substrate (substrate), or combined with a so-called condensing sheet, for example, in a specific direction, for example, By condensing in the front direction with respect to the element light emitting surface, the luminance in a specific direction can be increased.
  • a quadrangular pyramid having a side of 30 ⁇ m and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes thick, which is not preferable.
  • the condensing sheet for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • BEF brightness enhancement film
  • the shape of the prism sheet for example, a substrate may be formed with a triangle stripe having an apex angle of 90 degrees and a pitch of 50 ⁇ m, or the apex angle is rounded and the pitch is changed randomly. Other shapes may also be used.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • lighting devices home lighting, interior lighting
  • clock and liquid crystal backlights billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Examples include, but are not limited to, a light source of a sensor.
  • the light source can be effectively used for a backlight of a liquid crystal display device and a light source for illumination.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like when forming a film, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned.
  • a conventionally known method is used. Can do.
  • the organic EL element of the present invention can be used for a display device.
  • One mode of the display device of the present invention that includes the organic EL element of the present invention will be described.
  • the display device may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.
  • the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.
  • the configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary. Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc.
  • the present invention is not limited to these.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, a wiring unit C that electrically connects the display unit A and the control unit B, and the like.
  • the control unit B is electrically connected to the display unit A via the wiring unit C, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside. Sequentially emit light according to the image data signal, scan the image, and display the image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A in FIG.
  • the display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 2 shows a case where the light (emitted light) emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (details are shown in FIG. Not shown).
  • the pixel 3 When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
  • Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a schematic diagram showing a pixel circuit.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied to the drain of the switching transistor 11 from the control unit B shown in FIG. 1 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 When the scanning signal moves to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 holds the charged potential of the image data signal even if the driving of the switching transistor 11 is turned off, the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. good.
  • the potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 4 is a schematic diagram of a passive matrix type full-color display device according to the display unit A of FIG.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.
  • the pixel 3 has no active element, and the manufacturing cost can be reduced.
  • the organic EL element of the present invention can be used for a lighting device.
  • One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a 300 ⁇ m thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and illuminated as shown in FIGS.
  • a device can be made.
  • FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is to bring the organic EL element 101 into contact with the atmosphere.
  • a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas with a purity of 99.999% or higher).
  • FIG. 6 shows a cross-sectional view of the lighting device.
  • 105 denotes a cathode
  • 106 denotes an organic EL layer
  • 107 denotes a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • Comparative Compound 1 Compound disclosed in International Publication No. 2004/101707
  • Comparative Compound 2 Compound disclosed in Japanese Patent No. 5644050
  • Comparative Compound 3 Compound disclosed in Japanese Patent No. 5099013
  • Comparative Compound 4 Japanese Patent Laid-Open No. 2013-2003 Compound disclosed in Japanese Patent No. 040159
  • Example 1 ⁇ Production of Organic EL Element 1-1 >> Patterning was performed on a substrate (NA-45, manufactured by AvanStrate Co., Ltd.) on which a film of ITO (indium tin oxide) having a thickness of 100 nm was formed as an anode on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • ITO indium tin oxide
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of HT-1 as a hole injection material is put in a molybdenum resistance heating boat, and HT- as a hole transport material is put in another molybdenum resistance heating boat.
  • 200 mg of 2 and 200 mg of Comparative Compound 1 as a dopant in another molybdenum resistance heating boat, 200 mg of Host-1 as a host compound in another molybdenum resistance heating boat, and holes in another molybdenum resistance heating boat 200 mg of ET-1 was placed as a blocking material, and 200 mg of ET-2 was placed as an electron transport material in another molybdenum resistance heating boat, which was attached to a vacuum deposition apparatus.
  • the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing a heating boat containing HT-1, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection layer was formed.
  • the heating boat containing HT-2 was energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 30 nm.
  • the heating boat containing Comparative Compound 1 and Host-1 was heated by energization, and co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively, and the layer thickness was 40 nm. A light emitting layer was formed.
  • the heating boat containing ET-1 was heated by energization, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to form a hole blocking layer having a layer thickness of 10 nm.
  • the heating boat containing ET-2 was energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.
  • an organic EL element 1-1 was produced.
  • the compound used in this example has the following chemical structural formula.
  • Organic EL elements 1-2 to 1-10 were respectively prepared in the same manner as in the manufacture of the organic EL element 1-1 except that the comparative compound 1 and Host-1 were changed to the compounds shown in Table 1.
  • Host-2 in Table 1 has the following chemical structural formula.
  • External extraction quantum efficiency also referred to as luminous efficiency
  • the external extraction quantum efficiency ( ⁇ ) was calculated.
  • the measurement of emission luminance was performed using CS-1000 (manufactured by Konica Minolta Sensing), and the external extraction quantum efficiency was expressed as a relative value where the organic EL element 1-1 was 100.
  • Stability over time (power efficiency after storage / power efficiency before storage) ⁇ 100
  • the power efficiency was obtained by measuring the front luminance and luminance angle dependency of each organic EL element using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) and obtaining the front luminance of 1000 cd / m 2 . Using.
  • PEDOT / PSS polystyrene sulfonate
  • This transparent support substrate was fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of HT-2 as a hole transport material was placed in a molybdenum resistance heating boat, and Comparative Compound 1 as a dopant in another molybdenum resistance heating boat.
  • 200 mg of Host-1 was placed in another molybdenum resistance heating boat as a host compound, and 200 mg of ET-1 as an electron transport material was placed in another molybdenum resistance heating boat, which was attached to a vacuum deposition apparatus.
  • the heating boat containing HT-2 was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second, and the layer thickness was 20 nm.
  • the second hole transport layer was formed.
  • the heating boat containing Comparative Compound 1 and Host-1 was heated by energization, and co-deposited on the second hole transport layer at a deposition rate of 0.1 nm / second and 0.006 nm / second, respectively.
  • a 40 nm light emitting layer was formed.
  • the heating boat containing ET-1 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride is vapor-deposited on the light emitting layer to form an electron injection layer having a thickness of 0.5 nm
  • aluminum is vapor-deposited on the electron injection layer to form a cathode having a thickness of 110 nm. 2-1.
  • Organic EL devices 2-2 to 2-8 were respectively prepared in the same manner as in the manufacture of the organic EL device 2-1, except that Comparative Compound 1 and Host-1 were changed to the compounds shown in Table 2.
  • the substrate was transferred to a nitrogen atmosphere, and a solution obtained by dissolving 47 mg of HT-3 and 3 mg of HT-4 in 10 mL of toluene was used on the first hole transport layer under conditions of 1500 rpm and 30 seconds.
  • a thin film was formed by spin coating. Ultraviolet light was irradiated at 120 ° C. for 90 seconds to perform photopolymerization / crosslinking, and further vacuum dried at 60 ° C. for 1 hour to form a second hole transport layer having a layer thickness of about 20 nm.
  • a thin film was formed on the light-emitting layer by spin coating using a solution of 50 mg of ET-3 dissolved in 10 mL of hexafluoroisopropanol (HFIP) at 1500 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and the electron carrying layer with a layer thickness of about 20 nm was formed.
  • HFIP hexafluoroisopropanol
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, potassium fluoride was deposited on the electron transport layer and an electron injection with a thickness of 0.4 nm was made Then, aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm, and an organic EL element 3-1 was produced.
  • the compound used in this example has the following chemical structural formula.
  • Organic EL devices 3-2 to 3-8 were prepared in the same manner except that Comparative Compound 1 and Host-3 were changed to the compounds shown in Table 3 in the production of Organic EL device 3-1. Comparative compound 5 and Host-4 in Table 3 have the following chemical structural formulas.
  • Comparative compound 5 Compound disclosed in JP2013-040159A
  • a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al4083) to 70% by mass with pure water was used. After forming a thin film by the coating method, it was dried at 200 ° C. for 1 hour to form a first hole transport layer having a layer thickness of 30 nm.
  • a hole transport material Poly N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- A thin film was formed by spin coating using the chlorobenzene solution of No. 254). Heat drying at 150 ° C. for 1 hour to form a second hole transport layer having a layer thickness of 40 nm.
  • a thin film was formed by spin coating using Host-3 as a host compound and a butyl acetate solution of Comparative Compound 1 as a dopant, and dried by heating at 120 ° C. for 1 hour.
  • a light emitting layer having a thickness of 30 nm was formed.
  • a 1-butanol solution of ET-4 as an electron transport material was used and a thin film was formed by spin coating to form an electron transport layer having a layer thickness of 20 nm.
  • This substrate was attached to a vacuum deposition apparatus, and the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa.
  • lithium fluoride is vapor-deposited on the electron transport layer to form an electron injection layer having a thickness of 1.0 nm
  • aluminum is vapor-deposited on the electron injection layer to form a cathode having a thickness of 110 nm, and the organic EL element 4 -1 was produced.
  • the compound used in this example has the following chemical structural formula.
  • Organic EL elements 4-2 to 4-10 were respectively prepared in the same manner as in the manufacture of the organic EL element 4-1, except that Comparative Compound 1 and Host-3 were changed to the compounds shown in Table 4. Comparative compounds 6 and 7 in Table 4 have the following chemical structural formulas.
  • Comparative compound 6 Compound disclosed in Japanese Patent No. 5644050
  • Comparative compound 7 Compound disclosed in Japanese Patent No. 50990013
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of HT-6 as a hole injection material is put in a molybdenum resistance heating boat, and HT- as a hole transport material is put in another molybdenum resistance heating boat.
  • the pressure in the vacuum chamber was reduced to 4 ⁇ 10 ⁇ 4 Pa, and then heated by energizing a heating boat containing HT-6, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second. A hole injection layer was formed.
  • the heating boat containing HT-5 was energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 20 nm.
  • the heating boat containing Host-5, Comparative Compound 1, D-3 and D-4 was energized and heated, and the deposition rates were 0.1 nm / second, 0.025 nm / second, 0.0007 nm / second, Co-evaporation was performed on the hole transport layer at 0.0002 nm / second to form a light emitting layer having a layer thickness of 60 nm.
  • the heating boat containing ET-5 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 20 nm.
  • Element 5-1 was produced.
  • the compound used in this example has the following chemical structural formula.
  • Organic EL elements 5-2 to 5-9 were respectively prepared in the same manner as in the manufacture of organic EL element 5-1, except that Comparative Compound 1 and Host-5 were changed to the compounds shown in Table 5.
  • Host-6 in Table 5 has the following chemical structural formula.
  • Example 6 Production of Organic EL Element 6-1 >> An ITO (indium tin oxide) film having a thickness of 120 nm was formed as an anode on a glass substrate having a size of 50 mm ⁇ 50 mm and a thickness of 0.7 mm, followed by patterning. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. The transparent substrate was then used as a substrate holder for a commercially available vacuum deposition apparatus. Fixed to.
  • Each of the resistance heating boats in the vacuum evaporation apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication.
  • the resistance heating boat used was made of a resistance heating material made of molybdenum or tungsten.
  • the heating boat containing compound HT-1 was energized and heated, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec. A hole injection layer was formed.
  • compound HT-2 was vapor-deposited in the same manner on the hole injection layer, thereby forming a hole transport layer having a layer thickness of 30 nm.
  • Comparative Compound 1 and Host-5 were co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second so as to be 90% by volume and 10% by volume, respectively, to form a light emitting layer having a layer thickness of 30 nm. .
  • ET-1 was vapor-deposited on the light-emitting layer at a vapor deposition rate of 0.1 nm / second to form a first electron transport layer having a layer thickness of 10 nm.
  • the second electron transport layer having a layer thickness of 45 nm was formed.
  • lithium fluoride was deposited on the second electron transport layer to form an electron injection layer having a thickness of 1.0 nm, and then aluminum was deposited on the electron injection layer to form a cathode having a thickness of 100 nm.
  • An electrode extraction wiring is installed on the above element, covered with a can-shaped glass case filled with epoxy resin in a nitrogen glove box of 1 ppm or less of water and oxygen atmosphere, a moisture absorbent is incorporated in the package, and an organic EL element 6-1 was produced.
  • Organic EL elements 6-2 to 6-9 were prepared in the same manner except that Comparative Compound 1 and Host-5 were changed to the compounds shown in Table 6 in the production of Organic EL element 6-1.
  • Comparative compound 8 in Table 6 has the following chemical structural formula.
  • Comparative compound 8 Compound disclosed in JP2013-040159A
  • Example 7 Production of organic EL full-color display device >> In this example, an organic EL full-color display device was fabricated and evaluated as shown in FIGS. 7A to 7E. 7A to 7E are schematic configuration diagrams of the organic EL full-color display device.
  • a non-photosensitive polyimide partition wall 203 (width 20 ⁇ m, thickness 2.0 ⁇ m) was formed between the ITO transparent electrodes 202 by photolithography (see FIG. 7B).
  • a hole injection layer composition having the following composition is ejected and injected on the ITO electrode 202 between the partition walls 203 using an inkjet head (manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 200 seconds, and 60 ° C.
  • a hole injection layer 204 having a layer thickness of 40 nm was formed by a drying process for 10 minutes (see FIG. 7C).
  • a blue light-emitting layer composition, a green light-emitting layer composition, and a red light-emitting layer composition having the following compositions are respectively ejected and injected onto the hole injection layer 204 using an inkjet head in the same manner, at 60 ° C. for 10 minutes. Drying treatment was performed to form light emitting layers 205B, 205G, and 205R for each color (see FIG. 7D).
  • an electron transport material is deposited so as to cover each of the light emitting layers 205B, 205G, and 205R to form an electron transport layer (not shown) having a layer thickness of 20 nm, and further lithium fluoride is deposited to form a layer thickness of 0.6 nm.
  • An electron injection layer (not shown) was formed, and Al was vapor-deposited to form a cathode 206 having a thickness of 130 nm to produce an organic EL device (see FIG. 7E).
  • the produced organic EL elements showed blue, green, and red light emission by applying a voltage to the electrodes, respectively, and were found to be usable as a full-color display device.
  • an organic electroluminescence element As described above, when the compound having the structure represented by the general formula (1) according to the present invention is used, it is possible to obtain light emission with a significantly small second wave ratio. Furthermore, according to the present invention, there are provided an organic electroluminescence element, an illuminating device and a display device having high luminous efficiency, low driving voltage, long life, small increase in driving voltage, and excellent stability over time. be able to. Moreover, the organic EL element which has the said effect can be manufactured with a wet process.
  • the present invention has a small light emission ratio of components longer than the light emission maximum wavelength, high light emission efficiency, low drive voltage, long light emission life, small voltage increase during driving, and stability over time. It is suitable for providing an excellent organic electroluminescence element, a method for producing the element, a display device and a lighting device including the element, and an organic electroluminescence element material used for the element.

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Abstract

L'invention concerne un élément électroluminescent organique qui présente un faible rapport d'émission de lumière d'un composant qui a une longueur d'onde supérieure à la longueur d'onde de pic d'émission, une efficacité lumineuse élevée, une faible tension d'attaque, une longue durée d'émission et une excellente stabilité de longue durée, tout en supprimant une augmentation de tension pendant l'excitation. Cet élément électroluminescent organique comprend des couches organiques qui sont prises en sandwich entre une électrode positive et une électrode négative ; et au moins une des couches organiques contient un composé qui a une structure représentée par la formule générale (1). (Dans la formule générale (1), R représente un groupe alkyle, un atome d'halogène, un groupe alcoxy, un groupe aryloxy, un groupe alkylthio, un groupe arylthio, un groupe acyle, un groupe sulfinyle, un groupe sulfonyle, un groupe nitro, un groupe cyano, un groupe hydroxy ou un groupe mercapto ; Ar représente un groupe hydrocarboné aromatique ou un groupe hétérocyclique aromatique ; X1-L1-X2 représente un ligand bidentate ; et deux fragments adjacents parmi les fragments R1-R4 représentent des groupes représentés par une des formules générales (2)-(4).) (Dans les formules générales (2)-(4), chacun des fragments Y1-Y4 représente O, S ou N-R' ; chacun des fragments Y5 et Y6 représente CR'' ou N ; et chacun des fragments Z1-Z8 représente C-Rx ou N.) AA Formule générale
PCT/JP2016/083530 2015-12-15 2016-11-11 Élément électroluminescent organique, procédé de fabrication d'élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairage et matériau d'élément électroluminescent organique WO2017104325A1 (fr)

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KR1020187013567A KR102081011B1 (ko) 2015-12-15 2016-11-11 유기 일렉트로루미네센스 소자, 유기 일렉트로루미네센스 소자의 제조 방법, 표시 장치, 조명 장치 및 유기 일렉트로루미네센스 소자 재료
JP2017556424A JP6696512B2 (ja) 2015-12-15 2016-11-11 有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス素子の製造方法、及び有機エレクトロルミネッセンス素子材料

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