WO2004077888A1 - Materiau conçu pour un dispositif electroluminescent organique et dispositif electroluminescent produit a partir de celui-ci - Google Patents

Materiau conçu pour un dispositif electroluminescent organique et dispositif electroluminescent produit a partir de celui-ci Download PDF

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WO2004077888A1
WO2004077888A1 PCT/JP2004/002383 JP2004002383W WO2004077888A1 WO 2004077888 A1 WO2004077888 A1 WO 2004077888A1 JP 2004002383 W JP2004002383 W JP 2004002383W WO 2004077888 A1 WO2004077888 A1 WO 2004077888A1
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organic
group
integer
derivative
nitrogen atom
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PCT/JP2004/002383
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Japanese (ja)
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Kimihisa Yamamoto
Jun-Sang Cho
Norifusa Sato
Atsushi Kimoto
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Kanagawa Academy Of Science And Technology
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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/791—Starburst compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the invention of this application relates to a material for an organic EL device and an organic EL device using the same. More specifically, the invention of this application comprises a phenylazomethine-based compound or a phenylazomethine mono-rubazole-based compound useful as a material for a hole transport layer and Z or a light-emitting layer in an organic EL device. It is about materials. Background art
  • an organic EL device has a structure in which a hole transport layer, a light emitting layer, an electron transport layer, and the like are stacked between a transparent anode such as IT0 and a cathode made of a metal having a low work function. Then, by passing a direct current between the electrodes, holes are injected from the anode to the hole transport layer, and the electrons and holes injected from the cathode recombine in the light emitting layer to generate excitons. Is done. When this exciton is deactivated, light energy (fluorescence or phosphorescence) is released, and light emission occurs.
  • a transparent anode such as IT0
  • a cathode made of a metal having a low work function
  • OLEDs are self-luminous and do not require a backlight, thus reducing power consumption, response speed, viewing angle, and contrast. 2004/002383
  • the characteristics such as the ratio are much better than the conventional TFT liquid crystal display device.
  • there are still issues such as improvement of luminous efficiency, high brightness, and long life for practical use.
  • materials for the hole transport layer, the light emitting layer, and the electron transport layer have been studied as a method for improving the luminous efficiency of the organic EL device.
  • an organic EL element material an aromatic amine derivative having a low ionization potential and a high hole transporting property, or a polymer material having an aromatic amine in a side chain is used.
  • dimethylbenzene derivatives with a triphenylamine group and a vinyl group and derivatives with an oxadiazole group known as an electron transport material are used. Has been.
  • rare-earth metal complex-based materials that exhibit strong fluorescent properties ⁇ -conjugated polyphenylenevinylene (PPV), and non-conjugated polyvinyl carbazole (PVK) derivatives are also used as materials for the light-emitting layer and hole transport layer.
  • PV ⁇ -conjugated polyphenylenevinylene
  • PVK non-conjugated polyvinyl carbazole
  • the film formation state of each layer that is, the morphological stability of the thin film is extremely important. Furthermore, a reduction in drive voltage is desired to reduce the power consumption of the device.
  • the invention of this application has been made in view of the circumstances described above, and has as its object to solve the problems of the prior art and to provide an organic EL device having excellent luminous efficiency and high durability. I have. Disclosure of the invention
  • X is a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, heterocycle and its derivatives, porphyrin and its derivatives, fluorinine and its derivatives, cyclam and its derivatives, and vinyl polymer and its derivatives.
  • a core site selected from the group consisting of derivatives, wherein Y and W are the same or different;
  • N is a nitrogen atom
  • R 1 is selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group which may have a substituent.
  • R 2 is a phenyl group which may have one or more substituents, and m is an integer of 1 to 6)
  • a material for an organic EL device is provided. '
  • X is carbon atom, nitrogen atom, amine derivative, benzene and , A heterocyclic ring and its derivative, porphyrin and its derivative, furocyanine and its derivative, and a cyclam and its derivative, a core site selected from the group consisting of: N is a nitrogen atom; R 1 is substituted A substituent selected from the group consisting of an alkylene group which may have a group, a phenylene group and a heterocyclic group, or may be absent; and R 2 has one or more substituents. And m is an integer of 1 to 6, and 1 is an integer of 1 to 6 representing the number of dendron subunits bonded to X).
  • a material for an organic EL device which is characterized by comprising a methine dendrimer.
  • N is a nitrogen atom
  • n is an integer from 1 to 6
  • k is an integer representing the number of dendron subunits bonded to X
  • N is a nitrogen atom
  • X is a carbon atom, a nitrogen atom, an amine derivative, a benzene and its derivative, a heterocycle and its derivative, a porphyrin and its derivative, a phthalocyanine and its derivative, and a cycle and its derivative.
  • R 1 is a substituent selected from the group consisting of an optionally substituted alkylene group, a phenylene group and a heterocyclic group, or is present.
  • R 2 is a phenyl group which may have one or more substituents; m is an integer of 1 to 6, n is an integer of 1 to 6; k and 1 are Which is an integer satisfying the condition 1 ⁇ k + 1 ⁇ 6, which represents the number of dendron subunits, each of which is bonded to X). Yes To provide for the EL element material.
  • the present invention provides a material for an organic EL device having a structure selected from the group consisting of (a) to (m).
  • N is a nitrogen atom
  • R 1 is a substituent selected from an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or may be absent.
  • R 2 is a phenyl group which may have one or more substituents
  • m is an integer of 1 to 6
  • n is an integer of 1 to 6
  • p and Q are one or more integers representing the degree of polymerization.
  • the present invention provides a material for an organic EL device, comprising a phenylazomethine-potassium rubazole copolymer represented by the following formula:
  • N is a nitrogen atom
  • R 1 is a substituent selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or absent.
  • R 2 is a phenyl group which may have one or more substituents, m is an integer of 1 to 6), and a compound represented by the following formula (XI )
  • a method for producing a material for an organic EL device characterized by reacting a vinylcarbazole monomer represented by the following formula: .
  • a ninth aspect of the invention of this application is an organic EL comprising at least an anode, a hole transport layer formed on the anode, a light emitting layer in contact with the hole transport layer, and a cathode in contact with the light emitting layer.
  • the hole transporting layer or the light emitting layer is formed of a thin film containing any of the above-mentioned materials for an organic EL device.
  • the organic EL device is characterized in that the light-emitting layer is formed of a thin film containing a metal salt together with any one of the materials for an organic EL device described above, and, first, the hole transport layer or the light-emitting layer An organic EL device comprising a thin film obtained by photocrosslinking any of the above materials for an organic EL device.
  • the invention of the present application also provides, 12thly, a light-emitting or display device characterized by including any one of the above-mentioned organic EL devices.
  • FIG. 1 is a schematic diagram illustrating the organic EL device of the present invention.
  • 1 organic EL element
  • 21 transparent substrate
  • 22 anode
  • 3 hole transport layer
  • 4 light emitting layer
  • 5 cathode
  • 6 conducting wire
  • FIG. 2 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application.
  • the hole transport layer is a: phenylazomethine dendrimer (4th generation), b: phenylazomethine dendrimer (4th generation), high temperature measurement, c: phenylazomethine dendrimer (4th generation) ' Tin chloride, d: diaminomethyl-substituted phenylazomethine dendrimer (3rd generation)
  • FIG. 3 is a diagram showing the characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application.
  • the hole transport layer is a: phenylazomethine dendrimer (4th generation) ⁇ tin chloride / polyvinylcarbazole, b: polyvinylcarbazole
  • FIG. 4 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention.
  • the light-emitting layer is a: phenylazomethine dendrimer (4th generation) ⁇ tin chloride Z polyphenylenevinylene, b: polyphenylenevinylene)
  • FIG. 5 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application.
  • the hole transport layer is a: 4- (diphenylazomethine) styrene-vinyl carbazole copolymer
  • b 4- (diphenyl azomethine) styrene-vinyl carbazole copolymer ⁇ tin chloride
  • C Polyvinyl carpazole
  • FIG. 6 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention.
  • the hole transport layer is composed of a: phenylazomethine one-pot rubazolyl asymmetric dendrimer, b: phenyl azomethine one-pot lupusole asymmetric dendrimer Eu (0T f) 3
  • FIG. 7 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention.
  • b force Lubazolide dendrimer, uncrosslinking
  • FIG. 8 is a diagram showing the lifetime (time-luminance curve) of the organic EL device constructed in the example of the invention of this application.
  • the hole transport layer is a: Carpazole dendrimer (3rd generation)
  • Photocrosslinking b Force uncrosslinked rubazole dendrimer
  • the material for an organic EL device of the present invention has a phenyl azomethine dendron subunit having a metal accumulating ability and / or a carbazole dend subunit having an excellent hole transporting property, and is easily prepared by a solution casting method. It can form a thin film. In addition, the morphological characteristics of the interface of the obtained thin film are significantly improved as compared with conventional materials for organic EL devices.
  • X is a group consisting of a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, a heterocycle and its derivatives, porphyrin and its derivatives, phthalocyanine and its derivatives, cyclam and its derivatives, and a vinyl polymer and its derivatives.
  • Y and W are the same or different, and are represented by the following formula (II): 383
  • N is a nitrogen atom
  • R 1 is a substituent selected from the group consisting of an alkylene group which may have a substituent, a phenylene group and a heterocyclic group
  • R 2 is a phenyl group optionally having one or more substituents
  • m is an integer of 1 to 6
  • a phenylazomethine dendron subunit or
  • N is a nitrogen atom and n is an integer of 1 to 6).
  • m and n in equations (11) and (III) are integers of 1 to 6 representing the number of generations in each dendro subunit, and 1 and k in equation (I) are Represents the number of connected dendrosubunits, ie, Y and W.
  • the material for an organic EL device of the invention of the present application is characterized in that at least phenylazomethine or sorbazole dend It is a combination of ronsubunits.
  • Such compounds include dendrimers having X as a core and only Y, only W, or both Y and W as dendron subunits.
  • X represents a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, a heterocycle and its derivatives, porphyrin and its derivatives, phthalocyanine and its derivatives, and cyclam And its derivatives, but for X, the phenylazomethine dendron subunit (Y) and the rubazodyl dendron subunit (W) are 1 to 6 in total. Can be combined. The number of such Y and W can be appropriately selected according to the number of possible positions of X.For example, when X is benzene, Y and W can be combined up to a total of six.
  • Y and W can bond up to a total of four.
  • X that can combine more than 6 Y and W is considered, but in that case, attention must be paid to the steric hindrance of the dendrimer.
  • At least core structure X has the following formula (VI I)
  • the method for synthesizing such phenylazomethine dendrimer, carbazole dendrimer, and phenylazomethine monofunctional rubazole asymmetric dendrimer is not particularly limited, and the Divergent method for synthesizing from the center of the dendrimer outward.
  • a known method such as the Convergent method for synthesizing from outside the dendrimer toward the center can be applied.
  • dendrons Y and W of each generation are synthesized respectively, and a core compound X having a reactive group (for example, I, Br, NH 2, etc.) is subjected to a dehydration condensation reaction in the presence of a catalyst by a convergent method.
  • a phenylazomethine dendrimer and / or a phenylazomethine asymmetric rubazole asymmetric dendrimer can be synthesized (for example, Japanese Patent Application No. 2000-02). 0 1 0; Japanese Patent Application 2 0 0 2 — 0 6 6 1 9 1; Masayoshi Higuchi, Satoshi Shiki, and Kimihisa Yaiamoto, Org. Lett. 2000, Vol. 2, No. 20, 3079-3082; Masayoshi Higuchi, Satoshi Shiki, Katsuhiko Ariga, and Kiiihisa Yaiamoto, J. Am. Chew. Soc. 2001, 123, 4414-4420).
  • Such a phenylazomethine one-pot rubazole copolymer has the following formula (X)
  • n is the same as described above, which is obtained by reacting a vinyl carbazole monomer represented by the following formula: It proceeds by heating to 80.
  • a radical initiator such as tert-butyl hydroperoxide, benzoyl peroxide, and azobisisoptirononitrile (AIBN).
  • P and Q in the phenylazomethine-carpazole copolymer of the formula (VIII) represent the phenylazomethine dendrite subunit and the carbazole dendron subunit, respectively.
  • Phenyl of formula (VIII) The azomethine-potassium rubazole copolymer may be a random copolymer or a copolymer in which phenyl azomethine dendron subunits and carbazole monodentate subunits are alternately and regularly arranged. Is also good.
  • the ratio of p to q is not particularly limited, the purpose is that phenylazomethine dendron subunit has high metal accumulation ability, and carbazole dend subunit has high hole transport ability. It can be appropriately changed according to the characteristics of the material for the organic EL element to be used.
  • R 1 in phenylazomethine dendron subunit (Y) is a substituent selected from alkylene, phenylene, a heterocyclic group and a derivative thereof, Specific examples include heterocycles such as methylene, ethylene, propylene, phenylene, pyrrole, thiophene, and oxadiazole.
  • R 2 in Y is a phenyl group which may have one or more substituents, and these substituents may further have a substituent.
  • a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, an amino group, a cyano group, a dimethylamino group, or the like may be any one of the o-, m-, and p-positions. Or a substituted phenyl group bonded to two or more sites. Since the electron density of phenylazomethine dendron subunit changes depending on the nature of R 2 (electron donating property, Z electron withdrawing property, etc.), R 2 can be appropriately selected according to the purpose and used for organic EL devices. It is possible to adjust the properties of the whole material (or the luminous efficiency of the whole organic EL device).
  • fenilazomethine dendrosubunit (Y) and W By selecting the number of generations of the knit (W), that is, the values of m and n, the hole transport property and the light emission property can be adjusted.
  • phenylazomethine dendrimer has an electron gradient due to the electron density difference (basicity) of the next-generation imine site in the molecule, so that various metals must be added.
  • has been reported to produce a stepwise complexation with the imine site in the molecule for example, Masayos i Higuc i, Satoshi Siki, and Kimihisa Yamamoto, Org. Lett. 2000, Vol. 2, No. 20, 3079-3082; Masayoshi Higuchi, Satoshi Shiki, Katsuhiko Ariga, and Kimihisa Yamamoto, J. Am. Chem. Soc.
  • phenylazomethine dendrimer phenylazomethine-potassium asymmetric dendrimer or phenylazomethine-carbazolyl copolymer Metals can be complexed with the combined phenylazomethine dendron subunits.
  • the material for an organic EL device of the invention of this application can form a dense and high-strength thin film. Since such a thin film is electrochemically stable and exhibits high heat resistance, by using it as a hole transport layer or a light emitting layer, it is possible to realize excellent luminous efficiency and high durability. . Therefore, the invention of this application also provides an organic EL device having a hole transport layer or a light emitting layer formed of a thin film containing the material for an organic EL device as described above.
  • FIG. 1 shows an outline of the organic EL device of the present invention. That is, this
  • the organic EL element (1) of the invention of the application comprises at least an anode (22), a hole transport layer (3) formed on the anode (22), and a light emitting layer (3) in contact with the hole transport layer (3). 4) and a cathode (5) in contact with the light emitting layer (4), wherein at least one of the hole transport layer (3) and the light emitting layer (4) is at least one of the organic EL devices described above. What is necessary is just to be comprised by the thin film containing the material for use.
  • the hole transport layer (3) is in contact with the anode (22) and transports holes injected from the anode (22) to the light emitting layer (4).
  • Any material may be used as long as it contains the material for an organic EL device as described above.
  • the material for an organic EL device of the invention of this application has, for example, an electron gradient due to the electron density difference (basicity) of the next-generation imine site of phenylazomethine dendrimer. Therefore, in the organic EL device (1) of the invention of this application, by using such a material for an organic EL device for the hole transport layer (3), the energy of the anode (22) and the hole transport layer (3) can be improved. (1) The gap is reduced, and the hole injection into the hole transport layer (3) and the hole transport from the hole transport layer (3) to the light emitting layer (4) can be performed efficiently. Therefore, the luminous efficiency of the organic EL device (1) can be improved, the open discharge pressure can be reduced, and the drive voltage can be reduced.
  • the light emitting layer (4) in the organic EL device (1) of the invention of the present application is a place where recombination of injected holes and electrons takes place. Any material can be used as long as it reacts to emit light.
  • Various materials generally used for organic EL devices specifically, tris (8-quinolinolato) aluminum complex (A1Q3), bis (benzoquinolinolato) ) Beryllium complex (BeBd2), bis (8-quinolato) zinc complex (ZnoJ Metal complexes such as palladium complex (Eu (TTA) 3 (phen)) and low molecular weight fluorescent dyes such as perylene, quinacridone, and coumarin thinned by vapor deposition, poly (p-phenylenevinylene) (PPV) or polyfluorene
  • A1Q3 (8-quinolinolato aluminum complex
  • BeBd2 Beryllium complex
  • ZnoJ Metal complexes such as palladium complex (Eu (TTA)
  • a polymer obtained by dissolving a ⁇ -conjugated polymer such as (PF) or a polymer containing a fluorescent dye in a side chain such as polypinylcarbazole in a solvent and forming a thin film by a wet coating method can be suitably used.
  • the light emitting layer a polymer obtained by dissolving a ⁇ -conjugated polymer such as (PF) or a polymer containing a fluorescent dye in a side chain such as polypinylcarbazole in a solvent and forming a thin film by a wet coating method.
  • the light emitting layer such as (PF) or a polymer containing a fluorescent dye in a side chain such as polypinylcarbazole in a solvent and forming a thin film by a wet coating method.
  • the light emitting layer a polymer obtained by dissolving a ⁇ -conjugated polymer such as (PF) or a polymer containing a fluorescent dye in a
  • the light emitting layer (4) shall consist of a thin film containing any of the above-mentioned materials for an organic EL device together with a material which emits light in response to energy released by recombination of holes and electrons.
  • the light emitting layer (4) contains the above-mentioned material for an organic EL device, the light emitting characteristics of the device are improved, which is preferable.
  • the material for an organic EL device of the invention of this application is capable of complexing a metal to phenylazomethine dendron subunit.
  • An electron gradient is generated based on the electron density difference (basicity). Therefore, in the organic EL device (1) of the invention of this application, the hole transport layer (3) or the light emitting layer (4) is formed of a thin film containing a metal salt together with the organic EL device material. It may be.
  • the metal integrated in the phenylazomethine dendron subunit of the material for an organic EL device of the invention of this application may be any metal as long as it can form a complex with the imine group of phenylazomethine as a ligand.
  • a metal there is no particular limitation.
  • Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag ⁇ Au, Zn, Cd, Mo, W, Mn, Sn, Eu, Tb, Nd and the like can be mentioned.
  • transition metal chlorides such as tin (Sn) chloride (SnCl 2 ), copper (Cu), iron (Fe), and gold (Au) (eg, CuCl 2 , FeCl 3 , AuCl 3, etc.) , Europium (Eu), terbium (Tb) and other rare earth metal chlorides (eg EuCl 3 , TbCl 3 ), copper trifluoromethanesulfonic acid (Cu (0Ti) 3 ), dimethyl trifluoromethanesulfonic acid (Eu (0Ti) 3 ), terpium trifluoromethanesulfonic acid (Tb (0Ti ) 3 ), and neodymium trifluoromethanesulfone (Nd (OTf) 3 ).
  • Such a complex is formed by a metal which can form a complex with the solution of the material for the organic EL device using the imine group in the phenylazomethine structure as a ligand.
  • the solvent is not particularly limited, and for example, chloroform-formacetonitrile can be used.
  • the organic EL device (1) according to the invention of the present application is further characterized in that a thin film obtained by photocrosslinking the organic EL device material is used as a hole transport layer (3) or a light emitting layer (4). May be.
  • a solution of the organic EL element material is cast to form a thin film, and then the cast film is irradiated with light to crosslink the formed dendrimer.
  • the light to be irradiated may be at least light that includes an absorption wavelength region of phenylazomethine and / or carbazole in the material for an organic EL device, and various light sources are used.
  • the wavelength range of the irradiated light is an ultraviolet light range of 500 nm or less.
  • a thin film obtained by photocrosslinking a material for an organic EL device is a film in which a carbazole group-phenyl ring is crosslinked intra- or intermolecularly by a photocrosslinking reaction.
  • a cross-linking reaction occurs at either the 3-position or the 6-position in the carbazole dendron subunit by light irradiation, and the cross-linking occurs. It becomes a film.
  • a cross-linking reaction occurs between the adjacent 2-positions of a phenyl group, and a cross-linked film is formed.
  • Such a crosslinked film has low solubility in organic solvents and is almost insoluble in general organic solvents. Therefore, if the photocrosslinked thin film is used as the hole transport layer (3), the hole transport layer (3) can be formed even if the light emitting layer (4) is further formed by casting an organic solvent solution. Does not dissolve.
  • the anode (22) is preferably made of a material having a high hole injection ability (in other words, a material having a large work function).
  • a material having a high hole injection ability for example, indium Z tin oxide (IT0) ), Tin oxide, gold or the like.
  • I0 indium Z tin oxide
  • # 0 is suitable because it has high visible light transmittance and can take out light emitted from the organic EL device (1).
  • the anode (22) may be formed on a transparent substrate (21) such as glass or plastic, and the film thickness and the like are not limited. Of course, a commercially available conductive glass may be used as the anode (22).
  • the material and thickness of the cathode (5) are not particularly limited as long as the cathode (5) has conductivity and can achieve the purpose of injecting electrons ( ⁇ ) into the light emitting layer (4).
  • a group III metal such as an alkali metal, an alkaline earth metal, aluminum, gallium, and indium having a low work function is used.
  • alloys of magnesium and silver or copper, which are chemically stable and inexpensive, and aluminum alloys which are inexpensive and easy to form films Pum is preferred. These materials may be formed on a transparent substrate such as glass or plastic.
  • the organic EL device (1) of the invention of this application can be used as a flat panel display of various devices such as a mobile phone, a notebook computer, and a PDA by being combined with a conductor, a power cable, a filter, and the like. Things.
  • Anode A 3 mm wide anode was prepared by etching the IT0 surface of an IT0 glass electrode (20 mm X 20; Oji Tobi) with hydrochloric acid. .
  • Phenylazomethine dendrimer (4th generation) represented by the formula below is dissolved in 1 ml of 1 ml dendrimer with 1 ml of black-mouthed form, and spin-cast method (2,500 rpm, 2 times at 1 minute intervals) A 500 A thick hole transport layer was formed by casting.
  • Light-emitting layer A3 (Tokyo Kasei Co., Ltd.) was applied to the obtained hole-transporting layer using a vacuum evaporation apparatus (Ulvac VPC-410A) under a reduced pressure of 50 ⁇ 10 " 6 Torr to 2-3 A. Vacuum deposition was performed at a deposition rate of / sec to form a light emitting layer (electron transporting property) with a thickness of 500A.
  • A1 was vacuum deposited at a deposition rate of 2 to 5 A / sec under the same conditions as in (c) to form a cathode having a thickness of 1000 A.
  • the obtained organic EL device with an area of 0.1 cm 2 was 2383 Voltage-current and voltage-luminance measurements were performed.
  • the characteristics of the organic EL device are shown in FIG. 2a.
  • step (b) of forming the hole transport layer in Example 1 1 equivalent of tin chloride was used together with the phenylazomethine dendrimer of the formula (IV-a) (based on the number of imines in the phenylazomethine dendrimer).
  • tin chloride 1 equivalent of tin chloride was used together with the phenylazomethine dendrimer of the formula (IV-a) (based on the number of imines in the phenylazomethine dendrimer).
  • acetonitrile complexed, concentrated, and spin-cast under the same conditions as in Example 1 to form a 500 A thick hole transport layer.
  • the maximum luminance was 18000 cd / m 2 at 12 V, and the luminous efficiency at a luminance of 300 cd / m 2 was as high as 2.6 lm / W.
  • the turn-on voltage was about 4 V and the dendrimer alone was used as the hole transport layer, the voltage was reduced by 1.5 V or more compared to the case where the hole transport layer was used (Example 1).
  • phenylazomethine dendrimer-metal complex as a hole transport material significantly reduced the power consumption of organic EL devices. It was confirmed that it can be reduced.
  • the maximum luminance was 4500 cd / m 2 at 14 V, and the luminous efficiency at a luminance of 300 cd / m 2 was 1.8 lm / W. It also has a turn-on voltage of about -5.0 V, and unsubstituted phenylazomethine dendrites It was confirmed that the device exhibited higher device characteristics than the case where the mask was used as the hole transport layer (Example 1). This is probably because the introduction of an electron-donating dimethylamine group into the dendrimer terminal increased the electron density inside the dendrimer.
  • a mouth form solution of polyvinyl carpazole was prepared, and this mouth form solution was spin-cast under the same conditions as in Example 1 to form a hole transport layer having a thickness of 500 persons.
  • An oral form solution of polyvinyl carbazole was prepared, and the phenylazomethine dendrite of formula (IV-a) used in Example 1 (4th generation) was added to the polyvinyl carbazole. And 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer).
  • This black-hole form solution was spin-cast under the same conditions as in Example 1 to form a hole transport layer having a thickness of 500 A.
  • the obtained organic EL device showed a maximum brightness 1500 cd / m 2 at 10 V, the luminous efficiency at luminance 300 cd / m 2 showed a 3.5 li / W and high emission efficiency Was. Furthermore, the turn-on voltage reaching 0.1 cd / m 2 was about 3 V, and the polypinylcarbazole of Comparative Example 1 was used as the hole transport layer (without phenylazomethine dendrimer). V or more dropped. Therefore, low power consumption of the device was confirmed.
  • Hole transport layer An aqueous solution of poly (3,4-ethylenedioxythiophene) -polystyrenesulfonic acid (PED0T: PSS) was spin-cast under the same conditions as in Example 1 to obtain a 300-A thick layer. A hole transport layer was formed.
  • Light-emitting layer A benzene solution of a polyphenylenevinylene derivative (MEH-PPV) was prepared and spin-cast to form a light-emitting layer having a thickness of 500A.
  • MEH-PPV polyphenylenevinylene derivative
  • Fig. 4b shows the characteristics of the organic EL device.
  • a hole transport layer was formed in the same manner as in Comparative Example 2, and a phenylenevinylene derivative (MEH-PPV) was added thereto with 1% by weight of a phenylazomethine dendrimer of the formula (IV-a) (MEH-PPH).
  • MEH-PPV phenylenevinylene derivative
  • a chlorobenzene solution containing 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer) and 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer) was spin-cast to form a light emitting layer having a thickness of 500A.
  • This organic EL device exhibited a maximum luminance of 850 cd / i 2 at 11 V and a high luminous efficiency of 2.1 lm / at a luminance of 300 cd / m 2 .
  • the turn-on voltage reaching 0.1 cd / m 2 was 4.5 V, which was 1 V higher than that of the organic EL device in which only the MEH-PPV of Comparative Example 2 was used as the light emitting layer (does not include the ferazomethine dendrimer). It fell above. Therefore, low power consumption of the device Power consumption was confirmed.
  • the obtained compound was identified by GPC, 1H-NM, and UV.
  • Example 2 Compound b (2 mg) obtained in Example 1 was dissolved in black hole form, and a thin film having a thickness of 500 A was formed on an IT0 glass electrode by a spin casting method to form a hole transport layer. Aid was vacuum-deposited thereon to form a thin film having a thickness of 500 A, which was used as a light emitting layer and an electron transport layer. Further, A1 was formed as a cathode to a thickness of 1000 A, and an organic EL element having an area of 0.1 cm 2 was produced.
  • Example 7 An acetonitrile solution of the compound b used in Example 7 and an acetonitrile solution of tin chloride U equivalent (based on the imine number of the dendron of the copolymer) was mixed, and the solvent was concentrated. A thin film was formed in the same manner as in Example 7, and used as a hole transport layer. An organic EL device was manufactured in the same manner as in Example 7.
  • This organic EL device exhibited a maximum luminance of 9000 cd / m 2 at 10 V and a high luminous efficiency of 1.7 lm / W at a luminance of 300 cd / m 2 .
  • the turn-on (drive) voltage is about 4.1 V, which is 2.0 V or more, and that PVK is used as the hole transport layer when a hole transport layer not complexed with a metal is used (Example 5). 1.0V or more lower than the case (Comparative Example 3) It was confirmed that the power consumption of the device could be reduced.
  • the use of a copolymer in which metals are integrated (complexed) as a hole transport layer increased the luminous efficiency of the organic EL device and further reduced the turn-on (drive) voltage at the hole injection electrode. This is probably because the energy gap between a certain IT0 and the hole transport layer became smaller, and the efficiency of hole injection into the hole transport layer increased.
  • Table 1 shows the identification results of the obtained phenylazomethine monocyclic rubazole asymmetric dendrimers.
  • Example 7 a solution of the c-form of compound c and an acetonitrile solution of Eu (0Ti) 3 (1 equivalent: based on the number of imines of phenylazomethine dendron) were mixed and complexed, and the same as in Example 7 was performed.
  • the organic EL device was constructed in the following manner.
  • Anode IT0 glass electrode (20 mm x 20 bandages; Oji Tobi)
  • the IT0 surface was etched with hydrochloric acid to prepare a 3 nun-wide anode and used.
  • the carbazole dendrimer (3rd generation) represented by is dissolved in a black hole form and a hole transport layer having a thickness of 500 A was formed by spin casting.
  • Emission layer Thickness is determined by casting using a toluene solution of PPV.
  • the voltage-current and voltage-brightness of the obtained organic EL device were measured at room temperature in the atmosphere, and the results are shown in FIG. 7A.
  • Orange color light emission was confirmed by applying a voltage of 3 V or more with the IT0 electrode as the positive electrode.
  • the maximum luminance at 11 V was 8000 cd / m 2
  • the light emission efficiency at the time of light emission at 300 cd / m 2 was 1.51 mW.
  • the half-life at a luminance of 100 cd / i 2 under vacuum conditions was 1000 hours or more, confirming excellent durability.
  • a carbazole dendrimer having the same thickness is cast, dried without forming photocrosslinking to form a hole transport layer, and then spin-cast using a toluene solution of PPV as a light emitting layer.
  • the measurement results of the EL element formed and the back electrode were prepared are shown in FIGS. 7b and 8b.
  • the hole transport layer may be solubilized when the light emitting layer is cast. Either create the light emitting layer by vacuum evaporation or use a solution caster that uses a solvent that does not erode the hole transport layer. It was suggested that it is desirable to use a cross-linking method or to prepare a cross-linking method.
  • a phenylazomethine dendron subunit having a metal accumulating ability and / or a carbazole dendron subunit having an excellent hole transporting property are provided.
  • a material for an organic EL device having a thin film easily formed by a solution casting method.
  • a dense and high-strength film having improved morphological characteristics at the interface can be formed.
  • Such a thin film is electrochemically stable and exhibits high heat resistance.
  • it is expected that the luminous efficiency of the organic EL device is improved, the open-circuit voltage is reduced, and the drive voltage is further reduced. High usefulness.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un matériau conçu pour un dispositif électroluminescent organique, caractérisé en ce qu'il comprend au moins un composé de formule (I) : (W)k-X-(Y)1, dans laquelle X représente une fraction de noyau ; Y et M représentent, indépendamment l'un de l'autre, une sous-unité dendritique de phénylazométhine ou une sous-unité dendritique de carbazole ; 1 représente un nombre entier indiquant le nombre d'Y liés à X ; et k représente un nombre entier indiquant le nombre de W liés à X.
PCT/JP2004/002383 2003-02-27 2004-02-27 Materiau conçu pour un dispositif electroluminescent organique et dispositif electroluminescent produit a partir de celui-ci WO2004077888A1 (fr)

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JP2006188673A (ja) * 2004-12-07 2006-07-20 Sumitomo Chemical Co Ltd 高分子材料およびそれを用いた素子
US20160099419A1 (en) * 2014-10-02 2016-04-07 Samsung Display Co., Ltd. Organic electroluminescent material and organic electroluminescent device including the same

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JP2004018787A (ja) * 2002-06-19 2004-01-22 Fuji Photo Film Co Ltd カルバゾール誘導体、並びにそのポリマー、及びそれを含有する発光素子

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KIMIHISA YAMAMOTO ET AL.: "Stepwise radical complexation of imine groups in phenylazomethines dendrimers", NATURE, vol. 415, 31 January 2002 (2002-01-31), pages 509 - 511, XP002982578 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006188673A (ja) * 2004-12-07 2006-07-20 Sumitomo Chemical Co Ltd 高分子材料およびそれを用いた素子
US20160099419A1 (en) * 2014-10-02 2016-04-07 Samsung Display Co., Ltd. Organic electroluminescent material and organic electroluminescent device including the same

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