Classifications

• • 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
• • 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
  • 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
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/30—Coordination compounds
  • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
  • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2101/00—Properties of the organic materials covered by group H10K85/00
  • H10K2101/10—Triplet emission

Definitions

• the present invention relates to an organic electroluminescent element material having a carbazole skeleton, an organic luminescent element containing the organic electroluminescent element material, an illumination device, and a display element.
• an organic electroluminescence element (hereinafter, electroluminescence may be abbreviated as EL), a light emitting material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. It is a self-luminous element utilizing the principle.
• a doping method is generally used in which a host is doped with a light emitting material as a dopant. As the host, it is necessary to efficiently generate excitons from the charge injected from the carrier transport layer, transfer the excitons to the dopant, and as the dopant, convert the excitons to emission energy with high efficiency. It is done.
• an object of the present invention is to provide an organic EL material that is excellent in solvent solubility and suitable for production by a printing method, and that can emit light with high efficiency because of high triplet energy. It is another object of the present invention to provide an organic EL element, a display element, and a lighting device using the organic EL material.
• R 1 and R 2 are each independently a hydrogen atom; an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group; or polymerizable reactive group. Represents a group having
• an organic EL element characterized by using the organic EL material is provided.
• the display element and illumination device which have the said organic EL element are provided.
• the organic EL device material represented by the above formula (1) has a twist between carbazoles, the triplet energy is increased, and the reverse energy transfer from the dopant to the host is suppressed, so that highly efficient light emission is possible. Furthermore, since it is excellent in solvent solubility, it can be suitably used for the production of an organic EL device by a printing method.
• the organic EL device material of the present invention has a structure represented by the following formula (1).
• R 1 and R 2 are each independently a hydrogen atom; an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group; or polymerizable reactive group. Represents a group having
• the material for an organic EL device of the present invention may have a 1,3′-biscarbazole structure represented by the above formula (1), and the structure represented by the above formula (1) may be one or plural. Absent.
• the organic EL device material of the present invention has a 1,3′-biscarbazole structure having a twist between two carbazoles, and therefore has a small conjugate length and high triplet energy. Therefore, reverse energy transfer does not occur from the dopant to the host, and good light emission characteristics can be obtained. Since the material for an organic EL device of the present invention has a high triplet energy level, not only green and red phosphorescent materials but also blue phosphorescent materials are effective as host materials. Moreover, since the solubility in a solvent is excellent due to the twisted structure of the molecule, the organic EL element can be produced by a printing method using an ink for an organic EL element. Moreover, since Tg is high, it is excellent in heat resistance.
• R 1 and R 2 are each independently a hydrogen atom; an alkyl group which may have a substituent, An alkenyl group, an alkynyl group, an aryl group, a heteroaryl group; or a group having a polymerizable reactive group.
• hydrogen includes deuterium
• Alkyl groups having 1 to 10 carbon atoms are preferred, and are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclopentyl, cyclohexyl, cyclo A heptyl group etc. are mentioned.
• Group, spirofluorenyl group, and fluoranthenyl group, and when having a substituent, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a halogeno group, and a cyano group are preferable.
• one hydrogen atom is removed from pyridine, pyrazine, pyrimidine, pyridazine, and triazine.
• the monovalent group etc. which can be mentioned are mentioned.
• preferred substituents include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a halogeno group, a cyano group, a substituted amino group, a phenyl group, a biphenyl group, and a terphenyl group. And a naphthyl group.
• Examples of the polymerizable reactive group include a cationic polymerizable reactive group and a radical polymerizable reactive group.
• Examples of the cationic polymerizable reactive group include a cyclic ether group such as an epoxy group and an oxetanyl group, and a radical polymerizable reaction.
• Examples of the functional group include ethylenically unsaturated groups such as a vinyl group, a (meth) acryloyl group, an allyl group, a styryl group, and a maleimide group.
• These polymerizable groups may have a linking group such as an alkylene group, an alkyleneoxy group, an arylene group, or a heteroarylene group between 1,3′-biscarbazole.
• the structure represented by the above formula (1) may be a low molecular compound or a high molecular compound. When it has a polymerizable reactive group, it may be reacted with another monomer to form a copolymer.
• substituents an aryl group that may have a substituent, a heteroaryl group that may have a substituent, and an alkyl group that may have a substituent are preferable, and luminous efficiency is increased.
• An aryl group which may have a substituent and a heteroaryl group which may have a substituent are more preferable.
• the structure represented by the above formula (1) is obtained by heating and stirring 1,2,3,4-tetrahydrocarbazole in activated carbon, or by a coupling reaction of a 1-position halogenated carbazole derivative and a 3-position boronic acid carbazole derivative. Can be synthesized.
• the structure represented by the above formula (1) includes a portion other than the 1-position and 3′-position of the carbazole ring (2,3,4,5,6,1 ′, 2 ′, 4 ′, 5 ′, 6 ′).
• Each independently has a hydrogen atom; an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group; or a group having a polymerizable reactive group. be able to.
• alkyl group an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group which may have a substituent; or a group having a polymerizable reactive group is the same as the above definition.
• the structure represented by the above formula (1) includes a portion other than the 1-position and 3′-position of the carbazole ring (2,3,4,5,6,1 ′, 2 ′, 4 ′, 5 ′, 6 ′).
• Substituents can be easily modified by halogenation. From the viewpoint of ease of synthesis, the 4-position, 6-position and 6'-position are preferred as the position for modifying the substituent.
• the organic EL device material of the present invention can be used as an active layer material of an organic EL device.
• the active layer means a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, an electron injection layer, or the like of the organic EL element.
• the organic EL element material of this invention has a high triplet level, it is effective for a positive hole transport layer or a light emitting layer, Especially preferably, it is a light emitting layer.
• the organic EL device material of the present invention can be used in the fields of electrophotographic photoreceptors, transistors, solar cells, etc. in addition to the active layer material of the organic EL device.
• the organic EL device material of the present invention When used for a light emitting layer, it can be particularly suitably used as a host material. At this time, a known and commonly used material can be used as the light emitter, but it is preferably used as a host material of a phosphorescent light emitting material because of its large triplet level.
• an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold can be used.
• Preferred phosphorescent light emitting materials include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as Ir (bt) 2 .acac 3 , complexes such as PtOEt 3 and the like. . Specific examples of these complexes are shown below, but are not limited to the following compounds.
• the amount of the phosphorescent light emitting material contained in the light emitting layer is 1 to 25% by weight, preferably 5 to 20% by weight.
• the organic EL device material of the present invention may be 50% by weight or more, preferably 80 to 95% by weight.
• the organic EL device material of the present invention can be used as a vapor deposition material as it is, but since it is excellent in solvent solubility, it is preferably dissolved in a solvent and used as an organic EL device ink.
• Any organic solvent may be used, or two or more organic solvents may be mixed and used.
• aliphatic solvents such as n-hexane, n-octane, n-decane, and n-dodecane
• alicyclic solvents such as cyclohexane
• the organic EL element ink may contain other compounding materials in addition to the organic EL element material as long as the organic EL element characteristics are not impaired. It may contain a transport material, an electron injection material, an electron transport material, a light emitting material, a binder polymer and the like.
• the ink may contain a light emitting material in addition to the present material.
• a well-known and usual material can be used as a light-emitting body, since the organic EL element material of this invention has a large triplet level, it is preferable to use it for a phosphorescent light-emitting material.
• the amount of the phosphorescent light-emitting material contained in the organic EL element ink is 1 to 30% by weight, preferably 5 to 25% by weight, based on the organic EL element material of the present invention.
• the organic EL device material of the present invention may be 50% by weight or more, preferably 75 to 95% by weight.
• the blending amount of the organic EL element material of the present invention may be 0.1 wt% to 10 wt% in the organic EL element ink, preferably 0.1 wt% to 5.0% by weight.
• Organic EL device The structure of the organic EL element is not particularly limited, but generally an electroluminescent layer (light emitting layer) is included between a cathode (cathode) and an anode (anode) in which at least one of the electrodes is transparent. It is a waste. Furthermore, one or more electron injection layers and / or electron transport layers are inserted between the electroluminescent layer (light emitting layer) and the cathode, one or more hole injection layers and / or hole transport In some cases, a layer is inserted between the electroluminescent layer (light emitting layer) and the anode.
• the anode plays a role of hole injection into the hole injection layer and is usually made of metal such as aluminum, gold, silver, nickel, palladium, platinum, indium and / or tin oxide (ITO), etc. It is composed of a metal oxide, a metal halide such as copper iodide, carbon black, or a conductive polymer such as poly (3-methylthiophene, polypyrrole, polyaniline).
• metal such as aluminum, gold, silver, nickel, palladium, platinum, indium and / or tin oxide (ITO), etc. It is composed of a metal oxide, a metal halide such as copper iodide, carbon black, or a conductive polymer such as poly (3-methylthiophene, polypyrrole, polyaniline).
• the cathode plays a role of injecting electrons into the light emitting layer through the electron transport layer / or electron injection layer.
• the material used as the cathode is preferably a metal having a low work function in order to efficiently inject electrons, and an appropriate metal such as tin, magnesium, indium, calcium, cesium, aluminum, silver, or an alloy thereof is used. . Specific examples include a magnesium-silver alloy, a magnesium-indium alloy, and an aluminum-lithium alloy.
• the hole injection layer, hole transport layer, and electron transport layer can be any organic layer, but the hole injection layer is used for the purpose of increasing the efficiency of injecting holes from the anode into the hole transport layer.
• the hole transport layer and the electron transport layer serve to move holes and electrons to the light emitting layer, respectively.
• an electron injection layer can be provided between the cathode and the electron transport layer.
• the hole injection material examples include phthalocyanine compounds such as copper phthalocyanine (CuPc), organic compounds such as polyaniline and polythiophene, and metal oxides such as vanadium oxide, ruthenium oxide, and molybdenum oxide.
• phthalocyanine compounds such as copper phthalocyanine (CuPc)
• organic compounds such as polyaniline and polythiophene
• metal oxides such as vanadium oxide, ruthenium oxide, and molybdenum oxide.
• hole transport materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives such as NPB, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene Derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like can be given.
• a metal complex such as Alq 3, 10- hydroxy-benzo [h] quinoline metal complexes, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3- or 5-hydroxyflavone metal complexes, benzoxazole Metal complex, benzothiazole metal complex, trisbenzimidazolylbenzenequinoxaline compound, phenanthroline derivative, 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type Examples thereof include zinc sulfide and n-type zinc selenide.
• Examples of the electron injection layer include alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earth metal complexes, alkaline earth metal complex compounds, rare earth metals, rare earth metal complexes, and rare earth metal compounds. .
• the organic EL element material of the present invention is used as an organic EL element, a known and usual vapor deposition method may be used, but a coating method such as a printing method is preferably used.
• a coating method such as a printing method.
• the coating method used include a dipping method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and a liquid dropping method such as an inkjet method. Can be mentioned.
• the organic EL element having the organic EL element material of the present invention is excellent in heat resistance, it can be suitably used as a display device or a lighting device.
• the display element can be applied to both a display element having a structure arranged in an array and a display element having an anode and a cathode arranged in an XY matrix, and is applied to a full-color or multi-color panel. be able to.
• the lighting device can be applied to a monochromatic or dimmable lighting device.
• a white solid (compound 6) was prepared in the same manner as in Synthesis Example 1, except that 1-bromo-4-t-butylbenzene (1.287 g, 6.04 mmol) was used instead of 4-bromo-N, N′-diphenylaniline. ) 0.9 g (yield 60%) was obtained.
• 1 HNMR (CDCl 3 , 300 MHz): ⁇ 8.36 (s, 1H), 8.08 (d, 1H), 7.67-7.16 (m, 19H), 6.84 (t, 1H), 1 .35 (s, 18H)
• MS spectrum HPLC-MS (APCI), eluent; acetonitrile): m / z: 596
• GD-1 lithium fluoride 0.5 nm as an electron injection layer
• aluminum 100 nm as a cathode.
• the content of GD-1 was 10 wt%. After film formation up to the cathode, the substrate was transported to a glove box and sealed with a glass substrate to produce an organic EL device.
• a PEDOT / PSS film having a thickness of 45 nm was formed by spin coating as a hole injection layer and heated in the atmosphere at 180 ° C. for 15 minutes. Subsequently, a 10 nm film was formed by spin coating using a 0.3 wt% xylene solution of HT-2, and dried at 200 ° C. for 30 minutes in a nitrogen atmosphere.
• a 30 nm film was formed by spin coating using a toluene solution containing a host material and GD-1 at a weight ratio of 9: 1 and having a solid concentration of 0.8% by weight. And dried at 110 ° C. for 15 minutes. Thereafter, under a vacuum of 5 ⁇ 10 ⁇ 3 Pa, ET-1 as an electron transport layer was deposited to 45 nm, lithium fluoride as an electron injection layer was 0.5 nm, and aluminum as a cathode was sequentially deposited to 100 nm. After film formation up to the cathode, the substrate was transported to a glove box and sealed with a glass substrate to produce an organic EL device.
• Luminance measurement of organic EL element The organic EL element produced as described above was connected to an external power source, a DC voltage was applied, and light emission from the element was measured with a Topcon BM-9. Luminous efficiency was calculated from the value. The table below shows the voltage and luminous efficiency when 10 mA / cm 2 current was applied.
• Example 1 The results of evaluating the compounds of the present invention obtained in Examples 1 to 9 by the above evaluation method are shown in Table 1.
• the compound of the present invention exhibits high luminous efficiency in both the vapor deposition element and the coating element. It has been found that the compound of the present invention is advantageous in the production of a coating element because it is superior in solvent solubility than the conventional compound.
• the material for an organic EL element of the present invention can be suitably used for an organic EL element.

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• 2014
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