WO2012105600A1 - 有機エレクトロルミネッセンス素子の製造方法 - Google Patents
有機エレクトロルミネッセンス素子の製造方法 Download PDFInfo
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- WO2012105600A1 WO2012105600A1 PCT/JP2012/052247 JP2012052247W WO2012105600A1 WO 2012105600 A1 WO2012105600 A1 WO 2012105600A1 JP 2012052247 W JP2012052247 W JP 2012052247W WO 2012105600 A1 WO2012105600 A1 WO 2012105600A1
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- 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
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/125—Active-matrix OLED [AMOLED] displays including organic TFTs [OTFT]
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
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- 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
Definitions
- the present invention relates to a method of manufacturing an organic electroluminescent device.
- An organic EL display (hereinafter, referred to as an "organic EL display") using an organic electroluminescent element (hereinafter, referred to as an “organic EL element”) has attracted attention.
- An organic EL element used for an organic EL display includes an anode, a cathode, and a light emitting layer disposed between the anode and the cathode, and holes and electrons respectively injected from the anode and the cathode are It emits light by binding in the light emitting layer.
- the organic EL element has an advantage that an organic layer such as a light emitting layer can be formed by a coating method in which the manufacturing process is simple and the enlargement of the element is easy. Specifically, the organic layer can be formed using a solution containing the organic compound and the organic solvent contained in the organic layer.
- the method of forming the organic layer of the organic EL element the method of manufacturing the organic EL element having a water concentration of 1,000 ppm or less in the atmosphere for forming the light emitting layer (Patent Document 1)
- Patent Document 2 A method of manufacturing an organic EL element (Patent Document 2) has been proposed in which the organic layer is manufactured by a wet method in an inert gas atmosphere having an oxygen concentration of 10 ppm or less.
- JP 2002-352954 A Unexamined-Japanese-Patent No. 2006-185864
- the length of the light emission life of the organic EL device manufactured by the above method is not always sufficient, and a method capable of manufacturing an organic EL device having a longer light emission life has been desired.
- An object of the present invention is to provide a method capable of manufacturing an organic EL device having a long light emission lifetime, an organic EL device manufactured by the method, a planar light source provided with the organic EL device, a lighting device and a display device. .
- the present invention comprises a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode, wherein the organic layer contains an organic compound.
- a method, wherein the organic layer is An organic thin film forming step of forming an organic thin film containing an organic compound by a coating method on a surface of a layer on which the organic layer is formed under a low humidity atmosphere having a water concentration of 10 ppm or less on a volume basis; An organic thin film storage step of storing the organic thin film obtained by the organic thin film formation step under a high humidity atmosphere having an absolute humidity of 2.0 ⁇ 10 -3 kg / kg (dry air) or more based on weight; Provided is a method of manufacturing an organic EL device, which is formed by the method including.
- the high humidity atmosphere has an absolute humidity on a weight basis of 2.0 ⁇ 10 ⁇ 3 kg / kg (dry air) or more and 2.0 ⁇ 10 ⁇ 2 kg / kg (dry air) or less .
- the high humidity atmosphere has an absolute humidity on a weight basis of 5.0 ⁇ 10 ⁇ 3 kg / kg (dry air) or more and 1.5 ⁇ 10 ⁇ 2 kg / kg (dry air) or less .
- the low humidity atmosphere contains an inert gas.
- the low humidity atmosphere has an oxygen concentration of 10 ppm or less on a volume basis.
- the organic thin film forming step and the organic thin film storing step are performed by sequentially passing the substrate through the space of the atmosphere in which the organic thin film forming step is performed, the buffer space, and the atmosphere of the organic thin film storing step.
- the pressure in the buffer space is negative compared to the space for performing the organic thin film formation process and the space for performing the organic thin film storage process.
- the organic thin film formation step and the organic thin film storage step are performed by sequentially passing the substrate through the space of the atmosphere in which the organic thin film formation step is performed and the space of the atmosphere in which the organic thin film storage step is performed.
- the pressure in the space where the thin film formation process is performed is positive as compared to the space where the organic thin film storage process is performed.
- the step of storing the organic thin film is followed by the step of baking the organic thin film.
- the step of firing the organic thin film is performed under an atmosphere containing an inert gas.
- the step of firing the organic thin film is performed under an atmosphere having an oxygen concentration and a water concentration of 10 ppm or less on a volume basis.
- the step of firing the organic thin film is performed under a reduced pressure atmosphere having a pressure of 10 Pa or less.
- the first electrode is an anode and the second electrode is a cathode.
- the organic layer comprises a polymeric organic compound.
- the organic layer is a light emitting layer.
- the organic layer comprises a phosphorescent compound.
- the method further includes the step of forming a functional layer in contact with the light emitting layer.
- the functional layer is formed between the light emitting layer and the first electrode.
- the functional layer comprises a polymeric organic compound.
- this invention provides the organic EL element manufactured by the manufacturing method of the organic EL element in any one of the said.
- the present invention provides a planar light source comprising the organic EL element.
- the present invention provides a display device comprising the organic EL element.
- an organic EL element having a long light emission life can be manufactured. Further, such an organic EL element is suitably used as a flat or curved surface light source used for illumination and the like; a display device such as a segment display device and a dot matrix display device; a backlight such as a liquid crystal display device and the like.
- FIG. 1 is a view schematically showing one form of the organic EL device manufactured by the method of the present invention.
- the organic EL element 1 is provided on a substrate 2 and has a first electrode 3, a second electrode 7, and an organic layer 6 provided between the first electrode and the second electrode.
- the organic layer 6 contains an organic compound.
- a typical function of each of the layers constituting the organic EL element 1 is that the first electrode 3 is an anode, the second electrode 7 is a cathode, and the organic layer 6 is a light emitting layer.
- the organic layer 6 includes an organic thin film forming step of forming an organic thin film which is a thin film containing an organic compound on the first electrode 3, and an organic thin film storage step of storing the obtained organic thin film under high humidity atmosphere Are formed by a method including: Details of other components of the organic EL element 1 will be described later.
- the thin film containing the organic compound may be formed in the same manner as in the prior art, preferably by a coating method in which the manufacturing process is simple and the element can be easily enlarged.
- the coating method is preferably performed under a low humidity atmosphere having a water concentration of 10 ppm or less, preferably 5 ppm or less, more preferably 1 ppm or less on a volume basis. By doing so, the element characteristics of the organic EL element are improved.
- the organic thin film is preferably formed under atmospheric pressure or in an atmosphere containing an inert gas.
- the inert gas may, for example, be helium gas, argon gas, nitrogen gas, or a mixed gas thereof. Among them, nitrogen gas is preferable from the viewpoint of the easiness of device fabrication.
- the organic thin film may be formed in the atmosphere, or may be formed in an atmosphere in which the concentration of the inert gas in the atmosphere is equal to or higher than the concentration of the inert gas contained in the atmosphere.
- the organic thin film is preferably formed in an atmosphere having an oxygen concentration of 1,000 ppm or less on a volume basis, and more preferably formed in an atmosphere having an oxygen concentration of 100 ppm or less on a volume basis, from the viewpoint of device lifetime characteristics. More preferably, the oxygen concentration is 10 ppm or less by volume.
- the solvent used to form the organic thin film by the coating method is not particularly limited as long as it is a liquid at 1 atm and 25 ° C.
- it is selected from the group consisting of carbon atom, hydrogen atom, oxygen atom, nitrogen atom and sulfur atom
- It is a compound consisting of two or more atoms selected, more preferably a compound consisting of two or more atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, still more preferably carbon
- It is a compound which consists of 2 or more types of atoms chosen from the group which consists of an atom, a hydrogen atom, and an oxygen atom.
- organic solvents examples include halogenated solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, water. Further, two or more types of organic solvents may be used in combination.
- halogenated solvents include carbon tetrachloride, methylene chloride, chloroform, dichloroethane, tetrachloroethylene, chlorobenzene, bis (2-chloroethyl) ether, chloromethylethylether, chloromethylmethylether, 2-chloroethylethylether, -Chloroethyl methyl ether is mentioned.
- hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, decahydronaphthalene, petroleum ether, ligroin.
- aromatic hydrocarbon solvent examples include benzene, toluene, xylene, ethylbenzene, cumene, pseudocumene, trimethylbenzene, butylbenzene, tetramethylbenzene, tert-butylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, Examples include decatylbenzene, tetralin, cyclohexylbenzene, decalin and methyl naphthalene.
- ether solvent diethylether, ethylpropylether, dipropylether, diisopropylether, dibutylether, methyl tert-butylether, anisole, methylanisole, diphenylether, phenoxytoluene, phenoxyxylene, phenoxyxylene, ditolylether, tetrahydrofuran, dihydrofuran, dioxane, Tetrahydropyran, 4-methyl-1,3-dioxane, 4-phenyl-1,3-dioxane can be mentioned.
- the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2 -Pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, cyclopentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol , 2,2-dimethyl-1-propanol, 3-hexanol, 2-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol, 2,4-dimethyl-3- Pentanol, 3-Heptanol, 4-Heptanol, 2-Heptanol, 1-Heptanol, 2-Ethanol -1-hexanol, 2,6-dimethyl-4-h
- ketone solvent examples include acetone, methyl ethyl ketone, methyl iso-butyl ketone, cyclohexanone, isopropyl methyl ketone, 2-pentanone, 3-pentanone, 3-hexanone, diisopropyl ketone, 2-hexanone, cyclopentanone, 4-heptanone and iso.
- nitrile solvents include acetonitrile, acrylonitrile, trichloroacetonitrile, propionitrile, pivalonitrile, isobutyro nitrile, n-butyro nitrile, methoxyacetonitrile, 2-methylbutyro nitrile, isovaleronitrile, N- valeronitrile, n -Capronitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile, 3,3'-oxydipropionitrile, n-heptanenitrile, glycolonitrile, benzonitrile, ethylene cyanohydrin, succinonitrile, acetone Examples include cyanohydrin and 3-n-butoxypropionitrile.
- sulfoxide solvent examples include dimethyl sulfoxide, di-n-butyl sulfoxide, tetramethylene sulfoxide and methylphenyl sulfoxide.
- amide solvent examples include dimethylformamide, dimethylacetamide, acylamide, 2-acetamidoethanol, N, N-dimethyl-m-toluamide, trifluoroacetamide, N, N-dimethylacetamide, N, N-diethyldodecane amide, Epsilon-caprolactam, N, N-diethylacetamide, N-tert-butylformamide, formamide, pivalamide, N-butylamide, N, N-dimethylacetoacetamide, N-methylformamide, N, N-diethylformamide, N-formylethylamine Acetamide, N, N-diisopropyl formamide, 1-formylpiperidine, N-methylformanilide, N-methylpyrrolidone.
- one type of solvent is a solvent having a boiling point of 180 ° C. or more
- the other type of solvent is a solvent having a boiling point of 180 ° C. or less
- one solvent is a solvent having a boiling point of 200 ° C. or more
- the other solvent is a solvent having a boiling point of 180 ° C. or less.
- At least one of the three types of solvents is a solvent having a boiling point of 180 ° C. or higher, and at least one type of solvent has a boiling point of 180 from the viewpoint of film formability.
- at least one of the three solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is a solvent having a boiling point of 180 ° C. or less It is more preferable that
- Coating methods include spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating and A coating method such as a nozzle coating method, and a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method can be mentioned.
- Coating methods such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method are preferable in that pattern formation and multicolor separation are easy.
- the organic thin film storage step of storing the formed organic thin film is usually performed following the organic thin film formation step.
- the organic thin film formed in the organic thin film formation step is stored in the organic thin film storage step.
- the organic thin film storage step the organic thin film is stored under an atmosphere in which the absolute humidity on a weight basis is kept at 2.0 ⁇ 10 ⁇ 3 kg / kg (dry air) or more. By doing so, the light emission lifetime of the organic EL element is extended.
- the "absolute humidity on a weight basis” is expressed with a unit “kg / kg (dry air)” and is defined by "the weight of water vapor accompanying 1 kg of dry air". In the following, "kg / kg (dry air)” may be described as “kg / kg (DA)”.
- the formed organic thin film stores water on the surface by being stored in an environment higher in humidity than dry air.
- the moisture accumulated on the surface of the organic thin film affects the interface characteristics with the film formed on the surface.
- the resistance applied between the films slightly changes, and the influence such as a change in current amount is considered.
- the electrode when the electrode is formed on the surface of the organic thin film, the water present on the surface of the organic thin film causes the electrode to be slightly degraded.
- slightly degrading the electrode in advance before driving the organic EL element even if the electrode is degraded after driving the organic EL element, a sharp drop in the amount of current is prevented, and as a result, the light emission of the organic EL element Life is extended.
- the organic thin film has an absolute humidity of 2.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more and 2.0 ⁇ 10 ⁇ 2 kg / kg (DA) in terms of the life characteristics of the organic EL element. It is preferable to store under an atmosphere maintained below, and the absolute humidity on a weight basis is 5.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more, 2.0 ⁇ 10 ⁇ 2 kg / kg (DA) It is more preferable that it is the following.
- the absolute humidity on a weight basis is 5.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more, 1.5 ⁇ 10 ⁇ 2 kg It is further preferred that the organic thin film be stored under an atmosphere maintained at or below / kg (DA).
- the organic thin film is usually stored at a temperature in the range of 0 ° C. to 50 ° C., and preferably in the range of 15 ° C. to 30 ° C. from the viewpoint of the life characteristics of the organic EL element.
- the storage time is appropriately selected according to the type of the organic compound contained in the organic thin film, and is usually about 1 minute to 2 hours.
- a storage time of 10 minutes to 1 hour, preferably 20 minutes to 40 minutes is appropriate for accumulating moisture appropriately on the surface of the organic thin film.
- the organic thin film may be stored under an atmosphere containing an inert gas.
- the inert gas may, for example, be helium gas, argon gas, nitrogen gas, or a mixed gas thereof.
- the inert gas is preferably nitrogen gas from the viewpoint of the easiness of device fabrication.
- the organic thin film may be stored in the atmosphere if it is an atmosphere in which the absolute humidity on a weight basis is maintained at 2.0 ⁇ 10 -3 kg / kg (DA) or more, You may store under the atmosphere whose density
- the organic thin film is preferably stored in an atmosphere having an oxygen concentration of 1,000 ppm or less on a volume basis, and stored in an atmosphere having an oxygen concentration of 100 ppm or less on a volume basis, from the viewpoint of the life characteristics of the organic EL element More preferably, the oxygen concentration is stored in an atmosphere of 10 ppm or less on a volume basis.
- the method of forming the organic layer preferably includes the step of baking the organic thin film, which is performed subsequent to the organic thin film storage step.
- the baking of the organic thin film is performed to evaporate part or all of the organic solvent used in forming the organic thin film.
- the firing of the organic thin film is preferably performed at a temperature within the range of 50 ° C. to 250 ° C., and preferably performed at a temperature within the range of 50 ° C. to 200 ° C., from the viewpoint of light emission characteristics and lifetime characteristics of the organic EL element. More preferable.
- the baking time is appropriately selected according to the type of the organic compound contained in the organic thin film, and is usually about 5 minutes to 2 hours. In order to appropriately accumulate moisture on the surface of the organic thin film, the baking temperature is 150 ° C. or less, preferably 80 to 140 ° C., and the baking time is 3 to 20 minutes, preferably 5 to 15 minutes.
- the firing of the organic thin film is preferably performed in an atmosphere containing an inert gas from the viewpoint of prolonging the life of the organic EL element.
- the inert gas may, for example, be helium gas, argon gas, nitrogen gas, or a mixed gas thereof. Among these, nitrogen gas is preferable in terms of the ease of element fabrication.
- These inert gases are introduced into a storage device that stores the organic EL element precursor.
- the concentration of the inert gas in the atmosphere is usually 99% or more, preferably 99.5% or more, on a volume basis.
- the baking of the organic thin film is preferably performed in a state where the oxygen concentration and the water concentration in the atmosphere are each kept at 1000 ppm or less on a volume basis. By this baking, the solvent contained in the organic thin film is removed.
- the firing of the organic thin film is preferably performed in an atmosphere in which the oxygen concentration and the moisture concentration in the atmosphere are each kept at 600 ppm or less on a volume basis, from the viewpoint of light emission characteristics and life characteristics of the organic EL element, more preferably
- the oxygen concentration and the water concentration are each 300 ppm or less on a volume basis, more preferably the oxygen concentration and the water concentration are each 100 ppm or less on a volume basis, and particularly preferably the oxygen concentration and the water concentration are each 10 ppm on a volume basis It is below.
- the firing of the organic thin film is preferably performed in a reduced pressure atmosphere of 10 Pa or less from the viewpoint of prolonging the life of the organic EL element.
- the baking of the organic thin film is preferably carried out in a container which is depressurized while an inert gas is introduced. When the baking is performed in a reduced pressure atmosphere, the solvent contained in the organic thin film can be more effectively removed as compared with the baking at the atmospheric pressure.
- the organic thin film formation step and the organic thin film storage step are carried out by sequentially passing the substrate through the space of the atmosphere suitable for carrying out the respective steps.
- the space in which each process is performed may be divided as, for example, a room, and the atmosphere of each space may be appropriately adjusted.
- the atmosphere for performing the organic thin film forming process is preferably 10 ppm or less on a volume basis, more preferably 5 ppm from the viewpoint of improving device characteristics.
- the following is a low humidity atmosphere having a water concentration of preferably 1 ppm or less.
- the organic thin film storage step it is necessary to keep the water concentration in the atmosphere high.
- the atmosphere of the organic thin film storage step is, from the viewpoint of the life of the organic EL element, an absolute humidity on a weight basis of 2.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more, 2.0 ⁇ 10 ⁇ 2 kg / kg (DA) B) preferably has an atmosphere maintained below, and has an absolute humidity of 5.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more and 2.0 ⁇ 10 ⁇ 2 kg / kg (DA) or less on a weight basis Is more preferred.
- the absolute humidity on a weight basis is 5.0 ⁇ 10 ⁇ 3 kg / kg (DA) or more, 1.5 ⁇ 10 ⁇ 2 kg /
- An atmosphere maintained at or below kg (DA) is more preferred. Therefore, when the substrate passes through the boundary of the partitioned space, the moisture atmosphere in the room where the organic thin film storage process is performed flows into the room where the organic thin film formation process is performed, so that the formation of the organic thin film is not adversely affected. It is necessary to partition the space and adjust the atmosphere.
- FIG. 3 is a schematic diagram which shows the example of division of the space which performs an organic thin film formation process, and the space which performs an organic thin film storage process.
- the buffer space 13 is provided between the space 11 for performing the organic thin film formation process and the space 12 for performing the organic thin film storage process.
- the substrate 14 passes through the space 11 in which the organic thin film formation process is performed, the buffer space 13, and the space 12 in which the organic thin film storage process is performed.
- the pressure of the space 11 for performing the organic thin film forming process is the pressure A
- the pressure of the space 12 for performing the organic thin film storage process is the pressure B
- the pressure of the buffer space 13 located therebetween be the pressure C A> Air pressure C
- the atmosphere in the buffer space may be the same as the space in which the organic thin film formation step is performed except that the negative pressure is applied.
- the space 11 for performing the organic thin film forming process and the space 12 for performing the organic thin film storage process are adjacent to each other.
- the substrate 14 passes through the space 11 for performing the organic thin film forming process and the space 12 for performing the organic thin film storage process in this order.
- the pressure in the space where the organic thin film formation process is performed is atmospheric pressure A and the pressure in the space where the organic thin film storage process is performed is atmospheric pressure B, then the pressure A> pressure B, ie, the pressure in the space of the organic thin film formation process is organic Positive pressure compared to thin film storage process.
- the atmosphere in the organic thin film storage step is prevented from flowing into the atmosphere in the organic thin film formation step, and the preferable atmosphere of the present invention is realized.
- the organic compound contained in the organic layer 6 is solid at 1 atmosphere and 25 ° C.
- the organic compound is preferably a light emitting organic compound that mainly emits fluorescence and / or phosphorescence, or a dopant for assisting the light emitting organic compound, and is a phosphorescent compound. Is more preferred.
- the dopant is added, for example, to improve the light emission efficiency or to change the light emission wavelength.
- the organic compound may be a low molecular weight compound or a high molecular weight compound as long as the organic compound can be formed into a film by coating, but is preferably a high molecular weight compound having a polystyrene-equivalent number average molecular weight of 10 3 to 10 8 .
- a light emitting organic compound (Phosphorescent light emitting compound (Phosphorescent light emitting polymer compound) or a light emitting organic compound (Phosphorescent light emitting polymer compound) is used as the light emitting organic compound;
- the light emitting layer is formed using a phosphorescent compound (phosphorescent organic compound) and a composition of a polymer compound and a light emitting organic compound that emits phosphorescence (phosphorescent composition)
- the emission life of the organic EL device can be extended. The effect is particularly improved.
- the method of the present invention When the method of the present invention is used, a sudden change in resistance during driving is suppressed by slightly changing the resistance between the surface of the organic thin film and the film formed on the surface before driving. As a result, the effect of extending the light emission life of the organic EL element is improved.
- the fluorescent light emitting material has a large current density of the driving current, even when the resistance applied between the surface of the organic thin film and the film formed on the surface slightly changes before driving, The influence on the suppression of the rapid change of resistance is small.
- the phosphorescent light emitting material since the phosphorescent light emitting material has a low current density of the driving current, the resistance at the time of driving is changed by the change of the resistance applied between the surface of the organic thin film and the film formed on the surface before driving. Has a large impact on the suppression of sudden changes in That is, the phosphorescent material is relatively susceptible to the performance of the device.
- Preferred low molecular weight compounds as light emitting organic compounds include distyrylarylene derivatives, oxadiazole derivatives, carbazole derivatives such as 4,4'-bis (carbazolyl-9-yl) biphenyl (CBP), and the like.
- Preferred polymer compounds as light-emitting organic compounds include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, dye-based dopants as exemplified below Examples thereof include compounds obtained by polymerizing materials and metal complex dopant materials.
- a metal complex having light emission from a triplet excited state such as an iridium complex or a platinum complex can be mentioned.
- examples of compounds emitting blue light include distyrylarylene derivatives, oxadiazole derivatives, polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives and the like. . Among them, polyvinylcarbazole derivatives, polyparaphenylene derivatives and polyfluorene derivatives which are polymer compounds are preferable.
- a quinacridone derivative, a coumarin derivative, those polymers, a polyparaphenylene vinylene derivative, a polyfluorene derivative etc. can be mentioned.
- polyparaphenylene vinylene derivatives and polyfluorene derivatives which are high molecular compounds are preferable.
- a compound which light-emits red a coumarin derivative, a thiophene ring compound
- those polymers a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyfluorene derivative etc.
- polyparaphenylene vinylene derivatives, polythiophene derivatives and polyfluorene derivatives which are polymer compounds are preferable.
- Dopant material As the pigment based dopant material, for example, cyclopentamine derivative, tetraphenylbutadiene derivative compound, triphenylamine derivative, oxadiazole derivative, pyrazoloquinoline derivative, distyrylbenzene derivative, distyrylarylene derivative, pyrrole derivative, thiophene ring Compound, Pyridine ring compound, Perinone derivative, Perylene derivative, Oligothiophene derivative, Trifmanylamine derivative, Oxadiazole dimer, Pyrazoline dimer, Quinacridone derivative, Coumarin derivative, Rubrene derivative, Squarium derivative, Porphyrin derivative, Tetracene derivative, Pyrazolone derivative , Decacyclene and phenoxazone can be mentioned.
- the metal complex dopant material includes, for example, a central metal such as Al, Zn, Be, etc., or a rare earth metal such as Tb, Eu, Dy, etc., and a ligand such as oxadiazole, thiadiazole structure, phenylpyridine structure, Mention may be made of metal complexes having a phenylbenzimidazole structure, a quinoline structure and the like.
- the metal complex include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazolyl zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex and europium complex.
- the organic EL element 1 is manufactured.
- FIG. 2 is a view schematically showing another form of the organic EL device manufactured by the method of the present invention.
- the organic EL element 1 ′ includes a first electrode 3, a second electrode 7, and a first organic layer 4 provided between the first electrode and the second electrode on the substrate 2.
- Typical functions of the above-mentioned layers constituting the organic EL element 1 ′ are as follows: the first electrode 3 is an anode, the second electrode 7 is a cathode, the first organic layer 4 is a hole injection layer, and the second organic layer 5 is a hole transport layer, and the third organic layer 6 'is a light emitting layer.
- the organic layer 6 ′ is a light emitting layer
- the organic layer 6 ′ is formed by the same method as the organic layer 6 in the organic EL element 1 described above.
- the organic layers 4 and 5 are adjacent to the light emitting layer, and do not directly participate in light emission of the hole injection layer, the hole transport layer, the electron injection layer, the electron transport layer, etc. It corresponds to a layer having a transport function.
- examples of functional layers corresponding to the organic layers 4 and 5 include a hole injection layer or a hole transport layer.
- the organic EL element 1 ′ may have a functional layer such as an electron injection layer or an electron transport layer between the third organic layer 6 ′ as the light emitting layer and the second electrode 7 Good.
- the formation of the functional layer containing an organic compound may be carried out in the same manner as in the prior art, and preferably, it is carried out using a coating method in which the manufacturing process is simple and the element area can be easily enlarged.
- the functional layer is formed by applying an organic compound-containing solution on the layer on which the functional layer is formed, and then drying the solvent contained in the organic thin film to form the functional layer. Be done.
- the organic compound is preferably a polymer compound from the viewpoint of coatability.
- the solvent and coating method for forming the organic thin film by solution coating method are the same as the solvents and coating methods used for forming the organic thin film containing the organic compound in the formation of the organic layer 6 described above, and The application method is mentioned.
- the thin film containing the organic compound is preferably formed under atmospheric pressure and in an atmosphere containing an inert gas, from the viewpoint that the organic EL device can be easily manufactured.
- the inert gas may, for example, be helium gas, argon gas, nitrogen gas, or a mixed gas thereof. Among them, nitrogen gas is preferable from the viewpoint of the easiness of device fabrication.
- the thin film may be formed under an air atmosphere, or may be formed under an atmosphere in which the concentration of inert gas in the atmosphere is 99% or more by volume. From the viewpoint of prolonging the lifetime of the organic EL device, it is preferable that the concentration of the inert gas is 99.5% or more.
- the thin film is preferably formed in an atmosphere having an oxygen concentration of 1,000 ppm or less on a volume basis and / or a water concentration of 1,000 ppm or less on a volume basis, from the viewpoint of easiness of device fabrication. More preferably, it is formed under an atmosphere of 10 ppm or less and / or a water concentration of 10 ppm or less by volume.
- the thin film is preferable to bake the thin film while maintaining the oxygen concentration and the moisture concentration in the atmosphere at 1000 ppm or less on a volume basis, respectively. By this baking, the solvent contained in the thin film is removed.
- the firing is preferably performed at a temperature within the range of 50 ° C. to 250 ° C., and more preferably at a temperature within the range of 50 ° C. to 200 ° C., from the viewpoint of the light emission characteristics and the lifetime characteristics of the organic EL element.
- the baking time is appropriately selected depending on the organic compound contained in the thin film, and is usually about 5 minutes to 2 hours.
- the baking of the thin film is preferably performed in an atmosphere containing an inert gas or in an atmosphere of 10 Pa or less from the viewpoint of prolonging the life of the organic EL element.
- the inert gas may, for example, be helium gas, argon gas, nitrogen gas, or a mixed gas thereof. Among them, nitrogen gas is preferable from the viewpoint of the easiness of device fabrication.
- the formation of the thin film and the firing of the thin film are preferably performed in a state where the oxygen concentration and the moisture concentration in the atmosphere are each kept at 600 ppm or less on a volume basis, from the viewpoint of light emission characteristics and lifetime characteristics of the device.
- the oxygen concentration and the water concentration are each 300 ppm or less on a volume basis, more preferably the oxygen concentration and the water concentration are each 100 ppm or less on a volume basis, and particularly preferably the oxygen concentration and the water concentration are on a volume basis Each is 10 ppm or less.
- a first organic layer 4 and a second organic layer 5 are formed on the first electrode 3, and a thin film containing the organic compound contained in the organic layer 6 on the second organic layer 5.
- the light emitting layer which is the organic layer 6 ′ is formed by performing the forming step, the thin film storage step, and the baking step, and the second electrode 7 is formed thereon, whereby the organic EL element 1 ′ is manufactured. Ru.
- the organic EL element of the present invention has, as an essential component, a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode.
- the organic layer is a light emitting layer
- the light emitting layer may be provided between the first electrode (for example, the anode) and the second electrode (for example, the cathode), for example, to improve the device characteristics.
- further layers may be provided.
- the layer includes a functional layer provided adjacent to the light emitting layer.
- an electron injection layer As a layer provided between a cathode and a light emitting layer, an electron injection layer, an electron transport layer, a hole block layer etc. can be mentioned.
- the layer in contact with the cathode is referred to as the electron injection layer
- the layers other than the electron injection layer are referred to as the electron transport layer.
- the electron injection layer is a layer having a function of improving the electron injection efficiency from the cathode.
- the electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode.
- the hole blocking layer is a layer having a function of blocking the transport of holes. When the electron injection layer and / or the electron transport layer have a function of blocking the transport of holes, these layers may also function as a hole blocking layer.
- the hole blocking layer has a function of blocking the transport of holes can be confirmed, for example, by fabricating a device which allows only a hole current to flow. For example, a device that does not have a hole blocking layer and allows only a hole current to flow, and a device having a configuration in which a hole blocking layer is inserted into the device are manufactured, and the current value of the device having a hole blocking layer decreases. It can be confirmed that the hole blocking layer exhibits the function of blocking the transport of holes.
- a hole injection layer As a layer provided between an anode and a light emitting layer, a hole injection layer, a hole transport layer, an electron block layer etc. can be mentioned.
- the layer in contact with the anode is referred to as a hole injection layer, and the layers excluding the hole injection layer are positive. It may be called a hole transport layer.
- the hole injection layer is a layer having a function of improving the hole injection efficiency from the anode.
- the hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode.
- the electron blocking layer is a layer having a function of blocking the transport of electrons. When the hole injection layer and / or the hole transport layer have a function of blocking the transport of electrons, these layers may also function as an electron block layer.
- the electron blocking layer has a function of blocking the transport of electrons can be confirmed, for example, by fabricating a device which allows only an electron current to flow. For example, an element that does not have an electron block layer and allows only an electron current to flow and an element having a configuration in which the electron block layer is inserted into the element are manufactured, and the current value of the element provided with the electron block layer decreases. It can be confirmed to show the function of blocking the transport of electrons.
- the organic layer in the present invention may contain an organic compound, and may be any of a light emitting layer, a hole injection layer, a hole transport layer, an electron block layer, an electron injection layer, an electron transport layer, and a hole block layer. It is also good. Among them, a light emitting layer is preferable.
- anode / hole injection layer / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / electron injection layer / cathode c) anode / hole injection layer / light emitting layer / electron transport layer / cathode e) anode / Hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode f) anode / hole transport layer / light emitting layer / cathode d) anode / hole transport layer / light emitting layer / electron injection layer / cathode e) Anode / hole transport layer / light emitting layer / electron transport layer / cathode f) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode g) anode
- the organic EL device may have two or more light emitting layers.
- an organic EL device having two light emitting layers is shown in the following n)
- An element configuration can be mentioned.
- the charge generation layer is a layer in which holes and electrons are generated by applying an electric field.
- a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide and the like can be mentioned.
- the organic EL element may be further covered with a sealing member such as a sealing film or a sealing plate for sealing.
- a sealing member such as a sealing film or a sealing plate for sealing.
- all layers disposed on the side from which light is extracted with reference to the light emitting layer are transparent.
- the degree of transparency is preferably such that the visible light transmittance between the outermost surface of the organic EL element from which light is extracted and the light emitting layer is 40% or more.
- one exhibiting a light transmittance of 40% or more in the region is preferable.
- an insulating layer with a film thickness of 2 nm or less may be provided adjacent to the electrode for the purpose of improving adhesion with the electrode and charge injection from the electrode.
- a thin buffer layer may be inserted between the above-described layers in order to improve adhesion at the interface and prevent mixing.
- the order of layers to be stacked, the number of layers, and the thickness of each layer can be appropriately set in consideration of the light emission efficiency and the device life.
- the substrate one that does not change chemically in the process of manufacturing the organic EL element is suitably used, and for example, glass, plastic, polymer film, silicon substrate, and a laminate of these, etc. are used.
- a commercially available thing can be used as said board
- a transparent or translucent electrode As the anode, in the case of an organic EL element configured to extract light from the light emitting layer through the anode, a transparent or translucent electrode is used.
- the transparent electrode or the semitransparent electrode thin films of metal oxides, metal sulfides and metals having high electric conductivity can be used, and those having high light transmittance are suitably used.
- thin films of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper and the like are used, and among these, ITO, A thin film made of IZO or tin oxide is preferably used.
- Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
- an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.
- a material that reflects light may be used, and as the material, metals, metal oxides, and metal sulfides having a work function of 3.0 eV or more are preferable.
- the film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 40 nm to 500 nm. .
- Hole injection materials for forming the hole injection layer include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamines, starburst amines, phthalocyanines, amorphous carbon, polyaniline, and the like. And polythiophene derivatives.
- the hole injection layer there is a method of forming a thin film containing a hole injection material and thereafter baking or drying.
- a film forming method of a thin film containing a hole injection material for example, film formation from a solution containing a hole injection material can be mentioned, and from the viewpoint of prolonging the life, the same atmosphere as the organic layer forming step described above It is preferable to form a film in the inside.
- the solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole injection material, and is a chlorinated solvent such as chloroform, methylene chloride or dichloroethane, an ether solvent such as tetrahydrofuran, toluene or xylene Aromatic hydrocarbon solvents such as anisole, tetralin and phenylcyclohexane, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellsolve acetate, alcohol solvents such as isopropyl alcohol, Water can be mentioned, and what mixed these may be used.
- a chlorinated solvent such as chloroform, methylene chloride or dichloroethane
- an ether solvent such as tetrahydrofuran, toluene or xylene
- Aromatic hydrocarbon solvents such as anisole, t
- the film thickness of the hole injection layer has an optimum value depending on the material used, is appropriately set so that the driving voltage and the light emission efficiency become appropriate values, and at least a thickness that does not generate pinholes is required.
- a thick film is not preferable because the drive voltage of the device becomes high. Accordingly, the thickness of the hole injection layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- ⁇ Hole transport layer> As a hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine residue in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene Derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylenevinylene) And derivatives thereof, polyfluorene derivatives, polymer compounds having an aromatic amine residue, and the like.
- polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine residue in a side chain or a main chain, polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly Arylamine or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-thienylenevinylene) or a derivative thereof, a polyfluorene derivative, a polymer compound having an aromatic amine residue is preferable, and further, Preferred are polyvinyl carbazole or derivatives thereof, polyfluorene derivatives, and polymer compounds having an aromatic amine residue. In the case of a low molecular weight hole transport material, it is preferable to use it dispersed in a polymer binder.
- the method of forming the hole transport layer may be the same method as the method of forming the organic layer 6 included in the organic EL element 1.
- a method of forming the hole transport layer may be a method of forming a thin film containing a hole transport material and then baking or drying it.
- a film-forming method of the thin film containing a hole transport material In a low molecular weight hole transport material, film-forming from the liquid mixture containing a polymer binder and a hole transport material is mentioned. In the case of a polymeric hole transport material, film formation from a solution containing the hole transport material can be mentioned.
- Examples of the solvent used for film formation from a solution include the same solvents as the solvents used in forming the thin film containing the organic compound in the formation of the organic layer 6 described above.
- the same coating method as the coating method in the formation of the organic layer 6 described above can be mentioned, and from the viewpoint of prolonging the life, the same atmosphere as the functional layer forming step described above It is preferable to form a film in the inside.
- polystyrene examples include vinyl chloride and polysiloxane.
- the film thickness of the hole transport layer is appropriately set so that the driving voltage and the light emission efficiency become appropriate values, and at least a thickness that does not generate pinholes is required. If it is too thick, the drive voltage of the device is undesirably increased. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- Light emitting layer As an organic compound contained in a light emitting layer, the above-mentioned light emitting organic compound, the dopant which assists a light emitting organic compound, etc. are mentioned.
- Electrode transporting material constituting the electron transporting layer known materials can be used, and an oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyano anthracene Quinodimethane or a derivative thereof, fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof It can be mentioned.
- oxadiazole derivatives as an electron transport material, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinone or derivatives thereof, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinolines or derivatives thereof, polyquinoxalines or derivatives thereof, polyfluorene Or derivatives thereof are preferable, and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, polyquinoline and the like are further preferable. preferable.
- the method of forming the electron transport layer may be the same method as the method of forming the hole transport layer 5 included in the organic EL element 1 ′.
- the method of forming the electron transport layer may be a method of forming a thin film containing an electron transport material and then baking or drying it.
- a vacuum evaporation method from powder, or a film forming from a solution or a molten state can be mentioned.
- film formation from a solution or a molten state can be mentioned.
- a method of forming an electron transport layer from a solution the same film forming method as the method of forming a hole transport layer from the above-mentioned solution can be mentioned, and in the same atmosphere as the functional layer forming step described above It is preferable to form a film.
- the film thickness of the electron transport layer varies depending on the material used, is appropriately set so that the driving voltage and the light emission efficiency become appropriate values, and at least a thickness that does not cause pinholes is required, which is too thick This is not preferable because the drive voltage of the device is increased. Accordingly, the film thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- an optimum material is appropriately selected according to the type of the light emitting layer, and an alkali metal, an alkaline earth metal, an alloy containing one or more of an alkali metal and an alkaline earth metal, an alkali Mention may be made of metal or alkaline earth metal oxides, halides, carbonates or mixtures of these substances.
- alkali metals, oxides of alkali metals, halides and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride And rubidium oxide, rubidium fluoride, cesium oxide, cesium fluoride, lithium carbonate and the like.
- alkaline earth metals and oxides, halides and carbonates of alkaline earth metals magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, Barium fluoride, strontium oxide, strontium fluoride, magnesium carbonate and the like can be mentioned.
- the electron injection layer may be composed of a laminate in which two or more layers are stacked, and examples thereof include LiF / Ca.
- the electron injection layer is formed by a vapor deposition method, a sputtering method, a printing method, or the like.
- the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m.
- a material of the cathode As a material of the cathode, a material having a small work function, easy electron injection to the light emitting layer, and high electrical conductivity is preferable. In the organic EL element which extracts light from the anode side, a material having high visible light reflectance is preferable as a material of the cathode in order to reflect light from the light emitting layer toward the anode side by the cathode.
- alkali metals, alkaline earth metals, transition metals, and Group III-B metals can be used.
- Examples of materials for the cathode include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium and the like.
- a metal, an alloy of two or more of the metals, one or more of the metals, and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, or tin Alloys or graphite or graphite intercalation compounds are used.
- alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminium alloy, indium-silver alloy, lithium-aluminium alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminium alloy, etc. it can.
- a transparent conductive electrode made of a conductive metal oxide, a conductive organic substance or the like can be used as the cathode.
- indium oxide, zinc oxide, tin oxide, ITO, and IZO can be mentioned as the conductive metal oxide
- polyaniline or a derivative thereof, polythiophene or a derivative thereof can be mentioned as the conductive organic substance.
- the cathode may be comprised by the laminated body which laminated
- the film thickness of the cathode is appropriately set in consideration of electric conductivity and durability, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
- Examples of the method of producing the cathode include a vacuum evaporation method, a sputtering method, and a laminating method of thermocompression bonding of a metal thin film.
- the material of the insulating layer include metal fluorides, metal oxides, organic insulating materials, and the like.
- an organic EL element provided with an insulating layer having a film thickness of 2 nm or less, one having an insulating layer having a film thickness of 2 nm or less adjacent to the cathode and one having an insulating layer having a film thickness of 2 nm or less adjacent to the anode It can be mentioned.
- the organic EL element described above can be suitably used for a curved or flat illumination device, for example, a planar light source used as a light source of a scanner, and a display device.
- Examples of the display device provided with the organic EL element include an active matrix display device, a passive matrix display device, a segment display device, a dot matrix display device, a liquid crystal display device, and the like.
- the organic EL element is used as a light emitting element constituting each pixel in an active matrix display device or a passive matrix display device, and is used as a light emitting element constituting each segment in a segment display device, a dot matrix display device, In a liquid crystal display device, it is used as a backlight.
- the polystyrene equivalent number average molecular weight (Mn) and the polystyrene equivalent weight average molecular weight (Mw) were determined by GPC (manufactured by Shimadzu Corporation, trade name: LC-10 Avp).
- the polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 ⁇ L was injected into GPC. Tetrahydrofuran was used for the mobile phase of GPC, and it flowed at the flow rate of 0.6 mL / min.
- TSKgel SuperHM-H manufactured by Tosoh
- TSKgel SuperH 2000 manufactured by Tosoh
- RID-10A differential refractive index detector
- Example 1 The organic EL element was produced by the following method.
- a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid ("Baytron P" manufactured by Stark) is spin-coated on a glass substrate on which an ITO film (anode) having a thickness of 150 nm is formed by sputtering.
- ITO film anode
- the thin film was fired by heating on a hot plate at 200 ° C. for 10 minutes to obtain a hole injection layer.
- the thin film formation step and the baking step were performed in the air.
- the polymer compound 1 as a hole transport material was dissolved in xylene to prepare a xylene solution 1.
- the concentration of the polymer compound 1 in the xylene solution 1 was 0.8% by weight.
- xylene solution 1 is applied on the hole injection layer by spin coating, and the film thickness is 20 nm A thin film was formed, and the thin film was fired by heating at 180 ° C. for 1 hour in a nitrogen atmosphere controlled to 10 ppm or less in terms of volume and oxygen concentration and moisture concentration to obtain a hole transport layer.
- a 1.3 wt% xylene solution A of a phosphorescent composition was prepared by adding the phosphorescent organic compound 1 to the polymer compound 2 at a ratio of 7.5 wt%.
- xylene solution A is applied on the hole transport layer by spin coating, A thin film was formed.
- the thin film is stored for 30 minutes in wet nitrogen in which the oxygen concentration is controlled to 10 ppm or less by volume and the absolute humidity by weight is controlled to 1.3 ⁇ 10 ⁇ 2 kg / kg (DA), and the organic layer is It formed. Storage of the organic thin film was performed at room temperature (25 ° C.).
- the organic layer was baked at 130 ° C. for 10 minutes in a nitrogen atmosphere in which the oxygen concentration and the water concentration were controlled to 10 ppm or less on a volume basis.
- the firing of the organic layer was performed in an atmosphere at atmospheric pressure.
- the organic layer functions as a light emitting layer.
- the pressure in the thin film forming step and the baking step was atmospheric pressure.
- barium was deposited to a thickness of about 5 nm as a cathode, and then aluminum was deposited to a thickness of about 80 nm.
- sealing was performed using a glass substrate to fabricate an organic EL element.
- the manufactured organic EL element emits red light (CIE 1931: (0.62, 0.38)), and when driven at a constant current with an initial luminance of 12,000 cd / m 2 , the luminance reaches 75% of the initial luminance. (Brightness 75% life) was 67.1 hours.
- Example 2 In the formation of the organic layer, except that the thin film was stored in wet nitrogen in which the oxygen concentration was 10 ppm or less by volume and the absolute humidity by weight was controlled to 7.7 ⁇ 10 -3 kg / kg (DA), An organic EL device was produced in the same manner as in Example 1.
- the manufactured organic EL element emits red light (CIE 1931: (0.62, 0.38)), and when driven at a constant current with an initial luminance of 12,000 cd / m 2 , the luminance reaches 75% of the initial luminance. Time (brightness 75% life) was 62.0 hours.
- Comparative Example 1 In the formation of the organic layer, an organic EL device was produced in the same manner as in Example 1 except that the thin film was not stored in wet nitrogen.
- the manufactured organic EL element emits red light (CIE 1931: (0.62, 0.38)), and when driven at a constant current with an initial luminance of 12,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 47.9 hours.
- Example 3 The organic EL element was produced by the following method.
- a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid ("Baytron P" manufactured by Stark) is spin-coated on a glass substrate on which an ITO film (anode) having a thickness of 150 nm is formed by sputtering.
- ITO film anode
- the thin film was fired by heating on a hot plate at 200 ° C. for 10 minutes to obtain a hole injection layer.
- the thin film formation step and the baking step were performed in the air.
- the polymer compound 1 as a hole transport material was dissolved in xylene to prepare a xylene solution 1.
- the concentration of the polymer compound 1 in the xylene solution 1 was 0.8% by weight.
- xylene solution 1 is applied on the hole injection layer by spin coating, and the film thickness is 20 nm A thin film was formed, and the thin film was fired by heating at 180 ° C. for 1 hour in a nitrogen atmosphere controlled to 10 ppm or less in terms of volume and oxygen concentration and moisture concentration to obtain a hole transport layer.
- a 1.4% by weight xylene solution B of a phosphorescent composition was prepared by adding the phosphorescent organic compound 2 to the polymer compound 3 in a proportion of 30% by weight.
- xylene solution B is applied on the hole transport layer by spin coating, A thin film was formed.
- the thin film is stored for 30 minutes in wet nitrogen in which the oxygen concentration is controlled to 10 ppm or less by volume and the absolute humidity by weight is controlled to 1.3 ⁇ 10 ⁇ 2 kg / kg (DA), and the organic layer is It formed. Storage of the organic thin film was performed at room temperature (25 ° C.).
- the film was baked at 130 ° C. for 10 minutes in a nitrogen atmosphere in which the oxygen concentration and the water concentration were controlled to 10 ppm or less by volume.
- the firing of the organic layer was performed in an atmosphere at atmospheric pressure.
- the organic layer functions as a light emitting layer.
- the pressure in the thin film forming step and the baking step was atmospheric pressure.
- barium was deposited to a thickness of about 5 nm as a cathode, and then aluminum was deposited to a thickness of about 80 nm.
- sealing was performed using a glass substrate to fabricate an organic EL element.
- the manufactured organic EL element emits green light (CIE 1931: (0.32, 0.63)), and when driven at a constant current with an initial luminance of 8,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 17.4 hours.
- Example 4 In the formation of the organic layer, except that the thin film was stored in wet nitrogen in which the oxygen concentration was 10 ppm or less by volume and the absolute humidity by weight was controlled to 7.5 ⁇ 10 ⁇ 3 kg / kg (DA), An organic EL device was produced in the same manner as in Example 3.
- the manufactured organic EL element emits green light (CIE 1931: (0.32, 0.63)), and when driven at a constant current with an initial luminance of 8,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 14.3 hours.
- Comparative example 2 In the formation of the organic layer, an organic EL device was produced in the same manner as in Example 3, except that the thin film was not stored in wet nitrogen.
- the manufactured organic EL element emits green light (CIE 1931: (0.32, 0.63)), and when driven at a constant current with an initial luminance of 8,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 9.8 hours.
- Synthesis example 1 Synthesis of Polymer Compound 4 Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (5.20 g), bis (4-bromophenyl)- (4-Secondary butylphenyl) -amine (4.50 g), palladium acetate (2.2 mg), tri (2-methylphenyl) phosphine (15.1 mg), Aliquat 336 (0.91 g, from Aldrich), toluene (70 ml) ) Were mixed and heated to 105.degree.
- the polystyrene reduced number average molecular weight of the polymer compound 4 was 1.2 ⁇ 10 5 , and the polystyrene reduced weight average molecular weight was 2.6 ⁇ 10 5 .
- polymer compound 4 is a compound of formula
- the polymer is a polymer having a repeating unit represented by 1 in a 1: 1 (molar ratio).
- Synthesis example 2 Synthesis of Polymer Compound 5 In a 200 mL separable flask connected to a Dimroth, 3.18 g (6.0 mmol) of 9,9-dioctylfluorene-2,7-diboric acid ethylene glycol ester, 9,9-dioctyl-2,7 -Dibromofluorene 3.06 g (5.4 mmol), N, N'-bis (4-bromophenyl) -N, N'-bis (2,6-dimethyl-4-tert-butylphenyl) -1,4- 0.44 g (0.6 mmol) of phenylenediamine, 0.82 g of methyltrioctyl ammonium chloride (trade name: Aliquat 336 (registered trademark), manufactured by Aldrich), and 60 mL of toluene were added.
- the precipitate was filtered and then dried to obtain a solid.
- This solid was dissolved in 190 mL of toluene to prepare a solution, and this solution was passed through a silica gel / alumina column which had previously been flushed with toluene, and the obtained solution was dropped into 930 mL of methanol, whereby a precipitate was formed.
- the precipitate was filtered and then dried, to obtain a polymer compound 5 (4.17 g) having the repeating unit represented by the following formula in the following molar ratio according to the theoretical value determined from the charged raw materials.
- the polystyrene equivalent number average molecular weight Mn of the polymer compound 5 was 2.7 ⁇ 10 5
- the polystyrene equivalent weight average molecular weight Mw was 7.1 ⁇ 10 5 .
- Synthesis example 4 Synthesis of polymer compound 6 3.13 g of compound M-1, 3.58 g of 2,7-dibromo-9,9-dioctylfluorene under nitrogen atmosphere, 2.2 mg of palladium (II) acetate, tris (2-methoxyphenyl) 13.4 mg of phosphine and 80 mL of toluene were mixed and heated to 100.degree. To the reaction solution was added dropwise 21.5 ml of a 20% by weight aqueous solution of tetraethylammonium hydroxide, and the mixture was refluxed for 4.5 hours.
- the reaction solution was cooled to room temperature, and washed three times with 82 ml of water, three times with 82 ml of 3% by weight aqueous acetic acid solution, and three times with 82 ml of water.
- the organic layer was dropped into 1200 ml of methanol to form a precipitate, which was filtered and dried to obtain a solid.
- the solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column.
- the obtained eluate was added dropwise to 1500 ml of methanol to obtain 3.52 g of polymer compound 6.
- the polystyrene equivalent number average molecular weight of the polymer compound 6 was 3.0 ⁇ 10 5
- the polystyrene equivalent weight average molecular weight was 8.4 ⁇ 10 5 .
- the polymer compound 6 has the following formula:
- Example 5 and Comparative Example 3 The following formula was synthesized according to the method described in WO 2002/44189, using the polymer compound 4 synthesized in Synthesis Example 1 instead of the polymer compound 1, and instead of the phosphorescent organic compound 1.
- the phosphorescent organic compound 3 is used in place of the polymer compound 2 and the polymer compound 5 synthesized in Synthesis Example 2 is used in place of the polymer compound 5 in the polymer compound 5.
- An organic EL device is manufactured in the same manner as in Example 1 except that the xylene solution C of the phosphorescent composition is added in a proportion by weight (Example 5).
- the polymer compound 4 synthesized in Synthesis Example 1 is used, and instead of the phosphorescent organic compound 1, the phosphorescence organic compound 3 is used, and instead of the polymer compound 2, a synthesis example 2 except using the polymer compound 5 synthesized in 2 and adding the phosphorescent organic compound 3 to the polymer compound 5 in a ratio of 5.0% by weight, except using the xylene solution C of the phosphorescent composition
- An organic EL device is manufactured in the same manner as Comparative Example 1 (Comparative Example 3).
- the manufactured devices both emit red light. Then, when the characteristics of those organic EL elements are measured in the same manner as in Example 1, the time until the luminance reaches 75% of the initial luminance when driven at a constant current at least at an initial luminance of 12,000 cd / m 2 ( A remarkable improvement is observed in the organic EL element of Example 5 in comparison with the organic EL element of Comparative Example 3 with respect to the luminance 75% life).
- Example 6 and Comparative Example 4 instead of the polymer compound 1, the polymer compound 4 synthesized in Synthesis Example 1 is used, and instead of the phosphorescent organic compound 2, the following formula:
- the phosphorescent organic compound 4 was used as the polymer compound 6 in place of the compound 2 and the polymer compound 6 synthesized in Synthesis Example 4 was used in place of the polymer compound 3. .0.
- Xylene solution of a phosphorescent composition which is added in a proportion of 0% by weight But using D to produce the organic EL device in the same manner as in Comparative Example 2 (Comparative Example 4).
- the manufactured devices both emit green light. Then, when the characteristics of those organic EL elements are measured in the same manner as in Example 3, the time until the luminance reaches 75% of the initial luminance when driven at a constant current at least with an initial luminance of 8,000 cd / m 2 ( A remarkable improvement is observed in the organic EL element of Example 6 in comparison with the organic EL element of Comparative Example 4 with respect to the luminance 75% life).
- Synthesis example 7 Synthesis of Polymer Compound 7 Under an inert gas atmosphere, 2,7-dibromo-9,9-di (octyl) fluorene (9.0 g, 16.4 mmol), N, N'-bis (4-bromophenyl)- N, N'-bis (4-t-butyl-2,6-dimethylphenyl) 1,4-phenylenediamine (1.3 g, 1.8 mmol), 2,7-bis (4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di (4-hexylphenyl) fluorene (13.4 g, 18.0 mmol), tetraethylammonium hydroxide (43.0 g, 58.3 mmol) ), Palladium acetate (8 mg, 0.04 mmol), tri (2-methoxyphenyl) phosphine (0.05 g, 0.1 mmol), toluen
- polystyrene-equivalent weight average molecular weight of the obtained polymer compound 7 is 3.1 ⁇ 10 5
- molecular weight distribution index (Mw / Mn) is 2.9.
- the polymer compound 7 has the following formula:
- Synthesis example 6 Synthesis of Phosphorescent Organic Compound 5 A phosphorescent organic compound 5 represented by the following formula was synthesized according to the method described in JP-A-2006-188673.
- Example 7 The organic EL element was produced by the following method. A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Stark; Baytron P) is spin-coated on a glass substrate on which an ITO film (anode) having a thickness of 45 nm is formed by sputtering. The thin film was applied to form a thin film having a thickness of 65 nm, and the thin film was fired by heating on a hot plate at 200 ° C. for 10 minutes to obtain a hole injection layer. In the formation of the hole injection layer, the thin film formation step and the baking step were performed in the air.
- a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid manufactured by Stark; Baytron P
- ITO film anode
- the thin film was applied to form a thin film having a thickness of 65 nm, and the thin film was fired by heating on a
- the polymer compound 4 which is a hole transport material was dissolved in xylene to prepare a xylene solution 2.
- the concentration of the polymer compound 4 in the xylene solution 2 was 0.8% by weight.
- the xylene solution 2 is applied on the hole injection layer by spin coating, and the film thickness is 20 nm A thin film was formed, and the thin film was fired by heating at 200 ° C. for 1 hour in a nitrogen atmosphere controlled to have a volume ratio of oxygen concentration and water concentration of 10 ppm or less to obtain a hole transport layer.
- a 1.3 wt% xylene solution E of a mixture obtained by adding the phosphorescent organic compound 5 to the polymer compound 7 in a proportion of 5 wt% was prepared.
- the xylene solution E is applied on the hole transport layer by spin coating, and the film thickness is 65 nm.
- a thin film was formed.
- the oxygen concentration is 10ppm or less by volume
- the absolute humidity of the weight is at 9.9 ⁇ 10 -3 (kg / kg (DA)) wet nitrogen which is controlled, said at room temperature (25 ° C.)
- the thin film was stored for 30 minutes to form an organic layer.
- the oxygen concentration and the water concentration were baked at 130 ° C. for 10 minutes in a nitrogen atmosphere controlled to 10 ppm or less in volume ratio.
- the organic layer functions as a light emitting layer.
- the pressure in the thin film forming step and the baking step was atmospheric pressure.
- the manufactured organic EL element emits red light (CIE 1931: (0.65, 0.32)), and when driven at a constant current with an initial luminance of 12,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 16.9 hours.
- Comparative example 5 In the formation of the organic layer, an organic EL device was produced in the same manner as in Example 7 except that the thin film was not stored in wet nitrogen.
- the manufactured organic EL element emits red light (CIE 1931: (0.65, 0.32)), and when driven at a constant current with an initial luminance of 12,000 cd / m 2 , the luminance is 75% of the initial luminance.
- the time to reach (brightness 75% life) was 15.3 hours.
Abstract
Description
体積基準で10ppm以下の水分濃度を有する低湿度雰囲気下において、該有機層が上に形成される層の表面上に、塗布法により有機化合物を含む有機薄膜を形成する有機薄膜形成工程と、
2.0×10-3kg/kg(乾燥空気)以上の重量基準の絶対湿度を有する高湿度雰囲気下において、該有機薄膜形成工程によって得られた有機薄膜を保管する有機薄膜保管工程とを、
包含する方法によって形成される、有機EL素子の製造方法を提供する。
以下、図1に示す有機EL素子1を例として、有機層6を形成する方法について説明する。有機層6は、第1の電極3上に、有機化合物を含む薄膜である有機薄膜を形成する有機薄膜形成工程と、高湿度雰囲気下において、得られた有機薄膜を保管する有機薄膜保管工程とを含む方法によって形成される。有機EL素子1のその他の構成要素の詳細については、後述する。
パターン形成や多色の塗分けが容易であるという点で、グラビア印刷法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、反転印刷法、インクジェットプリント法などの塗布法が好ましい。
次に、前記有機層6に含まれる有機化合物について説明する。該有機化合物は、1気圧、25℃において固体である。有機層6が発光層である場合、該有機化合物は、主として蛍光及び/又は燐光を発光する発光性有機化合物、発光性有機化合物を補助するドーパントであることが好ましく、燐光発光性化合物であることが、より好ましい。ドーパントは、例えば、発光効率の向上や、発光波長を変化させるために加えられる。なお、有機化合物は、塗布により成膜可能であれば、低分子化合物でも高分子化合物でもよいが、ポリスチレン換算の数平均分子量が、103~108である高分子化合物であることが好ましい。発光性有機化合物として、燐光を発光する発光性高分子化合物(燐光発光性高分子化合物)を用いて発光層を形成すれば、又は、発光性有機化合物として、燐光を発光する発光性有機化合物(燐光発光性有機化合物)を用い、高分子化合物と燐光を発光する発光性有機化合物との組成物(燐光発光性組成物)を用いて発光層を形成すれば、有機EL素子の発光寿命の延長効果が特に向上する。
色素系ドーパント材料としては、例えば、シクロペンダミン誘導体、テトラフェニルブタジエン誘導体化合物、トリフェニルアミン誘導体、オキサジアゾール誘導体、ピラゾロキノリン誘導体、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ピロール誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン誘導体、ペリレン誘導体、オリゴチオフェン誘導体、トリフマニルアミン誘導体、オキサジアゾールダイマー、ピラゾリンダイマー、キナクリドン誘導体、クマリン誘導体、ルブレン誘導体、スクアリウム誘導体、ポルフィリン誘導体、テトラセン誘導体、ピラゾロン誘導体、デカシクレン、フェノキサゾンを挙げることができる。
不活性気体としては、ヘリウムガス、アルゴンガス、窒素ガス、及びこれらの混合ガスなどを挙げることができ、これらのなかでも素子作製の容易さの観点からは、窒素ガスが好ましい。
a)陽極/正孔注入層/発光層/陰極
b)陽極/正孔注入層/発光層/電子注入層/陰極
c)陽極/正孔注入層/発光層/電子輸送層/陰極
e)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
f)陽極/正孔輸送層/発光層/陰極
d)陽極/正孔輸送層/発光層/電子注入層/陰極
e)陽極/正孔輸送層/発光層/電子輸送層/陰極
f)陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
g)陽極/正孔注入層/正孔輸送層/発光層/陰極
h)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
i)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極
j)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
k)陽極/発光層/電子注入層/陰極
l)陽極/発光層/電子輸送層/陰極
m)陽極/発光層/電子輸送層/電子注入層/陰極
(ここで、記号「/」は、記号「/」を挟む各層が隣接して積層されていることを示す。
以下同じ。)
n)陽極/(繰り返し単位A)/電荷発生層/(繰り返し単位A)/陰極
また「(繰り返し単位A)/電荷発生層」を「繰り返し単位B」とすると、3層以上の発光層を有する有機EL素子としては、具体的には、以下のo)に示す素子構成を挙げることができる。
o)陽極/(繰り返し単位B)x/(繰り返し単位A)/陰極
ここで、記号「x」は2以上の整数を表し、「(繰り返し単位B)x」は、(繰り返し単位B)を「x」段積層した構成を表す。電荷発生層とは電界を印加することにより、正孔と電子とが発生する層である。電荷発生層としては、例えば、酸化バナジウム、インジウムスズ酸化物(Indium Tin Oxide:略称ITO)、酸化モリブデンなどから成る薄膜を挙げることができる。
基板は、有機EL素子を製造する工程において化学的に変化しないものが好適に用いられ、例えばガラス、プラスチック、高分子フィルム、及びシリコン基板、並びにこれらを積層したものなどが用いられる。前記基板としては、市販のものが使用可能であり、また公知の方法により製造することができる。
陽極は、陽極を通して発光層からの光を取出す構成の有機EL素子の場合、透明又は半透明の電極が用いられる。透明電極又は半透明電極としては、電気伝導度の高い金属酸化物、金属硫化物及び金属などの薄膜を用いることができ、光透過率の高いものが好適に用いられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、ITO、インジウム亜鉛酸化物(Indium Zinc Oxide:略称IZO)、金、白金、銀、及び銅などから成る薄膜が用いられ、これらの中でもITO、IZO、又は酸化スズから成る薄膜が好適に用いられる。陽極の作製方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法などを挙げることができる。また、該陽極として、ポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などの有機の透明導電膜を用いてもよい。
正孔注入層を構成する正孔注入材料としては、酸化バナジウム、酸化モリブデン、酸化ルテニウム、及び酸化アルミニウムなどの酸化物や、フェニルアミン系、スターバースト型アミン系、フタロシアニン系、アモルファスカーボン、ポリアニリン、及びポリチオフェン誘導体などを挙げることができる。
正孔輸送層を構成する正孔輸送材料としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミン残基を有するポリシロキサン誘導体、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリ(p-フェニレンビニレン)若しくはその誘導体、又はポリ(2,5-チエニレンビニレン)若しくはその誘導体、ポリフルオレン誘導体、芳香族アミン残基を有する高分子化合物などを挙げることができる。
正孔輸送層が機能層でない場合、正孔輸送層の形成方法としては、正孔輸送材料を含む薄膜を成膜し、その後焼成又は乾燥する方法があげられる。
正孔輸送材料を含む薄膜の成膜方法としては、特に制限はないが、低分子の正孔輸送材料では、高分子バインダーと正孔輸送材料とを含む混合液からの成膜を挙げることができ、高分子の正孔輸送材料では、正孔輸送材料を含む溶液からの成膜を挙げることができる。
発光層に含まれる有機化合物としては、前述の発光性有機化合物、発光性有機化合物を補助するドーパントなどが挙げられる。
電子輸送層を構成する電子輸送材料としては、公知のものを使用でき、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアントラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は8-ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体などを挙げることができる。
電子輸送層が機能層でない場合、電子輸送層の形成方法としては、電子輸送材料を含む薄膜を成膜し、その後焼成又は乾燥する方法があげられる。
電子輸送材料を含む薄膜の成膜法としては特に制限はないが、低分子の電子輸送材料では、粉末からの真空蒸着法、又は溶液若しくは溶融状態からの成膜を挙げることができ、高分子の電子輸送材料では溶液又は溶融状態からの成膜を挙げることができる。なお溶液又は溶融状態からの成膜する場合には、高分子バインダーを併用してもよい。溶液から電子輸送層を成膜する方法としては、前述の溶液から正孔輸送層を成膜する方法と同様の成膜法を挙げることができ、前述した機能層形成工程と同様の雰囲気中において成膜することが好ましい。
電子注入層を構成する材料としては、発光層の種類に応じて最適な材料が適宜選択され、アルカリ金属、アルカリ土類金属、アルカリ金属及びアルカリ土類金属のうちの1種類以上含む合金、アルカリ金属若しくはアルカリ土類金属の酸化物、ハロゲン化物、炭酸化物、又はこれらの物質の混合物などを挙げることができる。アルカリ金属、アルカリ金属の酸化物、ハロゲン化物、及び炭酸化物の例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、酸化リチウム、フッ化リチウム、酸化ナトリウム、フッ化ナトリウム、酸化カリウム、フッ化カリウム、酸化ルビジウム、フッ化ルビジウム、酸化セシウム、フッ化セシウム、炭酸リチウムなどを挙げることができる。また、アルカリ土類金属、アルカリ土類金属の酸化物、ハロゲン化物、炭酸化物の例としては、マグネシウム、カルシウム、バリウム、ストロンチウム、酸化マグネシウム、フッ化マグネシウム、酸化カルシウム、フッ化カルシウム、酸化バリウム、フッ化バリウム、酸化ストロンチウム、フッ化ストロンチウム、炭酸マグネシウムなどを挙げることができる。電子注入層は、2層以上を積層した積層体で構成されてもよく、例えばLiF/Caなどを挙げることができる。電子注入層は、蒸着法、スパッタリング法、印刷法などにより形成される。
陰極の材料としては、仕事関数の小さく、発光層への電子注入が容易で、電気伝導度の高い材料が好ましい。また陽極側から光を取出す有機EL素子では、発光層からの光を陰極で陽極側に反射するために、陰極の材料としては可視光反射率の高い材料が好ましい。
陰極には、例えばアルカリ金属、アルカリ土類金属、遷移金属及びIII-B族金属などを用いることができる。陰極の材料としては、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウムなどの金属、前記金属のうちの2種以上の合金、前記金属のうちの1種以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうちの1種以上との合金、又はグラファイト若しくはグラファイト層間化合物などが用いられる。合金の例としては、マグネシウム-銀合金、マグネシウム-インジウム合金、マグネシウム-アルミニウム合金、インジウム-銀合金、リチウム-アルミニウム合金、リチウム-マグネシウム合金、リチウム-インジウム合金、カルシウム-アルミニウム合金などを挙げることができる。また、陰極としては導電性金属酸化物及び導電性有機物などから成る透明導電性電極を用いることができる。具体的には、導電性金属酸化物として酸化インジウム、酸化亜鉛、酸化スズ、ITO、及びIZOを挙げることができ、導電性有機物としてポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などを挙げることができる。なお、陰極は、2層以上を積層した積層体で構成されていてもよい。
絶縁層の材料としては、金属フッ化物、金属酸化物、有機絶縁材料などを挙げることができる。膜厚2nm以下の絶縁層を設けた有機EL素子としては、陰極に隣接して膜厚2nm以下の絶縁層を設けたもの、陽極に隣接して膜厚2nm以下の絶縁層を設けたものを挙げることができる。
以下の方法で、有機EL素子を作製した。
スパッタ法により厚みが150nmのITO膜(陽極)が形成されたガラス基板に、ポリ(3,4)エチレンジオキシチオフェン/ポリスチレンスルフォン酸(スタルク製「Baytron P」)の懸濁液をスピンコート法により塗布し、厚みが65nmの薄膜を形成し、さらにホットプレート上で200℃、10分間加熱することによって薄膜を焼成し、正孔注入層を得た。なお正孔注入層の形成において、薄膜の形成工程及び焼成工程は大気雰囲気中においておこなった。
有機層の形成において、酸素濃度が体積基準で10ppm以下、重量基準の絶対湿度が、7.7×10-3kg/kg(DA)に制御された湿潤窒素中で薄膜を保管した以外は、実施例1と同様の方法で有機EL素子を作製した。
有機層の形成において、湿潤窒素中での薄膜の保管を行わない以外は、実施例1と同様の方法で有機EL素子を作製した。
以下の方法で有機EL素子を作製した。
スパッタ法により厚みが150nmのITO膜(陽極)が形成されたガラス基板に、ポリ(3,4)エチレンジオキシチオフェン/ポリスチレンスルフォン酸(スタルク製「Baytron P」)の懸濁液をスピンコート法により塗布し、厚みが65nmの薄膜を形成し、さらにホットプレート上で200℃、10分間加熱することによって薄膜を焼成し、正孔注入層を得た。なお正孔注入層の形成において、薄膜の形成工程及び焼成工程は大気雰囲気中においておこなった。
有機層の形成において、酸素濃度が体積基準で10ppm以下、重量基準の絶対湿度が、7.5×10-3kg/kg(DA)に制御された湿潤窒素中で薄膜を保管した以外は、実施例3と同様の方法で有機EL素子を作製した。
有機層の形成において、湿潤窒素中での薄膜の保管を行わない以外は、実施例3と同様の方法で有機EL素子を作製した。
高分子化合物4の合成
不活性雰囲気下、2,7-ビス(1,3,2-ジオキサボロラン-2-イル)-9,9-ジオクチルフルオレン(5.20g)、ビス(4-ブロモフェニル)-(4-セカンダリブチルフェニル)-アミン(4.50g)、酢酸パラジウム(2.2mg)、トリ(2-メチルフェニル)ホスフィン(15.1mg)、Aliquat336(0.91g,アルドリッチ製)、トルエン(70ml)を混合し、105℃に加熱した。この反応溶液に2重量モル炭酸ナトリウム水溶液(19ml)を滴下し、4時間還流させた。反応後、フェニルホウ酸(121mg)を加え、さらに3時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え80℃で4時間撹拌した。冷却後、水(60ml)で3回、3重量%酢酸水溶液(60ml)で3回、水(60ml)で3回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール(3L)に滴下し、3時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物4の収量は5.25gであった。
高分子化合物5の合成
ジムロートを接続した200mLセパラブルフラスコに、9,9-ジオクチルフルオレン-2,7-ジホウ酸エチレングリコールエステル 3.18g(6.0mmol)、9,9-ジオクチル-2,7-ジブロモフルオレン 3.06g(5.4mmol)、N,N’-ビス(4-ブロモフェニル)-N,N’-ビス(2,6-ジメチル-4-tert-ブチルフェニル)-1,4-フェニレンジアミン 0.44g(0.6mmol)、メチルトリオクチルアンモニウムクロライド(商品名:Aliquat336(登録商標)、アルドリッチ社製) 0.82g、及びトルエン60mLを加えた。窒素雰囲気下、ビストリフェニルホスフィンパラジウムジクロリド 4.2mgを加え、85℃に加熱した。得られた溶液に、17.5重量%炭酸ナトリウム水溶液 16.3mLを滴下しながら105℃に加熱した後、1.5時間攪拌した。次に、フェニルホウ酸 0.74g、及びビストリフェニルホスフィンパラジウムジクロリド 4.2mgとトルエン30mLを加え、105℃で17時間攪拌した。得られた溶液から、水層を除いた後、N,N-ジエチルジチオカルバミド酸ナトリウム三水和物 3.65g及びイオン交換水 36mLを加え、85℃で2時間攪拌した。有機層を水層と分離した後、有機層をイオン交換水 80mL(2回)、3重量%酢酸水溶液 80mL(2回)、イオン交換水 80mL(2回)の順番で洗浄した。洗浄した有機層をメタノール 930mLに滴下したところ、沈殿物が生じたので、該沈殿物をろ過した後、乾燥させ、固体を得た。この固体をトルエン 190mLに溶解させて溶液を調製し、あらかじめトルエンを通液したシリカゲル/アルミナカラムに該溶液を通液し、得られた溶液をメタノール930mLに滴下したところ、沈殿物が生じたので、沈殿物をろ過後乾燥させ、下記式で表される繰り返し単位を、仕込み原料から求めた理論値で、以下のモル比で有する高分子化合物5(4.17g)を得た。高分子化合物5のポリスチレン換算の数平均分子量Mnは2.7×105であり、ポリスチレン換算の重量平均分子量Mwは7.1×105であった。
化合物M-1の合成
LC-MS(ESI、positive):m/z+=573 [M+K]+
高分子化合物6の合成
窒素雰囲気下、化合物M-1 3.13g、2,7-ジブロモ-9,9-ジオクチルフルオレン3.58g、酢酸パラジウム(II)2.2mg、トリス(2-メトキシフェニル)ホスフィン13.4mg、及びトルエン80mLを混合し、100℃に加熱した。反応溶液に20重量%テトラエチルアンモニウムヒドロキシド水溶液21.5mlを滴下し、4.5時間還流させた。反応後、そこに、フェニルホウ酸78mg、酢酸パラジウム(II)2.2mg、トリス(2-メトキシフェニル)ホスフィン13.4mg、トルエン20mL、及び20重量%テトラエチルアンモニウムヒドロキシド水溶液21.5mlを加え、更に15時間還流させた。次いで、そこに、0.2Mのジエチルジチオカルバミン酸ナトリウム水溶液70mlを加え、85℃で2時間撹拌した。反応溶液を室温まで冷却し、水82mlで3回、3重量%の酢酸水溶液82mlで3回、水82mlで3回洗浄した。有機層をメタノール1200mlに滴下したところ沈殿が生じ、この沈殿を濾過した後、乾燥させ、固体を得た。この固体をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られた溶出液をメタノール1500mlに滴下したところ、高分子化合物6を3.52g得た。高分子化合物6のポリスチレン換算の数平均分子量は3.0×105であり、ポリスチレン換算の重量平均分子量は8.4×105であった。
高分子化合物1の代わりに合成例1で合成した高分子化合物4を用い、燐光発光性有機化合物1の代わりに国際公開第2002/44189号パンフレットに記載の方法に従って合成した下記式:
高分子化合物1の代わりに合成例1で合成した高分子化合物4を用い、燐光発光性有機化合物2の代わりに下記式:
高分子化合物7の合成
不活性ガス雰囲気下、2,7-ジブロモ-9,9-ジ(オクチル)フルオレン(9.0g、16.4mmol)、N,N’-ビス(4-ブロモフェニル)-N,N’-ビス(4-t-ブチル-2,6-ジメチルフェニル)1,4-フェニレンジアミン(1.3g、1.8mmol)、2,7-ビス(4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル)-9,9-ジ(4-ヘキシルフェニル)フルオレン(13.4g、18.0mmol)、テトラエチルアンモニウムヒドロキシド(43.0g、58.3mmol)、酢酸パラジウム(8mg、0.04mmol)、トリ(2-メトキシフェニル)ホスフィン(0.05g、0.1mmol)、トルエン(200mL)を混合し、混合物を、90℃で8時間加熱攪拌した。次いで、フェニルボロン酸(0.22g、1.8mmol)を添加し、得られた混合物を14時間撹拌した。放冷後、水層を除去し、ジエチルジチオカルバミン酸ナトリウム水溶液を添加し撹拌した後、水層を除去し、有機層を水、3%酢酸水で洗浄した。有機層をメタノールに注いでポリマーを沈殿させた後、濾取したポリマーを再度トルエンに溶解させ、シリカゲル及びアルミナのカラムに通液した。ポリマーを含む溶出トルエン溶液を回収し、回収した前記トルエン溶液をメタノールに注いでポリマーを沈殿させた。沈殿したポリマーを50℃で真空乾燥し、高分子化合物7(12.5g)を得た。ゲルパーミエーションクロマトグラフィーによれば、得られた高分子化合物7のポリスチレン換算の重量平均分子量は3.1×105であり、分子量分布指数(Mw/Mn)は2.9であった。
燐光発光性有機化合物5の合成
下記式で示される燐光発光性有機化合物5は、特開2006-188673号公報に記載の方法に従って合成した。
以下の方法で有機EL素子を作製した。
スパッタ法により厚みが45nmのITO膜(陽極)が形成されたガラス基板に、ポリ(3,4)エチレンジオキシチオフェン/ポリスチレンスルフォン酸(スタルク製;Baytron P)の懸濁液をスピンコート法により塗布し、厚みが65nmの薄膜を形成し、さらにホットプレート上で200℃、10分間加熱することによって薄膜を焼成し、正孔注入層を得た。なお正孔注入層の形成において、薄膜の形成工程及び焼成工程は大気雰囲気中においておこなった。
有機層の形成において、湿潤窒素中での薄膜の保管を行わない以外は、実施例7と同様の方法で有機EL素子を作製した。
2…基板、
3…第1の電極、
4…第1の有機層、
5…第2の有機層、
6…有機層、
6’…第3の有機層、
7…第2の電極、
11…有機薄膜形成工程を行う空間、
12…有機薄膜保管工程を行う空間、
13…緩衝空間、
14…基板。
Claims (21)
- 第1の電極と、第2の電極と、該第1の電極及び第2の電極間に設けられる有機層とを有し、該有機層が有機化合物を含む有機エレクトロルミネッセンス素子の製造方法であって、該有機層は、
体積基準で10ppm以下の水分濃度を有する低湿度雰囲気下において、該有機層が上に形成される層の表面上に、塗布法により有機化合物を含む有機薄膜を形成する有機薄膜形成工程と、
2.0×10-3kg/kg(乾燥空気)以上の重量基準の絶対湿度を有する高湿度雰囲気下において、該有機薄膜形成工程によって得られた有機薄膜を保管する有機薄膜保管工程とを、
包含する方法によって形成される、有機エレクトロルミネッセンス素子の製造方法。 - 前記高湿度雰囲気が2.0×10-3kg/kg(乾燥空気)以上、2.0×10-2kg/kg(乾燥空気)以下の重量基準の絶対湿度を有する請求項1に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記高湿度雰囲気が5.0×10-3kg/kg(乾燥空気)以上、1.5×10-2kg/kg(乾燥空気)以下の重量基準の絶対湿度を有する請求項1に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記低湿度雰囲気が不活性ガスを含有する請求項1~3のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記低湿度雰囲気が体積基準で10ppm以下の酸素濃度を有する請求項1~4のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜形成工程及び有機薄膜保管工程は、有機薄膜形成工程を行う雰囲気の空間、緩衝空間、及び有機薄膜保管工程を行う雰囲気の空間を、順に基板を通過させて行われ、該緩衝空間の気圧は、有機薄膜形成工程を行う空間及び有機薄膜保管工程を行う空間のそれぞれと比較して陰圧にされている請求項1~5のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜形成工程及び有機薄膜保管工程は、有機薄膜形成工程を行う雰囲気の空間、及び有機薄膜保管工程を行う雰囲気の空間を、順に基板を通過させて行われ、有機薄膜形成工程を行う空間の気圧は、有機薄膜保管工程を行う空間と比較して陽圧にされている請求項1~5のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜保管工程に次いで行われる有機薄膜を焼成する工程を包含する請求項1~7のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜を焼成する工程が不活性ガスを含有する雰囲気下で行われる請求項8に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜を焼成する工程が体積基準でそれぞれ10ppm以下の酸素濃度および水分濃度を有する雰囲気下で行われる請求項8または9に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機薄膜を焼成する工程が10Pa以下の圧力を有する減圧雰囲気下で行われる請求項8または9に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記第1の電極が陽極であり、前記第2の電極が陰極である請求項1~11のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機層が高分子有機化合物を含む請求項1~12のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機層が発光層である請求項1~13のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記有機層が燐光発光性化合物を含む請求項1~14のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記発光層に接して機能層を形成する工程を更に包含する請求項14または15に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記機能層が発光層と第1の電極との間に形成される請求項16に記載の有機エレクトロルミネッセンス素子の製造方法。
- 前記機能層が高分子有機化合物を含む請求項16または17に記載の有機エレクトロルミネッセンス素子の製造方法。
- 請求項1~18のいずれか一項に記載の有機エレクトロルミネッセンス素子の製造方法によって製造された有機エレクトロルミネッセンス素子。
- 請求項19に記載の有機エレクトロルミネッセンス素子を備える面状光源。
- 請求項19に記載の有機エレクトロルミネッセンス素子を備える表示装置。
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2012
- 2012-02-01 US US13/981,966 patent/US9093667B2/en active Active
- 2012-02-01 WO PCT/JP2012/052247 patent/WO2012105600A1/ja active Application Filing
- 2012-02-01 JP JP2012019798A patent/JP5980513B2/ja active Active
- 2012-02-01 KR KR1020137019950A patent/KR101918313B1/ko active IP Right Grant
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JP2007122914A (ja) * | 2005-10-25 | 2007-05-17 | Sharp Corp | 有機エレクトロルミネッセンスディスプレイの製造方法及びそれに用いる製造装置 |
JP2007234293A (ja) * | 2006-02-28 | 2007-09-13 | Seiko Epson Corp | 有機半導体素子の製造方法、有機el装置の製造方法および有機el装置の製造装置 |
JP2008235196A (ja) * | 2007-03-23 | 2008-10-02 | Toyota Industries Corp | 有機el装置の製造方法 |
JP2009266814A (ja) * | 2008-04-02 | 2009-11-12 | Mitsubishi Chemicals Corp | 有機電界発光素子の製造方法、有機電界発光素子、有機elディスプレイ及び有機el照明 |
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KR20140006848A (ko) | 2014-01-16 |
US20130306953A1 (en) | 2013-11-21 |
US9093667B2 (en) | 2015-07-28 |
KR101918313B1 (ko) | 2018-11-13 |
JP5980513B2 (ja) | 2016-08-31 |
JP2012178343A (ja) | 2012-09-13 |
TW201246652A (en) | 2012-11-16 |
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