JP2003297561A - Manufacturing method of organic film element and organic film element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing efficiently an organic film element such as an organic EL element that is superior in uniformity of light- emission quantity, luminous efficiency, and durability. <P>SOLUTION: The manufacturing method of the organic film element comprises a process in which a substrate having an film layer on the support body of the substrate is used and a transfer body is made by forming an organic film layer on a temporary support body by a wet method, and the transfer body is overlapped on the substrate so that the organic film layer side faces the above film layer and heated, then, by separating the temporary support body, the organic film layer is transferred on the film coated face of the substrate. The coefficient of linear thermal expansion of the substrate support body is 20 ppm/°C or less. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an organic thin film element suitable for a surface light source such as a full-color display, a backlight, an illumination light source and a light source array such as a printer, and an organic thin film element, and particularly excellent as an organic EL element. The present invention also relates to a method for manufacturing an organic thin film element having emission brightness and durability and an organic thin film element.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Organic EL
Organic light-emitting devices such as organic light-emitting devices can be easily applied to planar light-emitting devices, and are therefore attracting attention as new optical devices. Specifically, it is promising to be used as a solid-state light-emitting type inexpensive large-area full-color display device and a writing light source array, and is under active development.

Generally, an organic light emitting device includes a light emitting layer and a pair of counter electrodes (a back electrode and a transparent electrode) sandwiching the light emitting layer.
It consists of In the organic light emitting device, when an electric field is applied between the pair of counter electrodes, electrons are injected from the back electrode and holes are injected from the transparent electrode into the organic light emitting device. Electrons and holes are recombined in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band to emit light.

Most of the organic thin film layers of the organic EL device are manufactured by a vapor deposition method. For example, JP-A-9-167684 and JP-A-9-167684
2000-195665 proposes a method in which an organic layer is uniformly formed in advance on a temporary substrate of mica or film by a vapor deposition method, and then the substrate and the organic layer are brought close to each other and heating vapor deposition is performed. However, these methods have a problem that the manufacturing efficiency is low because the vapor deposition method is used. Further, since only low molecular weight organic compounds can be used for the organic thin film, when used for flexible displays and the like, the durability such as bending resistance and film strength is insufficient, which becomes a problem especially when the area is increased.

Polyparaphenylene vinylene which emits green light ("Nature", Vol. 347, page 539, 1990),
Poly 3-alkylthiophene that emits red light (Japanese Journal of Applied Physics,
30, L1938, 1991), blue light-emitting polyalkylfluorene (Japanese Journal of Applied Physics, 30, L1941, 1991) and other light-emitting thin films of polymers and low-molecular compounds. A polymer type element using a light emitting thin film in which is dispersed in a binder resin is also known. These polymer type devices are advantageous in increasing the area and are expected to be used for flexible displays, but as described above, the vapor deposition method cannot be applied to the formation of the organic light emitting thin film. Therefore, the thin film is usually formed directly on the substrate by a wet method.

However, in the wet method, the film thickness uniformity of the organic thin film becomes insufficient due to the surface tension of the solution, and when the organic thin film layers are laminated, each organic thin film layer is dissolved at the interface. is there. Therefore, the organic thin film device obtained by this method has a problem that the uniformity of light emission, the light emission efficiency and the device durability are poor.

[0007] WO 00/41893 proposes a method of thermal transfer by laser using an organic thin film and a donor sheet having a photothermal conversion layer. However, in the case of thermal transfer as in WO 00/41893, there is a problem in that gas is entrained in the bonding interface of the organic thin film layer and the device function deteriorates. There is also a problem that the light emitting efficiency and durability of the organic EL element and the uniformity of the light emitting surface differ depending on the state of the interface of the organic thin film layer.

In the case of patterned thermal writing using a thermal head or a laser used in the field of printing technology, a temperature distribution is generated around the pattern due to thermal diffusion, and the contour of the organic thin film pattern is cut cleanly from the donor side. Not done. For this reason, there are problems that variations in the amount of emitted light occur, electrical defects and defects due to thin film fragments occur, and durability deteriorates. In addition, there is a problem that the yield is lowered due to the misalignment of the substrate with the thermal head or the laser.

Accordingly, an object of the present invention is to provide a method for producing an organic thin film element which can easily form an organic thin film layer on a substrate and has good uniformity and a good bonding interface, and an organic thin film element obtained by the production method. In particular, by forming a uniform organic thin film layer using a wet method, it is possible to obtain an organic compound excellent in luminous efficiency, uniformity of luminous intensity, and durability.
It is intended to provide a method for efficiently manufacturing an organic thin film element such as an EL element and an organic thin film element obtained by the manufacturing method.

[0010]

As a result of earnest research in view of the above objects, the present inventors have found that the organic thin film layer constituting the organic thin film element is applied onto a temporary support by a wet method, and the organic thin film layer is formed. By transferring to the film formation surface on the substrate support with a linear thermal expansion coefficient of 20 ppm / ° C or less, organic thin film elements such as organic EL elements with excellent luminous efficiency, uniformity of light emission amount and durability can be efficiently used. The inventors have discovered that they can be manufactured and have conceived the present invention.

That is, the present invention has been achieved by the following means. (1) Using a substrate having a thin film layer on a substrate support, a transfer member is prepared by forming an organic thin film layer on a temporary support by a wet method, and the organic thin film layer side faces the thin film layer. As described above, there is a step of transferring the organic thin film layer to the film formation surface of the substrate by heating the transfer member on the substrate and heating it, and peeling off the temporary support, and at least the substrate support. A method for manufacturing an organic thin film element, which has a coefficient of linear thermal expansion of 20 ppm / ° C or less. (2) The method for manufacturing an organic thin film element according to (1) above, wherein the substrate support has flexibility. (3) In the method for manufacturing an organic thin film element according to (2) above, the water permeability of the flexible substrate support is 1 g /
A method for manufacturing an organic thin film element, characterized in that it is m ² · day · atm or less. (4) In the method for producing an organic thin film element according to (2) or (3), the flexible substrate support has an oxygen permeability of 1 cc / m ² · day · atm or less. And a method for manufacturing an organic thin film element. (5) In the method for manufacturing an organic thin film element according to any one of (2) to (4) above, the flexible substrate support is made of a metal foil provided with an insulating layer on one side or both sides. A method for manufacturing a characteristic organic thin film element. (6) The method for producing an organic thin film element according to (5) above, wherein the metal foil is an aluminum foil or a copper foil. (7) The method for producing an organic thin film element according to (5) or (6) above, wherein the insulating layer is made of a metal oxide and / or a metal nitride. (8) The method for manufacturing an organic thin film element according to (5) or (6), wherein the insulating layer is made of polyimide or liquid crystal polymer. (9) An organic thin film element manufactured by the method for manufacturing an organic thin film element according to any one of (1) to (8) above. (10) The organic thin film element according to (9) above, which has an anode, one or more organic thin film layers including at least a light emitting organic thin film layer, and a transparent cathode on the substrate support. (11) The organic thin film element according to (9) above, which has a cathode, at least one organic thin film layer including at least a light emitting organic thin film layer, and a transparent anode on the substrate support.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, a method for manufacturing an organic thin film element of the present invention will be explained, then a transfer body of an organic thin film layer will be explained, and finally an organic thin film element will be explained.

[1] Method of Manufacturing Organic Thin Film Element The method of the present invention uses a transfer body having an organic thin film layer formed on a temporary support by a wet method, and transfers the organic thin film layer onto a substrate by a peel transfer method. It is characterized by doing. In the peeling transfer method, the organic thin film layer is softened by heating the transfer body and adhered to the film formation surface of the substrate, and then the temporary support is peeled off to form only the organic thin film layer on the film formation surface. It is a method (transfer method) of leaving it in the. As the heating means, a generally known method can be used, and for example, a laminator, an infrared heater, a laser, a thermal head or the like can be used.
As the thermal head, for example, the first laminator VA-400
III (manufactured by Taisei Laminator Co., Ltd.) or a thermal head for thermal transfer printing can be used.

When the transfer member is superposed on the substrate and heated, it is preferable to apply pressure. The pressure is preferably 0.05 to 50 MPa, more preferably 0.1 to 20 MPa, even more preferably 0.1 to 10 MPa.

The transfer temperature is not particularly limited, and can be changed depending on the material of the organic thin film layer and the heating member, but generally 40 to 25
The temperature is preferably 0 ° C, more preferably 50 to 200 ° C, even more preferably 60 to 180 ° C. However, the preferable range of the transfer temperature is related to the heat resistance of the heating member, the transfer body, and the substrate, and changes as the heat resistance improves. The temperature at which the temporary support is peeled off is
It is preferably 10 ° C. or higher and lower than the transfer temperature. The substrate and / or the transfer body are preferably continuous webs.

The apparatus that can be used for manufacturing the organic thin film element is
For example, a device for feeding a transfer body having an organic thin film layer formed on a temporary support by a wet method and a device for forming the organic thin film layer on the substrate by pressing the transfer body against the film formation surface of the substrate while heating the transfer body. It has a device for transferring to the film surface and a device for peeling the temporary support from the organic thin film layer after the transfer.

FIG. 1 shows an example of an apparatus for carrying out the method of manufacturing an organic thin film element of the present invention. A transfer body 110 in which an organic thin film layer 112 is provided on a temporary support body 111 is supplied from a transfer body winding roll 113. The transfer device includes a heating roll 121 and a pressure (heating) roll 122. The pressure (heating) roll is a pressure roll that heats as needed. The substrate support 10 is provided between the heating roll 121 and the pressure (heating) roll 122.
A substrate 100 composed of 1 and a conductive layer (cathode or anode) 102 is arranged, and the conductive layer 102 of the substrate 100 is the organic thin film layer 112 of the transfer body 110.
So that the heating roll 121 and the conductive layer 102 of the substrate 100 are in contact with each other.
And the transfer body 110 is fed between. The organic thin film layer 112 is heated by the heating roll 121, or by applying pressure while heating by the heating roll 121 and the pressure (heating) roll 122.
To the conductive layer 102. The remaining temporary support 111 is wound by a temporary support winding roll 114.

In the present invention, a plurality of organic thin film layers can be laminated on the substrate by repeating the steps of transferring the organic thin film layer 112 and peeling the temporary support 111. The composition of the plurality of organic thin film layers may be the same or different. When the composition is the same, there is an advantage that layer omission due to transfer failure or peeling failure can be prevented. When different layers are provided, the function can be separated to improve the light emission efficiency. For example, the hole transporting organic thin film layer / light emitting organic thin film layer can be formed on the film formation surface by the transfer method of the present invention. / Electron transporting organic thin film layer, light emitting organic thin film layer / electron transporting organic thin film layer / electron injection layer, hole injection layer / hole transporting organic thin film layer / light emitting organic thin film layer / electron transporting organic thin film layer / electron Injection layers and the like can be laminated. At this time, the transfer temperature is preferably set such that the temperature at which the first transfer member is heated is equal to or higher than the temperature at which the next transfer member is heated so that the first transfer layer is not reversely transferred to the next transfer layer.

When forming a plurality of organic thin film layers, two or more kinds of transfer bodies having organic thin film layers having the same or different composition may be used, or two or more kinds of organic thin film layers having the same or different composition may be used. A transfer body may be used. The two or more organic thin film layers preferably contain at least one common component.

It is preferable to reheat the organic thin film layer transferred to the substrate or the new organic thin film layer transferred to the previously transferred organic thin film layer, if necessary. The reheating causes the organic thin film layer to adhere more closely to the substrate or the previously transferred organic thin film layer. At the time of reheating, it is preferable to apply pressure as needed. The reheating temperature is preferably in the range of the transfer temperature ± 50 ° C. and is equal to or higher than the glass transition temperature or the flow initiation temperature of the organic thin film layer.

In order to prevent reverse transfer of the first transfer layer to the next transfer layer, a surface treatment may be performed between the first transfer step and the next transfer step so as to improve the adhesion to the film-forming surface. Good. Examples of such surface treatment include activation treatments such as corona discharge treatment, flame treatment, glow discharge treatment, and plasma treatment. When the surface treatment is also used, the transfer temperature of the first transfer member may be lower than the transfer temperature of the next transfer member unless reverse transfer is performed.

Prior to the transfer, it is preferable to preheat the substrate and / or the transfer body. The preheating temperature of the substrate and / or the transfer body is preferably 30 ° C. or higher and + 20 ° C. or lower. The apparatus for manufacturing the organic thin film element preferably has means for preheating the substrate and / or the transfer body in this way. Further, it is preferable to have a cooling device in the latter stage of the transfer device. Further, it is preferable that an entrance angle adjusting unit is provided on the front surface of the transfer device and a peeling angle adjusting unit is provided on the rear surface of the transfer device or the cooling device. The angle of penetration of the transfer body with respect to the substrate is preferably 90 ° or less, and the peeling angle of the temporary support from the organic thin film layer is preferably 90 ° or more.

The method and apparatus for manufacturing an organic thin film element described in detail in Japanese Patent Application No. 2001-089663 can be applied to the present invention.

[2] Transfer Member (1) The constituent organic thin film layer is formed on a temporary support by a wet method. The transfer bodies may be produced individually or, as shown in FIG. 2, organic thin film layers may be provided in a frame sequential manner. In the transfer body shown in FIG. 2, 112a, 112b, 112c and a plurality of organic thin film layers are provided on a single temporary support in the order of proceeding method. This transfer 110
By using, it is possible to continuously form a plurality of organic thin film layers without the need to replace the transfer body.

By using a transfer body in which two or more organic thin film layers are preliminarily laminated on the temporary support, the multilayer film can be laminated on the film formation surface of the substrate in one transfer step. in this case,
If the interface of each organic thin film layer to be laminated is not uniform, the movement of holes and electrons will be uneven.Therefore, it is necessary to carefully select the solvent to make the interface uniform. It is necessary to select an organic compound for the thin film layer.

(2) Temporary Support The temporary support used in the present invention is preferably made of a material that is chemically and thermally stable and has flexibility. Specifically, fluorocarbon resin [eg, tetrafluoroethylene resin (PTFE), trifluorochloroethylene resin (PCTFE)],
Polyester (eg polyethylene terephthalate, polyethylene naphthalate (PEN)), polyarylate,
Polycarbonate, polyolefin (eg polyethylene, polypropylene), polyether sulfone (PES)
And the like, or a laminated body thereof is preferable. The thickness of the temporary support is appropriately 1 to 300 μm, and 3 to 20
The thickness is preferably 0 μm, more preferably 5 to 150 μm.

(3) Formation of Organic Thin Film Layer on Temporary Support In the present invention, the organic thin film layer on the temporary support is formed by a wet method. Specifically, the organic thin film layer material is dissolved in an organic solvent, and the resulting solution is applied to a temporary support. The solid content of the coating liquid is not particularly limited, and the viscosity of the coating liquid can be arbitrarily selected according to the type of wet method. The coating method is not particularly limited as long as a dry film thickness of the organic thin film layer is 200 nm or less and a uniform film thickness distribution can be obtained, and a spin coating method, a gravure coating method, a dip coating method, a casting method, a die coating method, a roll method. Examples thereof include a coating method, a bar coating method, an extrusion coating method, an inkjet method and the like. Among them, the extrusion coat method, which has high productivity by roll-to-roll, is preferable.

(4) Organic thin film layer The organic thin film layer is a layer constituting an organic thin film element, and from the respective characteristics, a light emitting organic thin film layer, an electron transporting organic thin film layer, a hole transporting organic thin film layer, and an electron injecting layer. , Hole injection layer and the like. The organic thin film layer preferably contains at least a light emitting organic compound or a carrier transporting organic compound. Further, various organic compounds for improving the color developability can be added to the organic thin film layer. For specific examples of the compound used for each layer, see, for example, “Monthly Display” 19
It is described in the "Organic EL Display" (Techno Times, Inc.) etc. in the October 1998 issue.

The glass transition temperature of the organic thin film layer itself or its polymer component is preferably 40 ° C. or higher and the transfer temperature + 40 ° C. or lower, more preferably 50 ° C. or higher and the transfer temperature + 20 ° C. or lower. More preferably, the temperature is not lower than 60 ° C. and not higher than the transfer temperature. Further, the flow initiation temperature of the organic thin film layer itself of the transfer member or its polymer component is preferably 40 ° C or higher and the transfer temperature + 40 ° C or lower, more preferably 50 ° C or higher and the transfer temperature + 20 ° C or lower. More preferably, the temperature is not lower than 60 ° C. and not higher than the transfer temperature. The glass transition temperature can be measured by, for example, a differential scanning calorimeter (DSC). The flow starting temperature can be measured using, for example, a flow tester CFT-500 manufactured by Shimadzu Corporation.

The solvent used for preparing the coating solution by dissolving the material of the organic thin film layer is not particularly limited, and a luminescent compound,
It can be appropriately selected depending on the type of host compound, hole transport material, electron transport material, polymer binder, and the like. Specific examples of usable solvents include halogen solvents such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane and chlorobenzene, and ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone and cyclohexanone. Solvents, benzene, toluene, aromatic solvents such as xylene, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, ester solvents such as diethyl carbonate, tetrahydrofuran, Examples thereof include ether solvents such as dioxane, amide solvents such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, water and the like.

(A) Luminescent Organic Thin Film Layer The luminescent organic thin film layer contains at least one luminescent compound. The light emitting compound is not particularly limited, and may be a fluorescent light emitting compound or a phosphorescent light emitting compound.
Further, the fluorescent compound and the phosphorescent compound may be used at the same time. In the present invention, it is preferable to use a phosphorescent compound from the viewpoint of light emission brightness and light emission efficiency.

Examples of the fluorescent compound include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, and perinone. Derivatives, oxadiazole derivatives, aldazine derivatives, pyraridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, aromatic dimethylidene compounds, metal complexes (8-quinolinol Derivative metal complex, rare earth complex, etc., polymer light emitting compound (polythiophene derivative, polyphenylene derivative, polyphenylene vinylene) Derivatives, polyfluorene derivatives and the like)
Etc. can be used. These may be used alone or in combination of two or more.

The phosphorescent compound is preferably a compound capable of emitting light from triplet excitons, and examples thereof include orthometallated complex and porphyrin complex. Among the porphyrin complexes, the porphyrin platinum complex is preferable. The phosphorescent compounds may be used alone or in combination of two or more.

The ortho-metallated complex is described by Akio Yamamoto in “Organometallic Chemistry: Fundamentals and Applications”, pages 150 and 232, Shokabosha (1982), H. Yersin, “Photochemistry and Photop
hysics of Coordination Compounds ", pp. 71-77 and 13
5 to 146, a generic name for a group of compounds described in Springer-Verlag (1987) and the like. The ligand forming the orthometallated complex is not particularly limited, but it is a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative, or 2- (2-thienyl)
Pyridine derivative, 2- (1-naphthyl) pyridine derivative or 2-
It is preferably a phenylquinoline derivative. These derivatives may have a substituent. In addition to these ligands essential for forming the orthometalated complex, other ligands may be contained. As the central metal forming the ortho-metallated complex, any transition metal can be used, and in the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. The organic thin film layer containing such an orthometallated complex is excellent in light emission brightness and light emission efficiency. Specific examples of orthometalated complexes are described in Japanese Patent Application No. 2000-254171.

The orthometallated complex that can be used in the present invention is described in Inorg. Chem., 30, 1685, 1991, Inorg. Che.
m., 27, 3464, 1988, Inorg. Chem., 33, 545, 1994, I
norg. Chim. Acta, 181, 245, 1991, J. Organomet. Ch
em., 335, 293, 1987, J. Am. Chem. Soc. 107, 1431,
It can be synthesized by a known method described in 1985 and the like.

The content of the luminescent compound in the luminescent organic thin film layer is not particularly limited, but is preferably 0.1 to 70% by mass, and more preferably 1 to 20% by mass.
The content of the luminescent compound is less than 0.1% by mass or 70
If the content is more than mass%, the effect may not be sufficiently exhibited.

The luminescent organic thin film layer may contain a host compound, a hole transport material, an electron transport material, an electrically inactive polymer binder and the like, if necessary. Note that the functions of these materials may be simultaneously achieved by one compound. For example, a carbazole derivative functions not only as a host compound but also as a hole transport material.

The host compound is a compound that causes energy transfer from its excited state to the light emitting compound, and as a result causes the light emitting compound to emit light. Specific examples thereof include a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, and a styrylanthracene derivative. , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidene compound, porphyrin compound, anthraquinodimethane derivative, anthrone derivative, diphenylquinone derivative, thiopyran dioxide Heterocyclic tetra derivatives such as derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, and naphthaleneperylene Rubonic anhydride, phthalocyanine derivative, metal complex (metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complex having benzoxazole or benzothiazole as a ligand, etc.), polysilane compound, poly (N-vinylcarbazole) derivative, Examples thereof include aniline copolymers, conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. The host compounds may be used alone or in combination of two or more. The content of the host compound in the light emitting organic thin film layer is preferably 0 to 99.9% by mass,
More preferably, it is ˜99.0 mass%.

The hole transport material is not particularly limited as long as it has any of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. It may be a low molecular weight material or a high molecular weight material. Specific examples thereof include carbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone derivative, styrylanthracene derivative. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N-
Vinylcarbazole) derivative, aniline copolymer, thiophene oligomer, conductive polymer such as polythiophene,
Examples thereof include polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like. These may be used alone or in combination of two or more. The content of the hole transport material in the light emitting organic thin film layer is preferably 0 to 99.9% by mass, and more preferably 0 to 80.0% by mass.

The electron transport material is not particularly limited as long as it has any of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking the holes injected from the anode. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives,
Thiopyran dioxide derivative, carbodiimide derivative,
Fluorenylidene methane derivatives, distyryl pyrazine derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, phthalocyanine derivatives, metal complexes (metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Metal complexes, etc.), aniline copolymers, conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylenevinylene derivatives, polyfluorene derivatives and the like. These may be used alone or in combination of two or more.
The content of the electron transport material in the light emitting organic thin film layer is 0.
It is preferably -99.9% by mass, more preferably 0-80.0% by mass.

As the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin,
Polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal and the like can be used. These may be used alone or in combination of two or more. The luminescent organic thin film layer containing a polymer binder can be easily formed by coating on a large area by a wet film forming method.

The thickness of the luminescent organic thin film layer is preferably 10 to 200 nm, more preferably 20 to 80 nm.
If the thickness exceeds 200 nm, the driving voltage may increase. On the other hand, if it is less than 10 nm, the organic thin film element may be short-circuited.

(B) Hole Transporting Organic Thin Film Layer The organic thin film element may have a hole transporting organic thin film layer made of the above hole transporting material, if necessary. The hole transporting organic thin film layer may contain the above polymer binder. The thickness of the hole transporting organic thin film layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. If the thickness exceeds 200 nm, the drive voltage may increase,
If it is less than 10 nm, the organic thin film element may be short-circuited.

(C) Electron Transporting Organic Thin Film Layer The organic thin film element may have an electron transporting organic thin film layer made of the above electron transporting material, if necessary. The electron transporting organic thin film layer may contain the polymer binder.
The thickness of the electron transporting organic thin film layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. Thickness is 200
If it exceeds 10 nm, the driving voltage may increase, and if it is less than 10 nm, the organic thin film element may short-circuit.

[3] Organic thin film element (1) Structure The whole structure of the organic thin film element is as follows: anode / light emitting organic thin film layer / cathode, anode / light emitting organic thin film layer / electron transporting organic thin film layer on a substrate support. / Cathode, anode / hole transporting organic thin film layer / luminescent organic thin film layer / electron transporting organic thin film layer / cathode, anode / hole transporting organic thin film layer / luminescent organic thin film layer / cathode, anode / luminescent organic thin film Layer / electron transporting organic thin film layer /
A structure in which an electron injection layer / cathode, an anode / hole injection layer / hole transporting organic thin film layer / light emitting organic thin film layer / electron transporting organic thin film layer / electron injection layer / cathode, etc. are laminated in this order, and these are laminated in reverse. It may be configured as described above. One or both of the anode and the cathode is made of a transparent conductive layer, and light is usually taken out from the transparent electrode. Specific examples of the compound used for each layer are described, for example, in "Organic EL Display" (Techno Times Co., Ltd.), which is a separate volume of "Monthly Display" October 1998 issue.

In order to form a plurality of organic thin film layers, in addition to the transfer method of the present invention, dry methods such as vapor deposition and sputtering, dipping, spin coating, dip coating, casting, die coating, roll coating A wet method such as a coating method, a bar coating method, a gravure coating method, a printing method, or the like can be used in combination.

(2) Substrate (a) Substrate support The substrate support used in the present invention has a linear thermal expansion coefficient of 20 ppm /
℃ (20 × 10 ^-6 / ℃) or less. The coefficient of linear thermal expansion is the rate of change of sample length when heated at a constant rate.
It is obtained from the measurement result by the method (thermo-mechanical analysis method). When the coefficient of linear thermal expansion is more than 20 ppm / ° C, cracks and peeling of the electrode and the organic thin film layer occur during heating and cooling after heat transfer, which causes deterioration of durability of the organic thin film element.
The substrate support may be colorless and transparent, colored and transparent, or opaque, but is preferably colorless and transparent because it does not scatter or attenuate the light emitted from the luminescent organic thin film layer. In particular, in the case of taking out light emission from the substrate support side, a colorless and transparent substrate support is used.

Examples of materials having a coefficient of linear thermal expansion of 20 ppm / ° C. or less include metal foils such as aluminum foil, copper foil, stainless steel foil, gold foil and silver foil, and plastic sheets such as polyimide and liquid crystalline polymer. it can. Hard to break,
From the viewpoint of ease of bending and lightness, it is preferable that the substrate support has flexibility.

The water permeability of the substrate support is 1 g / m ² · day · a
It is preferably tm or less, more preferably 0.01 g / m ² · day · atm or less. Oxygen permeability is 1cc / m ² · day ・
Atm or less is preferable, and 0.01 cc / m ² · day · atm or less is more preferable. Water permeability is JIS K 7129B
It can be measured by a method based on the method (1992) (mainly MOCON method (isobaric method)). The oxygen transmission rate is JIS K 7126.
It can be measured by a method (mainly MOCON method) based on the B method (1987). By suppressing the moisture permeability and the oxygen permeability of the substrate support to the above-mentioned levels, it is possible to prevent moisture and oxygen that cause deterioration of durability from entering the organic thin film element.

As the flexible substrate support satisfying the above-mentioned physical property conditions and not causing a short circuit when an electrode is formed, a substrate support provided with an insulating layer on one side or both sides of a metal foil is preferable.
The metal foil is not particularly limited, and metal foil such as aluminum foil, copper foil, stainless steel foil, gold foil, and silver foil can be used. Among them, aluminum foil and copper foil are preferable from the viewpoint of ease of processing and cost. The thickness of the metal foil is 10-100 μm
Is preferred. When the metal foil is thinner than 10 μm, the water permeability and the oxygen permeability of the substrate support become large and the gas barrier property becomes poor, so that the durability of the organic thin film element deteriorates. Further, when the metal foil is thicker than 100 μm, the substrate support has insufficient flexibility, which causes inconvenience in handling.

The insulating layer provided on one side or both sides of the metal foil is not limited, and examples thereof include inorganic substances such as inorganic oxides and inorganic nitrides, polyesters such as polyethylene terephthalate, polybutylene phthalate and polyethylene naphthalate, and
It can be formed from polystyrene, polycarbonate, polyether sulfone, polyarylate, allyl diglycol carbonate, polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), polyimide, plastic such as liquid crystal polymer, or the like. When providing a metal electrode on the insulating layer,
The coefficient of linear thermal expansion of the insulating layer is preferably equal to the coefficient of linear thermal expansion of the electrode metal and the metal foil. From this point of view, the linear thermal expansion coefficient of the insulating layer is preferably 20 ppm / ° C. or less. If it is larger than this, cracking or peeling occurs with heating, which causes deterioration of durability.

As the inorganic insulating material having a linear thermal expansion coefficient of 20 ppm / ° C. or less, metal oxides such as silicon oxide, germanium oxide, zinc oxide, aluminum oxide, titanium oxide and copper oxide, silicon nitride, germanium nitride, Metal nitrides such as aluminum nitride are preferable, and these can be used alone or in combination of two or more.

The thickness of the inorganic insulating layer is preferably 10 to 1000 nm. If the inorganic insulating layer is thinner than 10 nm, the insulation is too low. If the inorganic insulating layer is thicker than 1000 nm, cracks are likely to occur in the substrate support, pinholes will form, and the insulating properties will deteriorate.

The method for forming an insulating layer of a metal oxide and / or a metal nitride is not limited, and a dry method such as a vapor deposition method, a sputtering method, a CVD method or a wet method such as a sol-gel method,
Alternatively, a method in which particles of a metal oxide and / or a metal nitride are dispersed in a solvent and then applied can be used.

Polyimide and liquid crystal polymer are particularly preferable as the plastic insulating material having a linear thermal expansion coefficient of 20 ppm or less. Details of properties of these plastic materials are described in "Plastic Data Book" (edited by Asahi Kasei Amidas "Plastic" editorial department). When a sheet of polyimide or liquid crystal polymer is used as the insulating layer, the sheet and the aluminum foil can be laminated and attached. The thickness of the plastic insulating layer is preferably 10 to 200 μm. If the plastic insulating layer is thinner than 10 μm, it is difficult to handle when laminating, and if it is thicker than 200 μm, the flexibility is impaired and the handling becomes inconvenient.

The insulating layer may be provided on only one side or both sides of the metal foil. When the insulating layers are provided on both sides, both sides may be insulating layers made of metal oxide and / or metal nitride, or both sides may be plastic insulating layers such as a polyimide sheet. An insulating layer made of a metal oxide and / or a metal nitride may be provided on one surface of the metal foil, and a plastic insulating layer may be provided on the other surface.

The substrate support produced as described above has low moisture permeability and low oxygen permeability and has excellent flexibility. The shape, structure, size, etc. of the substrate support are not particularly limited, and can be appropriately selected depending on the application, purpose, etc. of the organic thin film element. Generally, the substrate support is plate-shaped. If necessary, the substrate support may be provided with a hard coat layer, an undercoat layer or the like.

(B) The thin film layer substrate has a thin film layer on the substrate support. The thin film layer is not particularly limited, and examples thereof include electrodes and other conductive layers, electron injection layers,
Examples thereof include a hole injection layer and an organic thin film layer. As the organic thin film layer, a hole transporting organic thin film layer, a light emitting organic thin film layer,
Examples thereof include an electron-transporting organic thin film layer. These organic thin film layers are formed by a method other than the transfer method of the present invention,
For example, dry methods such as vapor deposition and sputtering, dipping,
It is formed by a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, a wet method such as a gravure coating method, or a printing method. The thin film layer on the substrate support may be a single layer or a structure in which two or more layers are laminated.

(3) One or both of the electrode cathode and the anode is made of a transparent conductive layer. When one of the cathode and the anode is made of a transparent conductive layer, which one is used as the transparent electrode depends on the structure of the organic thin film element.

(A) Anode It is sufficient that the anode normally has a function as an anode for supplying holes to the organic thin film layer, and there is no particular limitation on its shape, structure, size, etc. It can be appropriately selected from known electrodes according to the use and purpose.

Examples of the material for the anode include simple metals or their alloys, metal oxides, organic conductive compounds or mixtures thereof, and materials having a work function of 4.0 eV or more are preferable. Specific examples include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO), and the like. Gold, silver, chrome,
Metals such as nickel, mixtures or laminates of these metals and conductive metal oxides, conductive inorganic substances such as copper iodide and copper sulfide, dispersions of conductive metal oxides or metal compounds, polyaniline, polythiophene , An organic conductive material such as polypyrrole, and a laminate of these with ITO.

Depending on the material of the anode, for example, a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method,
It can be formed on the substrate support by a chemical method such as a CVD method or a plasma CVD method. The forming method may be appropriately selected in consideration of the suitability of the material. For example, when ITO is used as the anode material, direct current or high frequency sputtering method,
A vacuum deposition method, an ion plating method or the like may be used. When an organic conductive material is used as the anode material, a wet film forming method may be used. From the viewpoint of increasing the area of the organic thin film element and productivity, it is preferable to use the wet film forming method.

The patterning of the anode layer can be performed by chemical etching such as photolithography, physical etching using a laser, or the like. Also, vacuum evaporation method using a mask, sputtering method, lift-off method,
You may pattern by a printing method etc.

The thickness of the anode layer may be appropriately selected depending on the material thereof, but is usually 10 nm to 50 μm, preferably 50 nm.
nm to 20 μm. The resistance value of the anode layer is preferably 10 ⁶ Ω / □ or less, more preferably 10 ⁵ Ω / □ or less. When the resistance value is 10 ⁵ Ω / □ or less, a large area light emitting device having excellent performance can be obtained by installing the bus line electrode. When it is a transparent anode, the anode may be colorless and transparent or colored and transparent. When a transparent cathode is provided, the anode may be colorless and transparent, colored and transparent, or opaque. In order to take out light emission from the transparent anode, its transmittance is preferably 60% or more, more preferably 70% or more. The transmittance can be measured according to a known method using a spectrophotometer.

The electrodes described in detail in "New Development of Transparent Conductive Film" (supervised by Yutaka Sawada, published by CMC, 1999) are also applicable to the present invention. Particularly when a plastic substrate support having low heat resistance is used, it is preferable to use ITO or IZO as the transparent conductive layer material and form the film at a low temperature of 150 ° C. or lower.

(B) Cathode The cathode generally has a function as an electrode for injecting electrons into the organic thin film layer, and its shape, structure, size, etc. are not particularly limited. It can be appropriately selected from known electrodes according to the use and purpose of the organic thin film element.

The cathode may have either a single layer structure or a laminated structure. As a material for forming the cathode, a simple metal or an alloy thereof, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4.5 eV or less is preferably used. As a specific example, an alkali metal (L
i, Na, K, Cs, etc.), alkaline earth metals (Mg, Ca, etc.),
Examples thereof include gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium-silver alloy, indium, rare earth metal (ytterbium, etc.) and the like. These may be used alone, but it is preferable to use two or more kinds in combination in order to achieve both stability and electron injection property.

Among the above materials, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injection property, and materials mainly containing aluminum are preferable from the viewpoint of storage stability. Here, the material mainly composed of aluminum is not only aluminum alone but also an alloy or a mixture of aluminum and 0.01 to 10% by mass of an alkali metal or an alkaline earth metal (lithium-aluminum alloy, magnesium-aluminum alloy, etc.). Point to. As the material of the cathode, those described in detail in JP-A Nos. 2-15595 and 5-121172 can be used.

When taking out light from the cathode side, it is necessary to use a transparent cathode. The transparent cathode may be substantially transparent to light. In this case, the cathode may have a two-layer structure of a thin metal layer and a transparent conductive layer in order to achieve both electron injection property and transparency. The thickness of the thin metal layer is 1-50
nm is preferred. If it is less than 1 nm, it is difficult to form a uniform metal thin film, and if it is more than 50 nm, the transparency decreases.

The material used for the transparent conductive layer is not particularly limited as long as it is a transparent material having conductivity or semiconductivity.
The material used for the anode can be preferably used.
Among them, for example, tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO) and the like can be mentioned. Thickness of transparent conductive layer is 30-500 nm
Is preferred. If the transparent conductive layer is thinner than 30 nm, the conductivity or semiconductivity is poor, and if it is thicker than 500 nm, the productivity is poor.

The method of forming the cathode is not limited, and a known method can be adopted, but it is preferably performed in a vacuum device. For example, vacuum evaporation method, sputtering method, physical method such as ion plating method, CVD method, plasma CVD
A chemical method such as a method is appropriately selected in consideration of suitability for the material of the cathode. For example, when a metal or the like is selected as the cathode material, a thin film can be formed by simultaneously or sequentially sputtering one kind or two or more kinds of metals. When an organic conductive material is used as the cathode material, a wet film forming method may be used. The patterning of the cathode layer can be performed in the same manner as the anode layer.

A dielectric layer made of a fluoride of an alkali metal or an alkaline earth metal is provided between the cathode and the organic thin film layer.
You may install with a thickness of 1-5 nm. The dielectric layer can be formed by a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like.

(4) Patterning In forming the fine patterned organic thin film layer, a mask (fine mask) having fine patterned openings can be used. The material of the mask is not limited, but a durable and inexpensive material such as metal, glass, ceramic, and heat resistant resin is preferable. Further, these materials can be used in combination. From the viewpoint of mechanical strength and transfer accuracy of the organic thin film layer, the thickness of the mask is preferably 2 to 100 μm, more preferably 5 to 60 μm. The mask opening is tapered so that it is larger on the transfer body side than on the substrate side so that the organic thin film layer of the transfer body adheres to the underlying conductive layer or other organic thin film layer exactly in the shape of the opening of the mask. Is preferred.

It is also possible to perform patterning by a method of transferring the convex portion of the imprinted transfer body. in this case,
(a) a transfer body forming step of forming one or a plurality of transfer bodies by forming at least one organic thin film layer on a temporary support; and (b) one of the above-mentioned transfer body or plurality of transfer bodies. A pattern forming step of forming a concavo-convex pattern corresponding to the concavities and convexities of the pressing member on the transfer body surface by pressing the transfer body surface with a pressing member having a concavo-convex pattern of a predetermined pattern on the transfer body surface, (c) At least one operation is performed in which the surface of one transfer member of one or a plurality of transfer members having an uneven pattern is superimposed on the film formation surface of the substrate, and the protrusions of the transfer member are transferred to the film formation surface. By doing so, it is possible to preferably use the method for manufacturing an organic thin film element, which includes a transfer step of forming an organic thin film layer pattern on the film formation surface.

(5) Other Layers As a layer constituting the organic thin film element, it is preferable to provide a protective layer or a sealing layer in order to prevent deterioration of light emitting performance. Further, in the transfer body, a release layer may be provided between the temporary support and the organic thin film layer or an adhesive layer may be provided between the organic thin film layer and the film formation surface in order to improve the transfer property if the light emitting performance is not affected. It may be provided.

(A) Protective Layer Organic Thin Film Element is disclosed in JP-A-7-85974, JP-A-7-192866 and JP-A-7-29866.
-22891, 10-275682, 10-106746 and the like may have a protective layer. The protective layer is formed on the uppermost surface of the organic thin film element. Here, the uppermost surface means, for example, a substrate support /
When stacking the anode / organic thin film layer / cathode in this order, it refers to the outer surface of the cathode, and, for example, when stacking the substrate support / cathode / organic thin film layer / anode in this order, it refers to the outer surface of the anode. The shape, size, thickness, etc. of the protective layer are not particularly limited. The material forming the protective layer is not particularly limited as long as it has a function of suppressing entry or permeation of an organic thin film element such as moisture or oxygen that deteriorates the element, for example, silicon monoxide, or dioxide. Silicon, germanium monoxide, germanium dioxide, etc. can be used.

The method of forming the protective layer is not particularly limited and includes, for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, plasma CVD method, A laser CVD method, a thermal CVD method, a coating method, etc. can be used.

(B) Sealing Layer The organic thin film element is preferably provided with a sealing layer for preventing moisture and oxygen from entering. As a material for forming the sealing layer, a copolymer of tetrafluoroethylene and at least one comonomer, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, polyethylene, polypropylene, polymethylmethacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene or copolymers of dichlorodifluoroethylene and other comonomers, water-absorbing substances with water absorption of 1% or more, water absorption of 0.1% The following moisture-proof substances, metals (In, Sn, P
b, Au, Cu, Ag, Al, Ti, Ni, etc., metal oxides (MgO, Si)
O, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , Y ₂ O ₃ , T
iO _2, etc.), metal fluorides (MgF ₂ , LiF, AlF ₃ , CaF _2, etc.),
Liquid fluorinated carbon (perfluoroalkane, perfluoroamine, perfluoroether, etc.), liquid fluorinated carbon in which an adsorbent for water or oxygen is dispersed, and the like can be used.

For the purpose of blocking moisture and oxygen from the outside,
It is preferable to seal the organic thin film layer with a sealing member such as a sealing plate or a sealing container. The sealing member may be provided only on the uppermost surface of the organic thin film element, or the entire organic thin film element may be covered with the sealing member. The shape, size, thickness, etc. of the sealing member are not particularly limited as long as the organic thin film layer can be sealed and the outside air can be blocked. Materials used for the sealing member include glass, stainless steel, metal (aluminum, etc.),
Plastics (polychlorotrifluoroethylene, polyester, polycarbonate, etc.), ceramics, etc. can be used.

A sealing agent (adhesive) may be used when the sealing member is placed on the organic thin film element. An ultraviolet curable resin, a thermosetting resin, a two-component curable resin, or the like can be used as the sealing agent. When the entire organic thin film element is covered with the sealing member, the sealing members may be heat-sealed without using the sealing agent.

Further, a water absorbent or an inert liquid may be inserted in the space between the sealed container and the organic thin film element. The water absorbent is not particularly limited, and specific examples include barium oxide,
Sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride,
Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieves, zeolite, magnesium oxide and the like can be mentioned. As the inert liquid, paraffins, liquid paraffins, fluorine-based solvents (perfluoroalkane, perfluoroamine, perfluoroether, etc.), chlorine-based solvents, silicone oils and the like can be used.

The organic thin film element of the present invention emits light by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 40 V) or a direct current between the anode and the cathode. Can be obtained. Regarding the driving of the organic thin film element of the present invention, JP-A No. 2-148687, 6-301355,
5-29080, 7-14558, 8-234685, 8-241047
No.2,784,615, U.S. Pat.Nos. 5,828,429, 6,02
The method described in 3,308, etc. can be used.

[0083]

EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited thereto.

Example 1 (A) Preparation of Transfer A On one side of a temporary support made of polyether sulfone (Sumitomo Bakelite Co., Ltd., thickness 188 μm), the following composition: polyvinylcarbazole (Mw = 63000, Aldrich Co., Ltd.): 40 parts by mass tris (2-phenylpyridine) iridium complex (orthometalated complex): 1 part by mass dichloroethane: A coating solution for a luminescent organic thin film layer having 3500 parts by mass is applied using a bar coater, 40 nm thickness by drying at room temperature
A transfer body A was prepared by forming the luminescent organic thin film layer of 1. above on a temporary support.

(B) Preparation of Transfer Body B On one side of a temporary support made of polyether sulfone (Sumitomo Bakelite Co., Ltd., thickness 188 μm), the following composition: polyvinyl butyral (Mw = 50000, manufactured by Aldrich) : 10 parts by mass Electron transporting compound represented by the following structural formula (Formula 1):
20 parts by mass 1-butanol: 3500 parts by mass

[0086]

[Chemical 1]

The coating liquid for an electron-transporting organic thin film layer having is coated with an extrusion type coating machine at 80 ° C.
By vacuum drying for 2 hours, a transfer body B was prepared in which an electron transporting organic thin film layer having a thickness of 60 nm was formed on a temporary support.

(C) Preparation of Transfer Body C On one side of a temporary support made of polyether sulfone (Sumitomo Bakelite Co., Ltd., thickness 188 μm), the following composition: represented by the following structural formula (Formula 2) Polymer compound (PTPD
ES): 40 parts by mass

[0089]

[Chemical 2]

Additive (TBPA) represented by the following structural formula (Formula 3): 10 parts by mass

[0091]

[Chemical 3]

Dichloroethane: A coating solution for an organic thin film layer containing 3500 parts by mass was applied using an extrusion type coating machine, and dried at room temperature,
A transfer body C was prepared in which a hole transporting organic thin film layer having a thickness of 40 nm was formed on a temporary support.

(D) Fabrication of organic EL device (1) Fabrication of film-forming surface On both sides of a 5 cm square (thickness: 30 μm) aluminum foil, a polyimide sheet (“UPILEX 50
S ", manufactured by Ube Industries, Ltd., was laminated using an adhesive to prepare a substrate support. The coefficient of linear thermal expansion of the substrate support is 10 p
It was pm / ° C (TMA measurement). The water permeability of the substrate support is 0.01 g / m ² · day · atm or less (MOCON method, 25 ° C, 90% R
H) and the oxygen transmission rate is 0.01 cc / m ² · day · atm or less (M
OCON method, 25 ° C., 0% RH). On this substrate support, Al was formed into a film with a thickness of 250 nm by a vapor deposition method to obtain a cathode.
LiF (electron injection material) having a film thickness of 3 nm was formed thereon by vapor deposition.

(2) The electron transporting organic thin film layer side of the transfer body B is superposed on the surface of the substrate obtained by transferring the organic thin film layer to the film formation surface, and a pair of rollers (one of which has a pressure of 0.3 MPa) is applied. 1
By passing it through a heating roller (60 ° C.) at a speed of 0.05 m / min, pressure was applied from the temporary support side of the transfer body B while heating. Then, the temporary support was peeled off from the transfer body B to transfer the electron transporting organic thin film layer B onto the substrate having the electrodes.

Similarly, the luminescent organic thin film layer side of the transfer member A was superposed on the upper surface of the substrate having the electron transporting organic thin film layer to form 0.3.
By passing between a pair of rollers having a pressure force of MPa (one of which is a heating roller of 155 ° C.) at a speed of 0.05 m / min, pressure was applied from the temporary support side of the transfer body A while heating. Then, the light-emitting organic thin film layer A was transferred onto the upper surface of the electron transporting organic thin film layer by peeling off the temporary support from the transfer member A.

Further, the hole transporting organic thin film layer side of the transfer member C is superposed on the upper surface of the substrate having the light emitting organic thin film layer to form 0.3.
By passing between a pair of rollers having a pressure force of MPa (one of which is a heating roller of 150 ° C.) at a speed of 0.05 m / min, pressure was applied from the temporary support side of the transfer body A while heating. Next, the hole-transporting organic thin film layer C was transferred onto the upper surface of the light-emitting organic thin film layer by peeling off the temporary support from the transfer member C.

(3) Preparation of transparent anode An ITO film having a thickness of 200 nm (indium: tin = 95 :) was formed on the prepared light-emitting organic thin film layer by DC magnetron sputtering.
5 (molar ratio)) was formed. Aluminum lead wires were connected to the cathode and the transparent anode, respectively, to produce a laminated structure.

(4) Sealing A portion other than the lead wire portion of the obtained laminated structure was covered with silicon nitride by a sputtering method to form a sealing film, and an organic EL element was produced.

(E) Evaluation The obtained organic EL device was evaluated by the following method. First, Source Measure Unit Model 2400 (Toyo Technica Co., Ltd.)
DC voltage was applied to the organic EL device to emit light. The luminous efficiency (η ₂₀₀ ) at 200 Cd / m ^{2 was} defined as the external quantum efficiency. Further, the number of defects per 1 mm ² was visually observed. The defect evaluation criteria are as follows. In addition, defects after storage for 20 days at 85 ° C and 90% RH (wet heat storage test) were also evaluated. The results are shown in Table 1. 1 mm ² per defect 5 or less: ◎ 1 mm ² per defect 6-20: ○ 1 mm ² per defect is 21 or more: ×

Example 2 An organic EL device was prepared and evaluated in the same manner as in Example 1 except that a copper foil (thickness: 50 μm) was used instead of the aluminum foil. The results are shown in Table 1. The coefficient of linear thermal expansion of the substrate support was 8 ppm / ° C (TMA measurement). The water permeability of the substrate support is 0.01 g / m ² · day · atm or less (MOCON method, the same conditions as in Example 1), and the oxygen permeability is 0.01 cc / m ² · da.
It was y · atm or less (MOCON method, the same conditions as in Example 1).

Example 3 An organic EL device was prepared and evaluated by the same method as in Example 1 except that a sputtered film of silicon oxide (thickness: 30 nm) was used as the insulating layer instead of the polyimide sheet. The results are shown in Table 1. The linear thermal expansion coefficient of the substrate support was 5 ppm / ° C (measured by TMA). The water permeability of the substrate support is 0.0
1 g / m ² · day · atm or less (MOCON method, same conditions as in Example 1) and oxygen permeability of 0.01 cc / m ² · day · atm or less (MOCON method, same conditions as in Example 1) there were.

Example 4 As an insulating layer, instead of laminating polyimide sheets on both sides of an aluminum foil, the same polyimide sheet as in Example 1 was laminated on one side and a silicon nitride film (thickness: 50 was formed on the other side by a sputtering method. (nm) was formed into a film by the same method as in Example 1, and then a cathode, an organic thin film layer and a transparent anode were formed on the silicon nitride insulating layer side to form an organic film.
An EL device was produced. The obtained organic EL device was evaluated by the same method as in Example 1. The results are shown in Table 1. The coefficient of linear thermal expansion of the substrate support was 3 ppm / ° C (TMA measurement). The water permeability of the substrate support is 0.01 g / m ² · day · atm or less (M
OCON method, the same conditions as in Example 1), with an oxygen permeability of 0.
It was less than 01 cc / m ² · day · atm (MOCON method, the same conditions as in Example 1).

Example 5 As an insulating layer, instead of laminating polyimide sheets on both sides of an aluminum foil, a silicon oxide film (thickness: 40 μm) was formed on only one side by a sputtering method in the same manner as in Example 1, An organic EL device was produced. The cathode, the organic thin film layer and the transparent anode were formed on the silicon oxide side. This organic EL device was evaluated by the same method as in Example 1. The results are shown in Table 1. The linear thermal expansion coefficient of the substrate support was 10 ppm / ° C (TMA
Measurement). The substrate support has a moisture permeability of 0.01 g / m ² · day.
-Atm or less (MOCON method, the same conditions as in Example 1), and oxygen permeability was 0.01 cc / m ² · day-atm or less (MOCON method, same conditions as in Example 1).

Example 6 As a substrate support, a polyimide sheet having a thickness of 100 μm (“Upilex 100S”, manufactured by Ube Industries, Ltd.) was used instead of an aluminum foil having polyimide sheet insulating films laminated on both sides.
Produced by the same method as in Example 1 except that
A device was produced. This organic EL device was evaluated by the same method as in Example 1. The results are shown in Table 1. The coefficient of linear thermal expansion of the substrate support was 10 ppm / ° C (TMA measurement). The substrate support has a moisture permeability of 0.3 g / m ² · day · atm or less (MOCON
Method, the same conditions as in Example 1) and an oxygen permeability of 0.55 c
c / m ² · day · atm or less (MOCON method, same conditions as in Example 1)
Met.

Example 7 As a substrate support, a liquid crystal polymer sheet having a thickness of 100 μm (“Bexter”, manufactured by Kuraray Co., Ltd.) was used alone instead of an aluminum foil having polyimide sheet insulating films laminated on both sides. An organic EL device was produced in the same manner as in Example 1. This organic EL device was evaluated by the same method as in Example 1. The results are shown in Table 1. The coefficient of linear thermal expansion of the substrate support was 20 ppm / ° C (TMA measurement). The water permeability of the substrate support is 0.03 g / m ² · day · atm or less (MOCON method, the same conditions as in Example 1), and the oxygen permeability is 0.21 cc / m ² · day.
-Atm or less (MOCON method, the same conditions as in Example 1).

Comparative Example 1 Example 1 except that a PET sheet having a thickness of 50 μm (Lumirror T60 manufactured by Toray Industries, Inc.) was used instead of the polyimide sheet.
An organic EL device was produced by the same method as described above. This organic EL device was evaluated by the same method as in Example 1. The results are shown in Table 1.
The coefficient of linear thermal expansion of the substrate support was 55 ppm / ° C (T
MA measurement). The water vapor transmission rate of the substrate support is 0.01 g / m ² · d.
ay · atm or less (MOCON method, the same conditions as in Example 1),
The oxygen transmission rate was 0.01 cc / m ² · day · atm or less (MOCON method, the same conditions as in Example 1).

[0107]

[Table 1]

As is clear from Table 1, the organic thin film element of the present invention was excellent in luminous efficiency and had few defects. Particularly, Examples 1 to 5 in which the oxygen permeability and the moisture permeability of the substrate support are low.
The organic thin film element (1) had excellent durability and had few defects after the wet heat storage test. The organic thin film element of Comparative Example 1 in which the substrate support had a large coefficient of linear thermal expansion had low luminous efficiency and many defects.

As a method for forming the electron transporting organic thin film layer, instead of transferring the transfer body B to the substrate, the same electron transporting compound as the transfer body B was vapor-deposited at a rate of 1 nm / sec to a thickness of 0.024 μm. Other than that, an organic EL device was produced by the same method as in the example. Moreover, the organic thin film element which changed the board | substrate support like Example 2-7 was produced. When these organic EL devices were evaluated by the same method as in Example 1, the same result as each example was obtained.

Example 8 (A) Preparation of Transfer A On one side of a temporary support made of polyethersulfone (Sumilite FS-5300 manufactured by Sumitomo Bakelite Co., Ltd.), the following composition: polyvinylcarbazole (Mw = 63000, Aldrich Co., Ltd.): 40 parts by mass tris (2-phenylpyridine) iridium complex (orthometalated complex): 1 part by mass dichloroethane: A coating solution for a luminescent organic thin film layer having 3500 parts by mass is applied using a bar coater, 40 nm thickness by drying at room temperature
A transfer body A was prepared by forming the luminescent organic thin film layer of 1. above on a temporary support.

(B) Preparation of Transfer Body B On one side of a temporary support made of polyether sulfone (Sumitomo Bakelite Co., Ltd., thickness: 188 μm), the following composition: polyvinyl butyral (Mw = 50000, manufactured by Aldrich) : 10 parts by mass Electron transporting compound represented by the following structural formula (Formula 4):
20 parts by mass 1-butanol: 3500 parts by mass

[0112]

[Chemical 4]

The coating liquid for an electron-transporting organic thin film layer having is coated with an extrusion type coating machine at 80 ° C.
By vacuum drying for 2 hours, a transfer body B was prepared in which an electron transporting organic thin film layer having a thickness of 60 nm was formed on a temporary support.

(C) Fabrication of organic EL device (1) Fabrication of film formation surface 5 cm square (thickness: 30 μm) on both sides of aluminum foil
50 μm thick polyimide sheet (“Upilex 50
S ", made by Ube Industries, Ltd., is laminated with an adhesive to form a base
A plate support was prepared. The coefficient of linear thermal expansion of the substrate support is 10 p
It was pm / ° C (TMA measurement). In addition, water permeation of the substrate support
Rate 0.01 g / m²・ Day ・ atm or less (MOCON method, 25 ℃, 90% R
H) and the oxygen transmission rate is 0.01 cc / m²・ Day ・ atm or less (M
OCON method, 25 ° C., 0% RH). This substrate support is true
Introduced into the empty chamber, SnO₂ITO with a content of 10% by mass
Use target (indium: tin = 95: 5 (molar ratio))
DC magnetron sputtering (condition: substrate support
Body temperature 250 ℃, oxygen pressure 1 × 10^-3 Pa), thickness 0.2μ
A transparent electrode (anode) made of an ITO thin film of m was formed. ITO
The surface resistance of the thin film was 10 Ω / □.

On the surface of the transparent anode, an aqueous dispersion of polyethylenedioxythiophene / polystyrenesulfonic acid (BAY
ER Co., Baytron P: solid content 1.3% by mass) was spin-coated and then vacuum-dried at 150 ° C. for 2 hours to form a hole-transporting organic thin film layer having a thickness of 100 nm.

(2) Transferring the organic thin film layer to the film formation surface The light emitting organic thin film layer side of the transfer body A is superposed on the upper surface of the substrate having the hole transporting organic thin film layer obtained, and a pressure of 0.3 MPa is applied. A pair of rollers (one is a heating roller of 155 ℃)
The pressure was applied while heating from the side of the temporary support of the transfer member A by passing the gap between the transfer members at a speed of 0.05 m / min. Next, transfer body A
The luminescent organic thin film layer A was transferred onto the upper surface of the hole transporting organic thin film layer by peeling off the temporary support from.

Similarly, the electron transporting organic thin film layer side of the transfer member B was superposed on the upper surface of the substrate having the light emitting organic thin film layer,
By passing between a pair of rollers having a pressure force of MPa (one of which is a heating roller of 150 ° C.) at a speed of 0.05 m / min, the transfer body B was heated and pressed from the temporary support side. Next, the temporary support was peeled off from the transfer body B to transfer the electron transporting organic thin film layer B onto the upper surface of the light emitting organic thin film layer.

(3) Preparation of transparent cathode LiF (electron injection material) having a film thickness of 3 nm was formed on the prepared light-emitting organic thin film layer by vapor deposition. Furthermore, Al was formed into a film with a thickness of 10 nm by a vapor deposition method to form a metal thin film layer of a transparent cathode. A 200 nm thick ITO film (indium: tin = 95: 5 (molar ratio)) was formed as a cathode transparent conductive layer on the obtained Al film by DC magnetron sputtering. Aluminum lead wires were respectively connected from the transparent anode and the transparent cathode to produce a laminated structure.

(4) Encapsulation The sealing film was formed by covering a portion other than the lead wire portion of the obtained laminated structure with silicon nitride by a sputtering method to form an organic EL element. Also, an organic EL device was prepared in which the substrate support was changed in the same manner as in Examples 2 to 7.

(D) Evaluation When these organic EL devices were evaluated by the same method as in Example 1, the same results as in Examples 1 to 7 were obtained.

[0121]

As described in detail above, the method for producing an organic thin film element of the present invention uses a substrate support having a coefficient of linear thermal expansion of 20 ppm / ° C. or less. An organic thin film element such as an organic EL element having excellent properties can be efficiently manufactured. Such an organic thin film element can be used for a full-color display, a backlight, a surface light source such as an illumination light source, a light source array for a printer, and the like.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an apparatus for carrying out a method for manufacturing an organic thin film element of the present invention.

FIG. 2 shows a transfer body having a plurality of organic thin film layers in a frame sequential manner.

[Explanation of symbols]

100 ... Substrate 101 ... Substrate support 102 ... Conductive layer 110 ... Transfer 111 ... Temporary support 112 ... Organic thin film layer 113 ・ ・ ・ Transfer roll 114 ... Roll for winding temporary support 121 ... Heating roll 122 ... Pressure (heating) roll

Claims (6)

[Claims] 1. A transfer body is produced by using a substrate having a thin film layer on a substrate support and forming an organic thin film layer on the temporary support by a wet method, wherein the organic thin film layer side is the thin film layer. In a method for manufacturing an organic thin film element, which comprises a step of heating the transfer body so as to face each other and heating the substrate and transferring the organic thin film layer to a film formation surface of the substrate by peeling off the temporary support. And a linear thermal expansion coefficient of at least the substrate support of 20 ppm / ° C. or less. 2. The method of manufacturing an organic thin film element according to claim 1, wherein the substrate support has flexibility. 3. The organic thin film element manufacturing method according to claim 2, wherein the flexible substrate support has a water permeability of 1 g / m ² · day · atm or less. Method for manufacturing thin film element. 4. The method for manufacturing an organic thin film element according to claim 2, wherein the flexible substrate support has an oxygen permeability of 1 cc / m ² · day · atm or less. Method for manufacturing organic thin film element. 5. The method for manufacturing an organic thin film element according to claim 2, wherein the flexible substrate support is made of a metal foil provided with an insulating layer on one side or both sides. And a method for manufacturing an organic thin film element. 6. An organic thin film element manufactured by the method for manufacturing an organic thin film element according to claim 1.