JP2003234184A - Manufacturing method of organic thin film element and transfer material used for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic thin film element having uniformity and a good junction interface, capable of forming an organic thin film layer on a substrate at low cost, by using a simple manufacturing device. <P>SOLUTION: A transfer material 110 is constituted by forming at least one- layer of an organic thin film layer 112 on a temporary support 111, and the temperature at the time when viscosity of at least one component constituting the organic thin film layer 112 becomes 1×10<SP>4</SP>Pa×s is 40 to 240°C. By putting the transfer material 110 on the substrate 100 so that the organic thin film layer 112 side faces a film-forming surface of the substrate 100, by carrying out heating and/or pressing, and by peeling off the temporary support 111, the organic thin film layer 112 is transferred to the film-forming surface of the substrate 100. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transfer material for an organic thin film element and a method for manufacturing an organic thin film element using the same.

[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 recombine in the light emitting layer, and when the energy level returns from the conduction band to the valence band, energy is emitted as light 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 the vapor deposition method is used, only low-molecular weight organic compounds can be used for the organic thin film, so that there is a problem that durability such as bending resistance and film strength is insufficient when used for flexible display applications, etc. It becomes a problem when the area is enlarged.

In view of the above problems caused by using a low molecular weight organic compound, a light emitting thin film made of a high molecular compound or a polymer type organic EL element using a light emitting thin film in which a low molecular weight compound is dispersed in a binder resin is also available. Proposed. For example, “Nature”, vol. 347, p. 539, 1990 proposes a polymer type green light emitting organic EL device using polyparaphenylene vinylene, “Japanese Journal of
Applied Physics '', Volume 30, L1938, 1991,
We have proposed a polymer-type red-orange light-emitting organic EL device using poly 3-alkylthiophene, and also "Japanese Journal of Applied Physics", Volume 30, L1941.
Page, 1991, proposes a polymer type blue light emitting organic EL device using polyalkylfluorene. These polymer type devices are also advantageous for increasing the area and are expected to be used for flexible displays, but since the vapor deposition method cannot be applied to the formation of organic light emitting thin films, the thin film is directly formed on the substrate by the wet method. is doing.

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

[0007] WO 00/41893 proposes a method of thermal transfer by laser using a donor sheet having an organic thin film and 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 state differ depending on the state of the interface of the organic thin film layer.

In the case of pattern-shaped 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 the thermal diffusivity, and the contour of the organic thin film pattern is neat. Is not disconnected from. As a result, there is a problem in that variations in the amount of emitted light occur, electrical defects and defects due to thin film debris 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.

Therefore, an object of the present invention is to provide a method for producing an organic thin film element which can form an organic thin film layer on a substrate at a low cost with a simple production apparatus and which has a uniform and good bonding interface. , Particularly by forming a uniform organic thin film layer on a temporary support, a method for efficiently producing an organic thin film element such as an organic EL element having excellent luminous efficiency, uniformity of light emission amount and durability, and use thereof It is to provide a transfer material.

[0010]

As a result of earnest research in view of the above-mentioned object, the present inventors have found that at least one organic thin film layer constituting an organic thin film element is provided on a temporary support, and the organic thin film layer is formed. When transferring to a substrate, by setting the predetermined viscosity attainment temperature of at least one component that constitutes the organic thin film layer to a desired level, it is possible to obtain an organic EL device having excellent emission efficiency, uniformity of emission amount, and durability. The present invention has been accomplished by discovering that an organic thin film element can be manufactured at low cost.

That is, the transfer material of the present invention comprises at least one organic thin film layer on a temporary support, and the viscosity of at least one component constituting the organic thin film layer is 1 × 10 ⁴ P.
It is characterized in that the temperature at the time of a · s is 40 to 240 ° C.

In the method for producing an organic thin film element of the present invention, a transfer material (at least one layer constituting the organic thin film layer is formed by forming at least one organic thin film layer on a temporary support.
When the viscosity of one component reaches 1 × 10 ⁴ Pa · s, the temperature is 40 to 2
40 ° C.), and by heating and / or pressing the transfer material on the substrate so that the organic thin film layer side faces the film formation surface of the substrate, and peeling off the temporary support. It is characterized in that the organic thin film layer is transferred to the film formation surface of the substrate.

In addition to the above, the following are preferred embodiments of the present invention. (1) A transfer material in which the organic thin film layer contains at least a light emitting organic compound or a carrier transporting organic compound. (2) A transfer material in which the transfer material and / or the substrate is a continuous web. (3) A transfer material having a dry film thickness of the organic thin film layer of 6 nm to 600 nm. (4) A method for producing an organic thin film element, in which at least one hole transporting organic thin film layer, a light emitting organic compound layer and an electron transporting organic thin film layer are provided in this order from the substrate side. (5) A method for manufacturing an organic thin film element, which uses a substrate composed of a substrate support and a transparent conductive film formed thereon.

[0014]

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

[1] Transfer Material (1) The constituent organic thin film layer is formed on a temporary support by a wet method. The transfer material provided with the organic thin film layer may be prepared as an independent transfer material, or a plurality of organic thin film layers may be provided in a frame-sequential manner on one temporary support. In this case, a plurality of organic thin film layers can be continuously formed without the need to replace the transfer material.

If a transfer material in which two or more organic thin film layers are preliminarily laminated on the temporary support is used, the multilayer film can be laminated on the film formation surface of the substrate in one transfer process. When preliminarily laminating on a temporary support, if the interface of each organic thin film layer to be laminated is not uniform, uneven movement of holes and electrons will occur, so it is necessary to carefully select the solvent to make the interface uniform. In addition, it is necessary to select an organic compound for the organic thin film layer that is soluble in the solvent.

(2) Temporary support The temporary support used in the present invention is made of a material that is chemically and thermally stable and has flexibility. Specifically, fluororesin [eg, tetrafluoroethylene resin (PTFE),
Thin sheet of trifluorochloroethylene resin (PCTFE)], polyester (eg polyethylene terephthalate, polyethylene naphthalate (PEN)), polyarylate, polycarbonate, polyolefin (eg polyethylene, polypropylene), polyether sulfone (PES), or These laminates are preferred. The thickness of the temporary support is appropriately 1 μm to 300 μm, more preferably 3 μm to 200 μm, and particularly preferably 5 μm to 150 μm.

The structure of the temporary support of the present invention may be a single layer or a laminate. In the case of a laminated body, a substrate and a smooth layer of at least one layer may be provided in this order on the side where the organic thin film layer is provided. The material forming the smooth layer is not particularly limited.

(3) Formation of an organic thin film layer on a temporary support At least one of the components constituting the organic thin film layer of the present invention
The component must satisfy the requirement that the temperature (viscosity reaching temperature) when the viscosity reaches 1 × 10 ⁴ Pa · s is 40 to 240 ° C.

If the temperature at which the predetermined viscosity reaches is less than 40 ° C., there is a risk of failure such as transfer onto the back surface of the upper transfer material when a plurality of transfer materials are stacked. Further, if the predetermined viscosity reaching temperature exceeds 240 ° C., it is difficult to transfer the organic thin film layer by a heating / pressurizing roll or the like. The lower limit of the predetermined viscosity reaching temperature is preferably 50 ° C, and particularly preferably 60 ° C. Further, the upper limit of the temperature at which the predetermined viscosity is reached is preferably 200 ° C. The viscosity of the constituent components of the organic thin film layer can be measured, for example, by a flow tester manufactured by Shimadzu Corporation.
It can be measured using CFT-500.

When a binder such as a polymer compound is used as a constituent component of the organic thin film layer of the present invention, it is preferable to select a polymer compound satisfying the requirement of the above-mentioned predetermined viscosity reaching temperature. As the polymer binder, polyvinyl chloride,
Polycarbonate, polystyrene, polymethylmethacrylate, polybutylmethacrylate, 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.
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 organic thin film layer containing a polymer compound as a binder is preferably formed on a temporary support by a wet method. For this, the material for the organic thin film layer is dissolved in an organic solvent to a desired concentration, and the resulting solution is applied to a temporary support. 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 coating 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 is characterized by its characteristics such as 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. Further, various layers for improving the color developability can be mentioned. The dry film thickness of the organic thin film layer is preferably 6 nm to 600 nm, more preferably 6 nm to 450 nm, further preferably 6 nm to 300 nm.

(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 orthometallated complex and porphyrin complex are preferred. 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 referred to in the present invention refers to Akio Yamamoto, "Organometallic Chemistry: Fundamentals and Applications," pages 150 and 232.
Pp. Shokabosha (1982), H. Yersin, “Photochemistr
y and Photophysics of Coordination Compounds ", 71
~ 77 and 135 ~ 146, Springer-Verlag (1987)
Etc. is a general term for a compound group described in. The ligand forming the orthometallated complex is not particularly limited, but it may be a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative or a 2-phenylpyridine derivative.
It is preferably a (2-thienyl) pyridine derivative, a 2- (1-naphthyl) pyridine derivative or a 2-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 orthometallated complex, any transition metal can be used, and in the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like are preferable. The organic compound layer containing such an orthometalated 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 ortho-metallated complex used in the present invention is In
org. Chem., 30, 1685, 1991, Inorg. Chem., 27, 346
4, 1988, Inorg. Chem., 33, 545, 1994, Inorg. Chim.
Acta, 181, 245, 1991, J. Organomet. Chem., 335, 2
93, 1987, J. Am. Chem. Soc., 107, 1431, 1985, etc., and can be synthesized by a known method.

The content of the light emitting compound in the light emitting 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 which 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 Carboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, metal phthalocyanine, metal complexes having benzoxazole or benzothiazole as a ligand, polysilane compounds, poly (N- vinylcarbazole)
Examples include derivatives, aniline copolymers, thiophene oligomers, conductive polymers such as polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylenevinylene derivatives, polyfluorene derivatives, and the like. The host compounds may be used alone or in combination of two or more.

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 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 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 derivative, distyryl pyrazine derivative, heterocyclic tetracarboxylic acid anhydride such as naphthalene perylene, phthalocyanine derivative, metal complex such as 8-quinolinol derivative, metallophthalocyanine, benzoxazole, benzothiazole, etc. as ligands Examples thereof include metal complexes, aniline copolymers, thiophene oligomers, conductive polymers such as polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylenevinylene derivatives, polyfluorene derivatives and the like.

The dry film thickness of the luminescent organic thin film layer is 2 to 200 nm.
The thickness is preferably 2 to 150 nm, more preferably 2 to 100 nm, and even more preferably 2 to 100 nm. Dry film thickness
If it exceeds 200 nm, the driving voltage may increase. On the other hand, if it is less than 2 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 dry film thickness of the hole transporting organic thin film layer is preferably 2 to 200 nm, more preferably 2 to 150 nm, further preferably 2 to 100 nm. Dry film thickness
If it exceeds 200 nm, the driving voltage may increase and 2 n
If it is less than m, 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 dry film thickness of the electron transporting organic thin film layer is preferably 2 to 200 nm, more preferably 2 to 150 nm, and
More preferably, it is 100 nm. If the dry film thickness exceeds 200 nm, the driving voltage may increase, and if it is less than 2 nm, the organic thin film element may short-circuit.

[2] Method for manufacturing organic thin film element The method of the present invention is to transfer an organic thin film layer onto a substrate by a peel transfer method using a plurality of transfer materials each having an organic thin film layer formed on a temporary support. Is characterized by. In the peeling transfer method, the organic thin film layer is softened by heating and / or pressurizing the transfer material to adhere it to the film formation surface of the substrate, and then the temporary support is peeled off to remove only the organic thin film layer. This is a method (transfer method) of leaving it on the film-forming surface. As 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, a fast laminator VA-400III (manufactured by Taisei Laminator Co., Ltd.) or a thermal head for thermal transfer printing can be used.

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 is generally preferably 40 to 250 ° C, more preferably 50 to 200 ° C.
Particularly, 60 to 180 ° C is preferable. However, the preferable range of the temperature for transfer is related to the heat resistance of the heating member, the transfer material, and the substrate, and changes as the heat resistance improves.

FIG. 1 shows an example of an apparatus for carrying out the method for manufacturing an organic thin film element of the present invention. The transfer material 110 in which the organic thin film layer 112 is provided on the temporary support 111 is supplied from the transfer material winding roll 113. The transfer device includes a heating roll 121 and a pressure (heating) roll 122. A substrate 100 including a substrate support 101 and a transparent conductive layer (cathode or anode) 102 is arranged between a heating roll 121 and a pressure (heating) roll 122, and the heating roll 121 and the transparent conductive layer 102 of the substrate 100. Between the board 1
The transfer material 110 is fed so that the transparent conductive layer 102 of 00 contacts the organic thin film layer 112 of the transfer material 110. Heating with the heating roll 121, or heating roll 121 and pressure (heating) roll 122
The organic thin film layer 112 is transferred onto the transparent conductive layer 102 of the substrate 100 by applying pressure while heating. Remaining temporary support
111 is wound up by a temporary support winding roll 114.

In the present invention, the steps of transferring the organic thin film layer 112 and peeling the temporary support 111 can be repeated to laminate a plurality of organic thin film layers on the substrate. The plurality of organic thin film layers may have the same composition or different compositions. In the case of the same composition, there is an advantage that it is possible to prevent the layer from coming off due to a transfer failure or a peeling failure. In the case where different layers are provided, the function can be separated so that the light emission efficiency can be improved. / Electron injection layer,
A hole injection layer / hole transporting organic thin film layer / light emitting organic thin film layer / electron transporting organic thin film layer / electron injection layer can be laminated.

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. Further, 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 formation surface so that the previous transfer layer is not reversely transferred to the next transfer layer. Examples of such surface treatment include activation treatments such as corona discharge treatment, flame treatment, glow discharge treatment, and plasma treatment.

[3] Organic thin film element (1) Structure The overall structure of the organic thin film element is as follows: transparent conductive layer / light emitting organic thin film layer / back electrode, transparent conductive layer / light emitting organic thin film layer / electron on a substrate support. Transportable organic thin film layer / back electrode, transparent conductive layer / hole transportable organic thin film layer / luminescent organic thin film layer / electron transportable organic thin film layer / rear electrode, transparent conductive layer / hole transportable organic thin film layer / luminescent organic Thin film layer / back electrode, transparent conductive layer / luminescent organic thin film layer / electron transporting organic thin film layer / electron injection layer / rear electrode, transparent conductive layer / hole injection layer / hole transporting organic thin film layer / luminescent organic thin film layer It may have a constitution in which / electron transporting organic thin film layer / electron injection layer / back electrode and the like are laminated in this order, and a constitution in which these are laminated in reverse. The light-emitting organic thin film layer contains a fluorescent light-emitting compound and / or a phosphorescent light-emitting compound, and light is usually taken out from the transparent conductive layer. 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.

(2) Substrate support The substrate support is a zirconia-stabilized yttrium (YS
Z), inorganic materials such as glass, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyethylene naphthalate, polystyrene, polycarbonate, polyether sulfone, polyarylate, allyl diglycol carbonate, polyimide, polycycloolefin, norbornene resin, polychloro It may be made of a polymer material such as trifluoroethylene, Teflon (registered trademark), or a polytetrafluoroethylene-polyethylene copolymer. The substrate support may be formed of a single material or two or more materials. Among them, a polymer material is preferable for forming a flexible organic thin film element, and is a polyester having excellent heat resistance, dimensional stability, solvent resistance, electrical insulation and processability, and low air permeability and low hygroscopicity. Further, polymer materials containing a fluorine atom such as polycarbonate, polyether sulfone, polychlorotrifluoroethylene, Teflon, and polytetrafluoroethylene-polyethylene copolymer are more preferable.

The shape, structure, size and the like of the substrate support can be appropriately selected according to the application and purpose of the organic thin film element. The shape is generally a plate. The structure may be a single layer structure or a laminated structure. The substrate support may be formed of a single member or two or more members. The substrate support may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate the light emitted from the luminescent organic thin film layer.

A moisture permeation preventive layer (gas barrier layer) may be provided on the electrode-side surface of the substrate support, the surface opposite to the electrode, or both of them. As a material forming the moisture permeation preventive layer, it is preferable to use an inorganic substance such as silicon nitride or silicon oxide. The moisture permeation preventive layer can be formed by a high frequency sputtering method or the like.
If necessary, the substrate support may be provided with a hard coat layer or an undercoat layer.

(3) Electrode (Cathode or Anode) Either the transparent conductive layer or the back electrode can be used as a cathode or an anode, and either one is determined by the composition constituting the organic thin film element.

(A) Transparent Conductive Layer (Transparent Electrode) The transparent conductive layer has a function as an anode for supplying holes to the organic compound layer, but can also function as a cathode. Hereinafter, the case where the transparent conductive layer is used as the anode will be described.

The shape, structure, size, etc. of the transparent conductive layer are not particularly limited and can be appropriately selected according to the use and purpose of the organic thin film element. As a material for forming the transparent conductive layer, a metal, an alloy, 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 eV or more is preferably used. Specific examples include antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), semiconducting metal oxides (tin oxide, zinc oxide, indium oxide, indium tin oxide (IT
O), zinc indium oxide (IZO), etc.), metals (gold, silver,
(Chromium, nickel, etc.), mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials (copper iodide, copper sulfide, etc.), organic conductive materials (polyaniline, polythiophene, polypyrrole, etc.) and this Examples thereof include a laminate with ITO.

The transparent conductive layer is formed by a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method and an ion plating method, a chemical method such as a CVD method and a plasma CVD method, and the like. Can be formed on. The forming method may be appropriately selected in consideration of suitability with the transparent conductive layer material. For example, as the material of the transparent conductive layer
When ITO is used, a 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 material of the transparent conductive layer, a wet film forming method may be used.

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

The formation position of the transparent conductive layer may be appropriately selected depending on the use and purpose of the organic thin film element, but it is preferably formed on the substrate support. At this time, the transparent conductive layer may be formed on the entire surface of the substrate support or only on a part thereof.

The thickness of the transparent conductive layer may be appropriately selected depending on the material thereof, but is usually 10 nm to 50 μm, preferably 50 nm to 20 μm. The resistance value of the transparent conductive layer is 10 ³ Ω /
It is preferably □ or less, and more preferably 10 ² Ω / □ or less. The transparent conductive layer may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent conductive layer side, its transmittance is preferably 60% or more.
% Or more is more preferable. 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) Back Electrode The back electrode has a function as a cathode for injecting electrons into the organic compound layer, but can also function as an anode.
The case where the back electrode is the cathode will be described below.

The shape, structure, size and the like of the back electrode are not particularly limited and can be appropriately selected according to the use and purpose of the organic thin film element. As a material for forming the back electrode, a metal, an alloy, 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. Specific examples include alkali metals (Li, Na, K, Cs, etc.), alkaline earth metals (Mg, Cs).
a), 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 these materials, alkali metal and alkaline earth metal are preferable from the viewpoint of electron injection property, and aluminum-based material is preferable from the viewpoint of storage stability. Here, the material mainly composed of aluminum is not only aluminum alone, but an alloy or a mixture of aluminum and 0.01 to 10 mass% of an alkali metal or an alkaline earth metal (lithium-aluminum alloy,
Magnesium-aluminum alloy). As the material for the back electrode, those detailed in JP-A Nos. 2-15595 and 5-121172 can be used.

The back electrode can be formed by 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, or a chemical method such as a CVD method or a plasma CVD method. it can. The forming method may be appropriately selected in consideration of the suitability for the back electrode material. For example, when two or more kinds of metals or the like are used as the material of the back electrode, the materials can be formed by sputtering simultaneously or sequentially. The back electrode can be patterned in the same manner as the transparent conductive layer.

The formation position of the back electrode may be appropriately selected according to the use and purpose of the organic thin film element, but it is preferably formed on the organic compound layer. At this time, the back electrode may be formed on the entire surface of the organic compound layer or only on a part thereof. In addition, a dielectric layer made of fluoride of alkali metal or alkaline earth metal is provided between the back electrode and the organic compound layer.
You may install with a thickness of 0.1-5 nm. The dielectric layer can be formed by a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the back electrode may be appropriately selected according to the material thereof, but is usually 10 nm to 5 μm, and preferably
50 nm to 1 μm. The back electrode may be transparent or opaque. The transparent back electrode comprises 1 to 3 layers of the above materials.
It may be formed by forming a thin film with a thickness of 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(4) Patterning To form the fine patterned organic thin film layer, a mask (fine mask) having fine patterned openings is 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,
5-60 micrometers is more preferable.

The mask opening is closer to the transfer material side than the substrate side so that the organic thin film layer of the transfer material adheres to the underlying transparent conductive layer or other organic thin film layer exactly in the shape of the opening of the mask. It is preferably tapered so as to be large.

(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. Furthermore, if the transfer material does not affect the light emitting performance, 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 transferability. It may be provided.

(A) Protective Layer Organic Thin Film Element is disclosed in JP-A Nos. 7-85974, 7-129866 and 8
-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 is, for example, a substrate support,
When the transparent conductive layer, the organic compound layer and the back electrode are laminated in this order, it indicates the outer surface of the back electrode, and, for example, when the substrate support, the back electrode, the organic compound layer and the transparent conductive layer are laminated in this order. Refers to the outer surface of the transparent conductive layer.
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 water or oxygen that may deteriorate the organic thin film element, for example, monoxide. Silicon, silicon dioxide, 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 sen epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, plasma CVD method, Laser CVD method, thermal CVD method, coating method and the like can be applied.

(B) Sealing Layer It is preferable that the organic thin film element is provided with a sealing layer for preventing invasion of moisture and oxygen. 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 compound layer with a sealing member such as a sealing plate or a sealing container. The sealing member may be provided only on the back electrode side, or the entire light emitting laminate 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 compound layer can be sealed and the outside air can be blocked. As a material used for the sealing member, glass, stainless steel, metal (aluminum or the like), plastic (polychlorotrifluoroethylene, polyester, polycarbonate or the like), ceramic or the like can be used.

When the sealing member is installed on the light emitting laminate,
A sealing agent (adhesive) may be used as appropriate. When the entire light emitting laminate is covered with the sealing member, the sealing members may be heat-sealed without using the sealing agent. An ultraviolet curable resin, a thermosetting resin, a two-component curable resin, or the like can be used as 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.

[0068]

EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited thereto. Examples 1-9, Comparative Examples 1-2

(A) Preparation of Transfer Material A Polyethersulfone (Sumitomo Bakelite Co., Ltd., thickness: 188 μm) was provided on one surface of a temporary support, and the polymer (PTPDES, Viscosity is 1 × 10 ⁴ P
a ・ s temperature = 186 ℃, Mw = 22000,): 40 parts by mass,
And dichloroethane: 3500 parts by mass

[0070]

[Chemical 1]

An organic thin film layer-containing coating solution containing is applied using an extrusion type coating machine and dried at room temperature to form a hole transporting organic thin film layer having a thickness of 30 nm on a temporary support. A transfer material A was prepared.

(B) Preparation of Transfer Materials B-1 to B-11 Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich) on one surface of a temporary support similar to Transfer Material A: 40 parts by mass. Each additive component shown: 15 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 containing 3500 parts by mass was applied using a bar coater. Transfer material B-1 with a 40 nm-thick luminescent organic thin film layer formed on a temporary support by drying at room temperature
~ B-11 was produced.

Each of the prepared transfer materials B-1 to B-11 was cut into 5 cm square pieces, and the test pieces obtained were stacked with the coated surface facing upward, and 20 g of the coated surface contacted with the back surface. The sample was placed on a load and left in an Ar atmosphere at 30 ° C. for 3 days. Transfer material
The surface quality was evaluated as x when a failure occurred on the coated surface of B-1 to B-11 and ◯ when nothing happened. The results are shown in Table 1.
Shown in.

[0074]

[Table 1] Note (1) Polyester manufactured by Kao Corporation. (2) Polyester manufactured by Toray Industries, Inc. (3) Polyester manufactured by Toyobo Co., Ltd. (4) Polyester manufactured by Toyobo Co., Ltd. (5) Polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd. (6) Polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd.

(C) Preparation of Transfer Material C On one surface of the same temporary support as the transfer material A, the following composition: polyvinyl butyral (trade name: 2000L, viscosity 1 × 10 ⁴ P
Temperature to become a ・ s = 135 ℃, Mw = 2000, Denki Kagaku Kogyo Co., Ltd.
Manufactured): 10 parts by mass Electron transport compound having the following structural formula (Formula 2): 20 parts by mass 1-butanol: 3500 parts by mass

[0076]

[Chemical 2]

The coating liquid for an electron-transporting organic thin film layer having is coated by using an extrusion type coating machine,
By vacuum drying for a period of time, a transfer material C was prepared in which an electron-transporting organic thin film layer having a thickness of 60 nm was formed on a temporary support.

(D) Preparation of organic EL device (1) Preparation of film formation surface A glass plate of 0.5 mm × 2.5 cm × 2.5 cm was used as a substrate support, and this substrate support was introduced into a vacuum chamber, Sn
DC magnetron sputtering (conditions: substrate support temperature 250 ° C., oxygen pressure 1 × 1) using an ITO target (indium: tin = 95: 5 (molar ratio)) with an O ₂ content of 10% by mass.
0 ^-3 Pa) was used to form a transparent electrode composed of an ITO thin film having a thickness of 0.2 μm. The surface resistance of the ITO thin film was 10 Ω / □. The glass plate on which the transparent electrode was formed was placed in a cleaning container, washed with isopropyl alcohol (IPA), and then subjected to oxygen plasma treatment.

(2) Forming an organic thin film layer on the film-forming surface On the surface of a transparent electrode which was subjected to oxygen plasma treatment, an aqueous dispersion of polyethylenedioxythiophene / polystyrenesulfonic acid (manufactured by BAYER, Baytron P: solid content 1.3 mass) %) By spin coating and vacuum drying at 150 ° C for 2 hours to give a thickness of 100
A hole transporting organic thin film layer D having a thickness of nm was formed.

Further, the hole transporting organic thin film layer side of the transfer material A was superposed on the surface of another transparent electrode which had been subjected to oxygen plasma treatment, and was placed between a pair of rollers (one of which is a heating roller of 160 ° C.) having a pressure of 0.3 MPa. Through 0.05 m / min,
The transfer material A was pressed from the side of the temporary support while being heated. Then, by peeling the temporary support from the transfer material A,
The hole transporting organic thin film layer A was transferred onto the surface of the transparent electrode.

The luminescent organic thin film layer side of the transfer materials B-1 to B-11 was superposed on the surface of the obtained substrate having the hole transporting organic thin film layer of D or A, and a pair of pressures of 0.3 MPa was applied. By passing between rollers (a heating roller of which one side is 160 ° C.) at a speed of 0.05 m / min, the transfer materials B-1 to B-11 were pressed from the side of the temporary support while being heated. Next, transfer materials B-1 to B-11
The luminescent organic thin film layers B-1 to B-11 were transferred onto the upper surface of the hole transporting organic thin film layer by peeling off the temporary support.

Similarly, the electron transporting organic thin film layer side of the transfer material C is superposed on the surface of the substrate having the light emitting organic thin film layers B-1 to B-11, and a pair of rollers (one side having a pressure of 0.3 MPa) Through a heating roller having a temperature of 160 ° C.) at a speed of 0.05 m / min to apply pressure while heating the transfer material C from the temporary support side. Then, the electron-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 material C.

(3) Preparation of Back Electrode A patterned mask for vapor deposition (mask having a light emitting area of 5 mm × 5 mm) was placed on the prepared light emitting organic thin film layer, and magnesium: silver = 10 in the vapor deposition apparatus. 1 (molar ratio) was evaporated to a thickness of 0.25 μm, and then silver was evaporated to a thickness of 0.3 μm to form the back electrode. Aluminum lead wires were respectively connected from the transparent electrode (which functions as an anode) and the back electrode to form a laminated structure.

(4) Sealing The laminated structure was placed in a glove box purged with nitrogen gas, and an ultraviolet curing adhesive (XNR5493, manufactured by Nagase Ciba Co., Ltd.) was placed in a glass sealing container. Sealed with
An organic EL device 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. With respect to the light emitting device that emitted light at 200 cd, uneven light emission was observed with a microscope of 50 times. The evaluation criteria for uneven light emission are as follows. The results are shown in Table 2. When 90% or more uniformly emits light: ◎ When light emission has light and shade, but 70% or more emits uniformly:
○ When light emission has light and shade and less than 70% uniformly emitted light: ×

[0086]

[Table 2]

The substrate support is made of a square glass plate and has a thickness of 75 μm.
When the organic thin film layer was transferred by the same method as in Example except that the continuous web of polyethylene terephthalate of m was used, the same result was obtained with good productivity.

[0088]

According to the present invention, by using a transfer material having a temperature of 40 to 240 ° C. when the viscosity of at least one component constituting the organic thin film layer becomes 1 × 10 ⁴ Pa · s,
When the peeling transfer method is used, an organic EL with excellent light emission uniformity
An organic thin film element such as an element can be manufactured at low cost.

[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. 100 substrate 101 substrate support 102 cathode or anode 110 transfer material 111 temporary support 112 organic thin film layer 113 transfer material winding roll 114 temporary support winding roll 121 heating roll 122 pressurizing (heating) roll

Continued front page    F-term (reference) 3K007 AB03 AB11 AB18 DB03 FA01                 4D075 AC43 AC95 AC96 BB93Y                       CB09 DA04 DA06 DB13 DB31                       DB48 DC24 EA07 EB12 EB15                       EB19 EB22 EB32 EB33 EB35                       EB36 EB38 EB39 EB42 EB44                       EC11

Claims (2)

[Claims] 1. An organic thin film having at least one layer on a temporary support.
In the transfer material formed by forming a layer, the organic thin film layer
The viscosity of at least one constituent is 1 x 10^Four Pa · s
Transfer characterized by a temperature of 40 to 240 ° C
material. 2. The transfer material according to claim 1 is stacked and heated and / or pressurized on the substrate so that the organic thin film layer side faces the film formation surface of the substrate, and the temporary support is peeled off. In this way, the organic thin film layer is transferred to the film formation surface of the substrate, thereby manufacturing the organic thin film element.