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WO2015005263A1 - Elément organique électroluminescent et procédé de production correspondant - Google Patents

Elément organique électroluminescent et procédé de production correspondant Download PDF

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Publication number
WO2015005263A1
WO2015005263A1 PCT/JP2014/068020 JP2014068020W WO2015005263A1 WO 2015005263 A1 WO2015005263 A1 WO 2015005263A1 JP 2014068020 W JP2014068020 W JP 2014068020W WO 2015005263 A1 WO2015005263 A1 WO 2015005263A1
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Prior art keywords
layer
organic
substrate
light emitting
electrode
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Japanese (ja)
Inventor
宏 石代
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Konica Minolta Inc
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Konica Minolta Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic electroluminescence element and a manufacturing method thereof. More specifically, the present invention relates to an organic electroluminescence element using a plastically deformed substrate and a manufacturing method thereof.
  • EL electroluminescence
  • a so-called organic electroluminescence element (hereinafter also referred to as an organic EL element) is a thin-film completely solid element that can emit light at a low voltage of several V to several tens V, and has high brightness, high luminous efficiency, thin thickness, It has many excellent features such as light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.
  • Such an organic EL element has a configuration in which a light emitting layer made of an organic material is disposed between two electrodes, and emitted light generated in the light emitting layer passes through the electrode and is extracted outside. For this reason, at least one of the two electrodes is configured as a transparent electrode, and emitted light is extracted from the transparent electrode side.
  • organic electroluminescence elements using a flexible substrate from the viewpoint of design freedom and the like.
  • organic electroluminescence devices that are usually flat but change their shape into a curved surface due to physically applied force and maintain their shape when stress is unloaded are also desired. There is.
  • a flexible organic electroluminescence element or a curved organic electroluminescence element uses a resin base material, a metal sheet, or a film-like metal substrate as a substrate (for example, Patent Document 1 and 2).
  • Patent Document 1 a metal sheet, a light emitting sheet, a transparent resin plate, a display sheet, and a transparent resin sheet are sequentially laminated, and the metal sheet is heated, whereby the light emitting sheet and the transparent resin are obtained by the transparent resin sheet.
  • a technique is disclosed in which a transparent resin plate is bent by the heating and the organic electroluminescence element is molded into a curved surface simultaneously with sealing the plate and the display sheet.
  • the transparent resin plate is deformed into a curved shape by heating the metal sheet, there is a problem that the element itself deteriorates and the adhesion between the sheets deteriorates.
  • the unevenness on the surface of the metal sheet affects the adhesion with the upper layer, and it is easy for the substrate and the light emitting sheet to float or peel off during molding. There is a problem that a short circuit (short circuit) or delamination occurs.
  • Patent Document 2 discloses an organic electroluminescence element in which an insulating layer, a lower electrode, an organic light emitting layer, and an upper electrode are formed directly on a film-like metal substrate. Although it is a flexible organic electroluminescence element that can be stored in a wound shape, it is assumed that a material that maintains its shape when stress is unloaded after applying a force to form a curved surface is assumed. However, if the molding into a curved shape is repeated many times, the film-like metal substrate has a relatively high elasticity, and thus there is a problem that peeling is likely to occur between the insulating layer or the lower electrode.
  • the present invention has been made in view of the above problems and situations, and the solution to the problem is usually flat, but the shape is changed to a curved surface by the force applied physically, and the stress is unloaded.
  • To provide an organic electroluminescence device that sometimes has the property of maintaining its shape and does not float or peel between the substrate and the electrode during deformation. Moreover, it is providing the manufacturing method of the said organic electroluminescent element.
  • the present inventor uses a substrate that is plastically deformed as the substrate of the organic electroluminescence element in the process of examining the cause of the above-described problem, so that the planar shape is curved by applying force.
  • the present inventors have found that it is possible to provide an organic electroluminescence device that maintains the curved surface shape even after the stress is removed and does not float or peel off between the substrate and the electrode during deformation.
  • An organic electroluminescence device comprising at least a plastically deformed substrate, a smooth layer, a lower electrode, an organic light emitting layer, an upper electrode, and a transparent sealing substrate in this order.
  • the plastically deformed substrate is made of aluminum (Al), copper (Cu), iron (Fe), nickel (Ni), gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), cadmium (Cd ) And at least one metal selected from titanium (Ti) or an alloy thereof.
  • the smoothing layer is a smoothing layer containing a non-conductive polymer, or a smoothing layer containing at least one of polysilazane and a polysilazane modified product.
  • the organic electroluminescent element of the item is a smoothing layer containing a non-conductive polymer, or a smoothing layer containing at least one of polysilazane and a polysilazane modified product.
  • the shape is usually flat, but the shape changes to a curved surface by a physically applied force, and has the property of maintaining the shape when the stress is unloaded, and It is possible to provide an organic electroluminescence element that does not float or peel off between the substrate and the electrode during deformation.
  • the present invention is an organic electroluminescence element using a plastically deformed substrate.
  • Organic electroluminescence elements using transparent resin base materials such as PET and stainless steel (SUS) substrates return to their original shape even when bent because the substrate has high elasticity, and the bent shape cannot be maintained. In order to form a curved surface, it is necessary to prepare a curved frame or the like separately.
  • the organic electroluminescence device of the present invention is usually planar by using a plastically deformed substrate, but the shape is changed to a curved surface by the force applied physically, and the stress is unloaded. Since the shape is sometimes maintained, preparation of the curved frame or the like is not necessary, and it is possible to easily form a curved organic electroluminescence element.
  • the plastically deformed substrate since a plastically deformed substrate is used, the deformation due to the heat treatment as described in Patent Document 1 is not necessary, so that it is possible to improve the problem that the element itself deteriorates and the adhesion between the sheets deteriorates. Furthermore, the plastically deformed substrate generates less stress due to the effect of promoting gentle deformation compared to the generation of stress when the elastically deformed substrate such as a normal flexible substrate is deformed. It is presumed that floating and peeling do not easily occur between the electrodes.
  • the smooth layer according to the present invention is formed, and further, the lower electrode is provided, so that the fine unevenness due to the roughening of the substrate has an anchor effect on the smooth layer.
  • the schematic diagram which shows an example of a structure of the organic EL element of this invention The schematic diagram which shows an example of the vacuum ultraviolet irradiation apparatus used for formation of the smooth layer based on this invention
  • the organic electroluminescence device of the present invention is characterized by comprising at least a plastically deformed substrate, a smooth layer, a lower electrode, an organic light emitting layer, an upper electrode, and a transparent sealing substrate in this order.
  • This feature is a technical feature common to the inventions according to claims 1 to 6.
  • the plastically deformed substrate is made of aluminum (Al), copper (Cu), iron (Fe), nickel (Ni), gold (Au), silver More preferably, it is made of at least one metal selected from (Ag), magnesium (Mg), zinc (Zn), cadmium (Cd) and titanium (Ti), or an alloy thereof. Roughening is preferable from the viewpoint of improving the adhesion between the substrate and the electrode.
  • the smooth layer is a smooth layer containing a non-conductive polymer, or a smooth layer containing a polysilazane and a polysilazane modified product.
  • the adhesion with the substrate is further improved.
  • an electrical short circuit due to floating or peeling between the substrate and the electrode can be prevented even during deformation or storage over time, which is preferable.
  • the method for producing an organic electroluminescence element of the present invention includes a step of performing a heat treatment on the plastically deformed substrate, a step of forming the smooth layer on the substrate, the lower electrode, the organic light emitting layer, and the upper electrode.
  • it is produced by a step of forming in this order, and a step of laminating and sealing at least the entire organic light emitting layer with the transparent sealing substrate, and the heat treatment is performed at a temperature in the range of 150 to 300 ° C.
  • the above-mentioned anchor effect can further enhance the adhesion with the smooth layer, which is preferable.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the organic EL device of the present invention comprises at least a plastically deformed substrate, a smooth layer, a lower electrode, an organic light emitting layer, an upper electrode, and a transparent sealing substrate in this order.
  • a plastically deformed substrate With such a configuration, it is usually planar, but the shape changes to a curved surface due to physically applied force, and has the property of maintaining its shape when stress is unloaded, and It has been found that an organic EL element that does not float or peel off between the substrate and the electrode during deformation can be provided.
  • plastically deforming refers to the property of causing permanent deformation in its shape when a material is deformed by applying force. When a load is applied to a material, it initially elastically deforms. However, if a load is continuously applied after passing the yield point, the deformation does not return even if the stress is removed. Such a state is said.
  • the “plastically deformed substrate” as used in the present invention refers to a planar substrate having a size of 5 cm ⁇ 5 cm in a semicircular roll having a ⁇ (diameter) of 50 mm under an environment of a temperature of 23 ° C. and 55% RH.
  • the substrate is defined as a substrate that maintains its shape when a force is applied so as to be in the shape of the roll, wound into a curved surface, and then the stress is unloaded.
  • the configuration of the organic EL element 100 of the present invention includes an organic light emitting layer 103 composed of a smooth layer 110b, a lower electrode 101, an organic material, etc., and an upper electrode (counter electrode) 102, at least in order from the substrate 110a that undergoes plastic deformation. , And the transparent sealing substrate 105 are laminated in this order.
  • the smooth layer 110b is not necessarily a single layer and may be a plurality of layers.
  • the end of the lower electrode 101 has the shape of an extraction electrode, and the lower electrode 101 and an external power source (not shown) are electrically connected via the extraction electrode.
  • the organic EL element 100 is a top emission type configured such that generated light (emitted light h) is extracted from the transparent sealing substrate 105 side.
  • the plastically deformed substrate, the smooth layer, the lower electrode, the organic light emitting layer, the upper electrode, and the transparent sealing substrate are all flexible.
  • “flexibility” means that no cracks or the like occur before and after winding around a ⁇ (diameter) 50 mm roll and winding with a constant tension.
  • the “flexibility” in the present invention is included in the “flexibility”.
  • the layer structure of the organic EL element 100 includes a plastically deformed substrate, a smooth layer, a lower electrode, an organic light emitting layer, an upper electrode, and a transparent sealing substrate in this order, the other layers are limited. It may be a general layer structure.
  • the lower electrode 101 functions as an anode (that is, an anode)
  • the upper electrode 102 functions as a cathode (that is, a cathode).
  • the organic light emitting layer 103 has a structure in which a hole injection layer 103a / a hole transport layer 103b / a light emitting layer 103c / an electron transport layer 103d / an electron injection layer 103e are stacked in this order from the lower electrode 101 side which is an anode.
  • a hole injection layer 103a / a hole transport layer 103b / a light emitting layer 103c / an electron transport layer 103d / an electron injection layer 103e are stacked in this order from the lower electrode 101 side which is an anode.
  • the hole injection layer 103a and the hole transport layer 103b may be provided as a hole transport injection layer.
  • the electron transport layer 103d and the electron injection layer 103e may be provided as an electron transport injection layer.
  • the electron injection layer 103e may be made of an inorganic material.
  • the organic light emitting layer 103 may be laminated with a hole blocking layer, an electron blocking layer, or the like as required.
  • the light emitting layer 103c may have a structure in which each color light emitting layer that generates light emitted in each light wavelength region is stacked, and each of these color light emitting layers is stacked via a non-light emitting intermediate layer.
  • the intermediate layer may function as a hole blocking layer and an electron blocking layer.
  • the upper electrode 102 serving as the cathode may also have a laminated structure as necessary. In such a configuration, only a portion where the organic light emitting layer 103 is sandwiched between the lower electrode 101 and the upper electrode 102 becomes a light emitting region in the organic EL element 100.
  • an auxiliary electrode (not shown) may be provided in contact with the electrode layer of the lower electrode 101 for the purpose of reducing the resistance of the lower electrode 101.
  • the organic EL element 100 configured as described above is sealed on the substrate 110 by the transparent sealing base material 105 for the purpose of preventing deterioration of the organic light emitting layer 103 formed using an organic material or the like. Yes.
  • the transparent sealing substrate 105 is fixed to the surface of the substrate 110 via an adhesive layer.
  • the extraction electrode portion of the lower electrode 101 and the terminal portion of the upper electrode 102 are provided on the substrate 110 so as to be exposed from the transparent sealing base material 105 while being insulated from each other by the organic light emitting layer 103.
  • the transparent sealing substrate 105 preferably has a gas barrier layer in order to protect the organic light emitting layer 103 from the humidity of the external environment.
  • an electrode protective layer 104 between the upper electrode 102 and the transparent sealing substrate 105, and the upper electrode surface is protected and planarized, and the transparent sealing substrate 105 is bonded to the transparent sealing substrate 105 by solid sealing. Therefore, stronger sealing can be achieved, which is preferable.
  • the organic EL device manufacturing method of the present invention includes a step of performing a heat treatment to roughen the surface of the plastically deformed substrate, a step of forming the smooth layer on the substrate, the lower electrode, and an organic light emitting layer. And a step of forming the upper electrode in this order, and a step of laminating and sealing at least the entire organic light emitting layer with the transparent sealing substrate.
  • the substrate 110 that is plastically deformed is roughened by heat treatment, and the adhesion to the upper layer can be further improved.
  • the arithmetic average roughness Ra which is an index of the roughness of the substrate surface, is heat-treated so as to be in the range of 1 to 100 ⁇ m.
  • the arithmetic average roughness Ra represents the arithmetic average roughness based on JIS B0601-2001.
  • the surface roughness (arithmetic mean roughness Ra) is an uneven cross-section measured continuously with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope: Digital Instruments). It is calculated from the curve, and is measured three times in a section having a measurement direction of 30 ⁇ m with a stylus with a very small tip radius, and is determined from the average roughness regarding the amplitude of fine irregularities.
  • the conditions for the heat treatment can be appropriately changed depending on the type and thickness of the metal used for the plastically deformed substrate, the size of the substrate, the degree of roughening of the substrate surface, etc. Further, the heating is preferably performed at a temperature in the range of 150 to 300 ° C., and the heat treatment time is appropriately determined, but it is preferably performed for about 10 minutes to 10 hours. The heat treatment time may be a long time if the heating temperature is low, or a short time if the temperature is high.
  • the heat treatment method includes a hot plate, an oven, hot air treatment, a heating roller, a heating belt, an infrared irradiation method, a radiant heat method, and the like, which can be appropriately selected or combined.
  • an oven that can uniformly heat the entire substrate.
  • a commercially available oven can be appropriately used as the oven.
  • a heating means such as a heating wire, a heater, etc. is provided inside as the heating means, and air is introduced therein and blown to the substrate as hot air.
  • the substrate is heated to a predetermined temperature.
  • the surface heater is a heating member in which a heating element of nichrome wire is laid flat and covered with an aluminum plate or the like, taking advantage of the characteristics of the aluminum plate, You may make it contact with a board
  • a radiant heat heating means for example, a halogen lamp, a far infrared heater or the like can be used as the heat source.
  • the pipe-shaped metal core is mainly composed of metal, and examples of the metal constituting the metal core include metals such as iron, aluminum, and copper, and alloys thereof.
  • the smooth layer 110b is formed by a coating method or a vapor deposition method.
  • the layer thickness is preferably in the range of 0.01 to 1 ⁇ m.
  • the lower electrode 101 serving as the anode is produced by vapor deposition or the like.
  • an extraction electrode portion connected to an external power source is formed at the end of the lower electrode 101 by an appropriate method such as vapor deposition.
  • a hole injection layer 103a, a hole transport layer 103b, a light emitting layer 103c, an electron transport layer 103d, and an electron injection layer 103e are stacked in this order on this, thereby forming the organic light emitting layer 103.
  • each of these layers includes spin coating, casting, inkjet, vapor deposition, and printing, but vacuum vapor deposition is easy because a homogeneous layer is easily obtained and pinholes are difficult to generate.
  • the method or spin coating method is particularly preferred. Further, different formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, etc., but generally a resistance heating boat is used and the boat heating temperature is 50 to 450 ° C., and the degree of vacuum is 1 ⁇ 10 ⁇ 6 to It is desirable to appropriately select each condition within the range of 1 ⁇ 10 ⁇ 2 Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of ⁇ 50 to 300 ° C., and layer thickness of 0.1 to 5 ⁇ m.
  • an upper electrode 102 serving as a cathode is formed thereon by an appropriate forming method such as vapor deposition or sputtering.
  • the upper electrode 102 is patterned in a shape in which a terminal portion is drawn from the upper side of the organic light emitting layer 103 to the periphery of the substrate 110 while maintaining an insulating state with respect to the lower electrode 101 by the organic light emitting layer 103.
  • the electrode protective layer 104 is preferably formed by an appropriate method such as the coating method or the vapor deposition method so that the layer thickness is 1 ⁇ m or less, preferably in the range of 10 to 100 nm.
  • the transparent sealing substrate 105 provided with the adhesive layer is laminated and sealed so as to cover at least the entire organic light emitting layer by a method such as thermocompression bonding, and the organic EL element 100 is manufactured.
  • the plastically deformable substrate 110a according to the present invention is characterized by using a resin material or a metal material having a property of plastic deformation, and among them, a metal material is preferable.
  • a metal material aluminum ( Selected from Al), copper (Cu), iron (Fe), nickel (Ni), gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), cadmium (Cd) and titanium (Ti)
  • a metal material made of at least one kind of metal or an alloy thereof. In view of strength, mass, ease of handling, cost, and the like when manufacturing the organic EL device of the present invention, aluminum (Al) or copper (Cu) is more preferable.
  • the metal of the substrate serves as a gas barrier layer that minimizes the transmission of oxygen and moisture to the organic EL element.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2% RH) measured by a method according to JIS K 7129: 1992 is 0.01 g / (m 2 ⁇ 24 hours.
  • the following gas barrier properties are preferred, and the oxygen permeability measured by a method according to JIS K 7126: 1987 is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 hours ⁇ atm) or less, water vapor It is more preferable that the gas permeability is 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 hours) or less.
  • the thickness of the substrate needs to be designed so that the metal plate is plastically deformed, for example, and satisfies the above gas barrier properties, preferably in the range of 10 to 500 ⁇ m, more preferably It is in the range of 30 to 250 ⁇ m, and more preferably in the range of 60 to 200 ⁇ m from the viewpoint of plastic deformability, gas barrier properties, flatness, handling properties, and the like.
  • the thickness of the substrate is in the range of 10 to 500 ⁇ m, it can be plastically deformed with a small force and a stable gas barrier property can be obtained.
  • the smoothing layer 110b is an insulating layer having electrical insulation with respect to the lower electrode, and further is an intermediate layer that improves the adhesion between the substrate and the upper layer, particularly the substrate and the lower electrode, and forms the lower electrode. In order to facilitate, it is a layer that smoothes the roughened substrate surface.
  • electrical insulation refers to a state in which electricity does not easily flow, and the sheet resistance value measured by a method in accordance with JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is used. It means higher than 1 ⁇ 10 8 ⁇ / ⁇ .
  • the smooth layer 110b according to the present invention has a flatness that allows the lower electrode 101 to be satisfactorily formed thereon, and the surface property is within the range of the arithmetic average roughness Ra of 0.5 to 50 nm.
  • the upper limit is 30 nm or less, particularly preferably 10 nm or less, and most preferably 5 nm or less. That is, by setting the arithmetic average roughness Ra of the surface of the smooth layer 110b on the organic light emitting layer 103 side within the range of 0.5 to 50 nm, it is possible to suppress defects such as a short circuit of the lower electrode to be laminated.
  • the arithmetic average roughness Ra 0 nm is preferable, but 0.5 nm is set as a lower limit value as a practical level limit value.
  • the smoothing layer 110b receives light emitted from the organic light emitting layer 103. Therefore, the average refractive index nf of the smooth layer 110 b is preferably a value close to the refractive index of the organic functional layer included in the organic light emitting layer 103. Specifically, since an organic material having a high refractive index is generally used for the organic light emitting layer 103, the smoothing layer 110b has the shortest emission maximum wavelength among the emission maximum wavelengths of the emitted light from the organic light emitting layer 103.
  • the high refractive index layer preferably has an average refractive index nf of 1.50 or more, particularly 1.65 or more and less than 2.50.
  • the average refractive index nf is 1.65 or more and less than 2.50, it may be formed of a single material or a mixture.
  • the average refractive index nf of the smooth layer 1 uses a calculated refractive index calculated by a total value obtained by multiplying the refractive index specific to each material by the volume ratio.
  • the refractive index of each material may be less than 1.65 or more than 2.50, and the average refractive index nf of the mixed film should satisfy 1.65 or more and less than 2.50. That's fine.
  • the “average refractive index nf” of the smooth layer is the refractive index of a single material when formed of a single material, and in the case of a mixed system, the desired volume based on the density of each material.
  • the refractive index is measured by preparing a smooth layer single film and irradiating the light having the shortest light emission maximum wavelength among the light emission maximum wavelengths of the light emitted from the light emitting unit in an atmosphere at 25 ° C. (DR-M2 manufactured by ATAGO) was used.
  • a layer containing a non-conductive polymer or a layer containing a polysilazane and a modified polysilazane is preferable to use.
  • Non-conductive polymer The non-conductive polymer according to the present invention is preferably a non-conductive polymer having a hydroxy group, and further a self-dispersing polymer having a dissociable group. Is preferred.
  • Non-conductive polymer having a hydroxy group As the non-conductive polymer having a hydroxy group used in the present invention, it is preferable to use a compound represented by the following general formula (I).
  • R represents a hydrogen atom or a methyl group
  • Q represents C ( ⁇ O) O, or C ( ⁇ O) NRa.
  • Ra represents a hydrogen atom or an alkyl group
  • A represents a substituted or unsubstituted alkylene.
  • the non-conductive polymer having a hydroxy group means a polymer that is water-soluble and dissolves 0.001 g or more in 100 g of water at 25 ° C. The solubility can be measured with a haze meter or a turbidimeter.
  • the non-conductive polymer having a hydroxy group used in the present invention has a structure containing at least the structural unit represented by the general formula (I), and is a homopolymer represented by the general formula (I).
  • other components may be copolymerized.
  • the structural unit represented by the general formula (I) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.
  • the water-insoluble binder resin described later is preferably contained in the smooth layer in an amount of 40% by mass to 80% by mass, and more preferably 50% by mass to 70% by mass.
  • R represents a hydrogen atom or a methyl group.
  • Q represents C ( ⁇ O) O or C ( ⁇ O) NRa, and
  • Ra represents a hydrogen atom or an alkyl group.
  • the alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group. Moreover, these alkyl groups may be substituted with a substituent.
  • substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyls
  • A represents a substituted or unsubstituted alkylene group, or — (CH 2 CHRbO) x — (CH 2 CHRb) —.
  • the alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent described above.
  • Rb represents a hydrogen atom or an alkyl group.
  • the alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group. Moreover, these alkyl groups may be substituted with the above-mentioned substituent.
  • x represents the average number of repeating units, and is preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.
  • the self-dispersing polymer having a dissociable group means a polymer that does not contain a surfactant or an emulsifier that assists micelle formation and can be dispersed in an aqueous solvent by itself.
  • “Dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration.
  • the size of the colloidal particles is generally about 0.001 to 1 ⁇ m (1 to 1000 nm).
  • the size of the colloidal particles is preferably in the range of 3 to 500 nm, more preferably in the range of 5 to 300 nm, and still more preferably in the range of 10 to 100 nm.
  • the main skeleton of the self-dispersing polymer having a dissociable group is polyethylene, polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polybutadiene, polybutadiene-polystyrene, polyolefin copolymer, polyamide (nylon) , Polyvinylidene chloride, polyester, polyacrylate, polyacrylate-polyester, polyacrylate-polystyrene, polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-polyacrylate, silicone, silicone-polyurethane, silicone- Polyacrylate, polyvinylidene fluoride-polyacrylate, polyfluoroolefin-polyvinyl ether Etc.
  • PVA polyethylene-polyvinyl alcohol
  • PVA polyethylene-polyvinyl
  • copolymerization using another monomer may be the main skeleton.
  • a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, and a polyethylene resin emulsion having an ethylene skeleton are preferable.
  • Polysol FP3000 polyethylene resin, anion, core: acrylic, shell: polyester, manufactured by Showa Denko KK
  • Vironal MD1480 polyyester resin, anion, manufactured by Toyobo
  • Vironal MD1245 polyyester resin, anion, Toyobo Co., Ltd.
  • Bironal MD1500 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Bironal MD2000 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Bironal MD1930 polyyester resin, anion, manufactured by Toyobo Co., Ltd.
  • Plus Coat RZ105 polyyester resin, anion
  • Plus Coat RZ570 polyyester resin, anion, manufactured by Tatemono Chemical Co., Ltd.
  • Plus Coat RZ571 polyyester resin, anion, manufactured by Tatemono Chemical Co., Ltd.
  • Hitech S-9242 polyethylene resin, anion,
  • a self-dispersing polymer having a dissociable group can be dispersed in an aqueous solvent.
  • the aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent.
  • the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.
  • the pH of the above dispersion at 25 ° C. is not particularly problematic as long as the desired non-conductivity can be obtained, but is preferably 0.1 to 7.0, more preferably 0.3 to 5.0.
  • binders that can be uniformly dispersed in an aqueous solvent are uniform.
  • Other binders that can be dispersed can also be used.
  • the binder is preferably a transparent binder.
  • the binder that can be uniformly dispersed in the aqueous solvent is not particularly limited as long as it is a medium for forming a layer.
  • Examples of the binder that can be uniformly dispersed in the aqueous solvent include: acrylic resin emulsion, aqueous urethane resin, and the like.
  • Boncourt AN-155-E Boncourt AC-501, Boncourt AN-200, Boncourt R-3380-E (acrylic resin emulsion (anionic)), Bondick 1940NE (water-dispersed polyurethane resin, polyether) -Based urethane resin), Bondick 2210, Bondick 2220 (water-dispersed polyurethane resin, polyester-based urethane resin), Hydran 140SF, Hydran AP-40 (F), Hydran AP-40N (Ionomer-type water-based urethane resin, polyester-based urethane) Resin), Hydran HW-312B, Hydran WLS-201 (ionomer-type water-based urethane resin, polyether-based urethane resin) (all manufactured by DIC).
  • One or more binders that can be uniformly dispersed in the aqueous solvent can be used.
  • the amount of the binder that can be uniformly dispersed in the aqueous solvent is preferably 1 to 200% by mass, more preferably 5 to 100% by mass with respect to the non-conductive polymer.
  • non-conductive polymer layer As a method of forming a layer containing a non-conductive polymer on the substrate according to the present invention, both high productivity and reduction in production cost are achieved, and environmental load is reduced. From the viewpoint, it is preferable to use a liquid phase film forming method such as a coating method or a printing method.
  • coating methods known roll coating methods, bar coating methods, dip coating methods, spin coating methods, casting methods, die coating methods, blade coating methods, bar coating methods, gravure coating methods, curtain coating methods, spray coating methods, doctors A coating method or the like can be used.
  • a letterpress (letter) printing method As a printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, or the like can be used.
  • the dry film thickness of the non-conductive polymer layer can be appropriately selected in consideration of the sheet resistivity, but is preferably 30 to 2000 nm.
  • the thickness is more preferably 200 nm or more from the viewpoint of non-conductivity, and more preferably 1000 nm or less from the viewpoint of transparency.
  • the smooth layer according to the present invention is preferably a smooth layer containing at least one of polysilazane and a polysilazane modified body.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 made of Si—N, Si—H, N—H, etc., Si 3 N 4 and both intermediate solid solutions SiOxNy, etc. It is a ceramic precursor inorganic polymer.
  • Polysilazane and polysilazane derivatives are represented by the following general formula (P).
  • the modified polysilazane is a compound containing at least one selected from silicon oxide, silicon nitride, and silicon oxynitride, which is produced by modifying polysilazane.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. .
  • Perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms, is particularly preferred from the viewpoint of the denseness of the resulting layer.
  • the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane is hard and brittle.
  • the ceramic film can be provided with toughness, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing liquid. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.
  • a coating layer containing polysilazane it is preferable to prepare a coating layer containing polysilazane, and apply a coating solution for forming a smooth layer containing polysilazane on the substrate to form a smooth layer.
  • organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating solution for forming a smooth layer containing polysilazane varies depending on the layer thickness of the smooth layer and the pot life of the coating solution, but is preferably in the range of 0.2 to 35% by mass.
  • the coating solution for forming a smooth layer includes an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, and an Rh compound such as Rh acetylacetonate.
  • a metal catalyst can also be added. In the present invention, it is particularly preferable to use an amine catalyst.
  • Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.
  • the amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass, and preferably in the range of 0.2 to 5% by mass with respect to the total mass of the smooth layer forming coating solution. More preferably, it is more preferably in the range of 0.5 to 2% by mass.
  • Arbitrary appropriate wet coating methods may be employ
  • Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the thickness of the coating film can be appropriately set according to the purpose.
  • the thickness of the coating film is preferably in the range of 50 nm to 2 ⁇ m as the thickness after drying, more preferably in the range of 70 nm to 1.5 ⁇ m, and in the range of 100 nm to 1 ⁇ m. Is more preferable.
  • the modification treatment is preferably performed on a coating layer formed by applying a smooth layer forming coating solution containing polysilazane to the substrate.
  • a known method based on the conversion reaction of polysilazane can be selected.
  • heat treatment at 450 ° C. or higher is necessary, and it may be difficult to apply depending on the type of substrate. Therefore, it is preferable to use a method such as plasma treatment, ozone treatment, or ultraviolet irradiation treatment capable of allowing the conversion reaction to proceed at a low temperature.
  • modification treatment used in the present invention plasma irradiation, ultraviolet irradiation, and vacuum ultraviolet irradiation are desirable, and vacuum ultraviolet irradiation is particularly preferable in terms of the modification effect of polysilazane.
  • Plasma irradiation treatment As the plasma irradiation treatment as the modification treatment, a known method can be used, but atmospheric pressure plasma treatment is preferable. In the case of atmospheric pressure plasma treatment, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • the atmospheric pressure plasma treatment is one in which two or more electric fields having different frequencies are formed in the discharge space as described in International Publication No. 2007/026545. It is preferable to form an electric field superimposed with a high-frequency electric field.
  • the above patent can be referred to for details.
  • UV irradiation treatment As a modification treatment method, treatment by ultraviolet irradiation is also preferred. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and it is possible to produce silicon oxide or silicon oxynitride having high density and insulation at low temperature. .
  • the base material is heated, and O 2 and H 2 O contributing to ceramicization (silica conversion) and polysilazane itself are excited and activated, so that polysilazane is excited and promotes the ceramicization of polysilazane.
  • the resulting ceramic film becomes denser.
  • the ultraviolet irradiation may be performed at the time of preparing the coating solution for forming the smooth layer, or may be performed after applying the coating solution for forming the smooth layer.
  • a more preferable method for the modification treatment is a treatment by vacuum ultraviolet irradiation.
  • the treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the silazane compound, and only bonds photons called photon processes to bond atoms.
  • This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of.
  • a rare gas excimer lamp is preferably used.
  • illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is in the range of 30 ⁇ 200mW / cm 2, and more preferably in a range of 50 ⁇ 160mW / cm 2. If it is 30 mW / cm 2 or more, there is no concern about a reduction in the reforming efficiency, and if it is 200 mW / cm 2 or less, the coating film is preferably not ablated.
  • Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200 ⁇ 10000mJ / cm 2, and more preferably in a range of 500 ⁇ 5000mJ / cm 2. If it is 200 mJ / cm 2 or more, the modification can be sufficiently performed, and if it is 10000 mJ / cm 2 or less, it is not over-reformed and cracking and thermal deformation can be prevented.
  • the lower electrode 101 is an anode (anode) and the upper electrode 102 is a cathode (cathode).
  • the lower electrode 101 is a cathode and the upper electrode 102 is It may be an anode.
  • the organic EL element 100 of the present invention shown in FIG. 1 will be described as an example. Since the organic EL element 100 is a top emission type, the lower electrode 101 functioning as an anode does not necessarily need to be translucent. A reflective electrode may be used, and a reflective electrode is preferable.
  • the electrode layer constituting the lower electrode 101 is made of a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO (Indium Tin Oxide) An oxide semiconductor such as ZnO, TiO 2 , and SnO 2 ; Among these, in the case of a reflective electrode, it is preferable to use aluminum.
  • the lower electrode 101 can be formed of these conductive materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the lower electrode 101 is several hundred ⁇ / sq. The following are preferable, and the thickness is usually selected in the range of 5 to 5000 nm, preferably 5 to 200 nm.
  • the upper electrode 102 is an electrode layer that functions as a cathode for supplying electrons to the organic light emitting layer 103, and a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof are used.
  • the upper electrode 102 all the electrodes that can be normally used for the organic EL element can be used similarly to the lower electrode. Specifically, aluminum, silver, magnesium, lithium, magnesium / same mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO 2 , An oxide semiconductor such as SnO 2 can be given.
  • the upper electrode is preferably a transparent electrode, and it is preferable to use highly transparent ITO, silver, or an alloy containing silver as a main component.
  • a method for forming the upper electrode 102 As a method for forming the upper electrode 102, a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like. And a method using the dry process. In particular, the vapor deposition method is preferably applied.
  • the upper electrode 102 is a layer composed of silver or an alloy containing silver as a main component, and can form a thin and highly transparent electrode layer, which is suitable for a top emission type organic EL element. Can be used.
  • Examples of the alloy mainly composed of silver (Ag) constituting the upper electrode 102 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn). ) And the like.
  • the upper electrode is an electrode layer composed of silver or an alloy containing silver as a main component
  • the compound containing a nitrogen atom constituting the underlayer is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule, but is preferably a compound having a heterocycle having a nitrogen atom as a heteroatom.
  • the heterocycle having a nitrogen atom as a hetero atom include aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, Examples include isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and
  • a dry process such as a method using a wet process such as a coating method, an inkjet method, a coating method, or a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, or a CVD method is used.
  • a vapor deposition method resistance heating, EB method, etc.
  • a sputtering method or a CVD method
  • the upper electrode 102 as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.
  • the upper electrode 102 preferably has a layer thickness in the range of 5 to 30 nm.
  • the layer thickness is less than 30 nm, the absorption component or reflection component of the layer is small, and the transmittance of the upper electrode 102 is increased.
  • the layer thickness is thicker than 5 nm, the conductivity of the layer can be sufficiently secured.
  • the range is preferably 8 to 20 nm, and more preferably 9 to 15 nm.
  • Organic light emitting layer 103 includes at least a light emitting layer 103c.
  • the phosphor layer 103c used in the present invention preferably contains a phosphorescent compound as a luminescent material.
  • a fluorescent material may be used as the light emitting material, or a phosphorescent light emitting compound and a fluorescent material may be used in combination.
  • the light emitting layer 103c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 103d and holes injected from the hole transport layer 103b, and the light emitting portion is the light emitting layer 103c. Even within the layer, it may be the interface between the light emitting layer 103c and the adjacent layer.
  • the structure of the light emitting layer 103c is not particularly limited as long as the included light emitting material satisfies the light emission requirements. There may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, a non-light emitting intermediate layer (not shown) is preferably provided between the light emitting layers 103c.
  • the total thickness of the light emitting layer 103c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained.
  • the sum of the layer thicknesses of the light emitting layer 103c is a layer thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers 103c.
  • the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. preferable.
  • the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.
  • the light emitting layer 103c as described above is formed by forming a known light emitting material or host compound by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. be able to.
  • a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.
  • a host compound and a light emitting dopant (also referred to as a light emitting dopant compound) contained in the light emitting layer will be described.
  • the host compound means that the compound contained in the light emitting layer has a mass ratio of 20% or more in the layer and is phosphorus at room temperature (25 ° C.).
  • a compound having a phosphorescence quantum yield of photoluminescence of less than 0.1 is defined.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • known host compounds may be used alone or in combination of two or more.
  • the organic EL element can be made highly efficient.
  • the light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).
  • a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.
  • the light emitting layer of the organic EL device of the present invention preferably contains a phosphorescent dopant simultaneously with the host compound.
  • the phosphorescent dopant used in the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is Although defined as a compound of 0.01 or more at 25 ° C., a preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • the energy transfer type that obtains light emission from the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained.
  • the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.
  • At least one light emitting layer 103c may contain two or more types of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 103c is the thickness of the light emitting layer 103c. It may change in the direction.
  • the phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 103c.
  • Examples of the fluorescent light emitting material used for the light emitting layer 103c include, for example, a coumarin dye, a pyran dye, a cyanine dye, a croconium dye, a squalium dye, an oxobenzanthracene dye, a fluorescein dye, a rhodamine dye, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • injection layer (hole injection layer, electron injection layer)
  • the injection layer is a layer provided between the electrode and the light-emitting layer 103c in order to lower the drive voltage and improve the light emission luminance.
  • the injection layer can be provided as necessary.
  • the hole injection layer 103a may exist between the anode and the light emitting layer 103c or the hole transport layer 103b, and the electron injection layer 103e may exist between the cathode and the light emitting layer 103c or the electron transport layer 103d.
  • hole injection layer 103a Details of the hole injection layer 103a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like.
  • Specific examples include phthalocyanine represented by copper phthalocyanine.
  • examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • the details of the electron injection layer 103e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically represented by strontium, aluminum and the like. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide.
  • the electron injection layer 103e of the present invention is desirably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 ⁇ m although it depends on the material.
  • the hole transport layer 103b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 103a and the electron blocking layer are also included in the hole transport layer 103b. .
  • the hole-transport layer 103b can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • hole transport material those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
  • a so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.
  • the hole transport layer 103b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. be able to.
  • the layer thickness of the hole transport layer 103b is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer 103b may have a single layer structure composed of one or more of the above materials.
  • Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer 103d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 103e and a hole blocking layer (not shown) are also included in the electron transport layer 103d.
  • the electron transport layer 103d can be provided as a single-layer structure or a stacked structure of a plurality of layers.
  • an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 103c was injected from the cathode. What is necessary is just to have the function to transmit an electron to the light emitting layer 103c.
  • any one of conventionally known compounds can be selected and used.
  • Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group are also used as the material for the electron transport layer 103d.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
  • Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the material for the electron transport layer 103d.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 103d.
  • a distyrylpyrazine derivative exemplified also as a material of the light-emitting layer 103c can be used as a material of the electron-transport layer 103d, and n-type Si, n-type similarly to the hole-injection layer 103a and the hole-transport layer 103b.
  • An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 103d.
  • the electron transport layer 103d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the layer thickness of the electron transport layer 103d is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer 103d may have a single-layer structure made of one or more of the above materials.
  • the electron transport layer 103d can be doped with an impurity to increase the n property.
  • examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer 103d contains potassium, a potassium compound, or the like.
  • the potassium compound for example, potassium fluoride can be used.
  • the material (electron transporting compound) of the electron transport layer 103d the same material as that constituting the base layer described above may be used.
  • the electron transport layer 103d also serving as the electron injection layer 103e, and the same material as that for the above-described underlayer may be used.
  • Blocking layer (hole blocking layer, electron blocking layer)
  • the blocking layer may be further provided as the organic light emitting layer 103 in addition to the above functional layers. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of the electron transport layer 103d in a broad sense.
  • the hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved.
  • the structure of the electron carrying layer 103d mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer is preferably provided adjacent to the light emitting layer 103c.
  • the electron blocking layer has a function of the hole transport layer 103b in a broad sense.
  • the electron blocking layer is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, By blocking electrons while transporting holes, the probability of recombination of electrons and holes can be improved. Further, the structure of the hole transport layer 103b can be used as an electron blocking layer as necessary.
  • the layer thickness of the hole blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • Film formation of each of the hole injection layer 103a, the hole transport layer 103b, the light emitting layer 103c, the electron transport layer 103d, and the electron injection layer 103e described above is performed by a spin coating method, a casting method, an ink jet method, an evaporation method, and a printing method.
  • the vacuum deposition method or the spin coating method is particularly preferable from the viewpoints that a homogeneous film is easily obtained and pinholes are hardly generated.
  • different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10. It is desirable to appropriately select each condition in the range of ⁇ 2 Pa, the deposition rate of 0.01 to 50 nm / second, the substrate temperature of ⁇ 50 to 300 ° C., and the layer thickness of 0.001 to 5 ⁇ m.
  • the extraction electrode is for electrically connecting the lower electrode 101 and the upper electrode 102 to an external power source, and the material thereof is not particularly limited and a known material can be preferably used.
  • a metal film such as a MAM electrode (Mo / Al ⁇ Nd alloy / Mo) having a layer structure can be used.
  • the auxiliary electrode is provided for the purpose of reducing the resistance of the lower electrode 101 and the upper electrode 102, and is provided in contact with the electrode layer 101 b of the lower electrode 101 and the electrode layer of the upper electrode 102.
  • the material for forming the auxiliary electrode is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface.
  • auxiliary electrodes examples include vapor deposition, sputtering, printing, ink jet, and aerosol jet.
  • the line width of the auxiliary electrode is preferably 50 ⁇ m or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode is preferably 1 ⁇ m or more from the viewpoint of conductivity.
  • Electrode protective layer In the present invention, forming an electrode protective layer 104 containing an organic or inorganic compound between the upper electrode 102 and the transparent sealing substrate 105 makes the surface of the upper electrode smooth and mechanical. This is preferable for providing sufficient protection. In addition, by containing an organic or inorganic compound, when the transparent sealing substrate 105 is laminated, since it is solid-sealed, the adhesive strength is high.
  • the electrode protective layer 104 as described above preferably has flexibility, and a thin polymer film or a thin metal film can be used.
  • the organic compound used in the base layer or the organic light emitting layer can be used. It is also preferable that the layer is appropriately selected and formed by the coating method or the vapor deposition method.
  • the electrode protective layer according to the present invention preferably contains a metal oxide from the viewpoint of solid sealing, and specific examples of the metal oxide include molybdenum oxide.
  • the preferred thickness of the electrode protective layer according to the present invention can be appropriately set according to the purpose, but is preferably about 10 nm to 10 ⁇ m, more preferably about 15 nm to 1 ⁇ m, and more preferably 20 to 500 nm. More preferably, it is the range.
  • the transparent sealing substrate 105 has a function of laminating and sealing the organic EL element 100, and as shown in the illustrated example, for example, an adhesive layer containing an adhesive (not shown) By this, it is fixed to the electrode protective layer 104 side and the substrate 110 side.
  • Such a transparent sealing substrate 105 is provided in a state in which the terminal portions of the lower electrode 101 and the upper electrode 102 in the organic EL element 100 are exposed and at least the organic light emitting layer 103 is completely covered.
  • the transparent sealing substrate 105 according to the present invention preferably has flexibility and preferably has gas barrier properties.
  • the transparent sealing substrate 105 is preferably composed of a transparent resin substrate as a support and one or more gas barrier layers.
  • the transparent sealing substrate 105 is a conventionally known substrate, for example, acrylic resins such as acrylic ester, methacrylic ester, PMMA, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate. (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfonate, polyimide , Polyetherimide, polyolefin, epoxy resin, and the like, and cycloolefin-based and cellulose ester-based films can also be used.
  • acrylic resins such as acrylic ester, methacrylic ester, PMMA, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate. (PC), polyarylate, polyvinyl
  • a heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a resin film obtained by laminating two or more layers of the resin material, etc. Can be mentioned.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • acrylic resin acrylic resin
  • a biaxially stretched polyethylene terephthalate (PET) film and a biaxially stretched polyethylene naphthalate (PEN) film are preferred in terms of transparency, heat resistance, ease of handling, strength, and cost.
  • the thickness of the transparent resin substrate is preferably in the range of 10 to 500 ⁇ m, more preferably in the range of 20 to 250 ⁇ m, and still more preferably in the range of 30 to 150 ⁇ m.
  • the thickness of the resin base material is in the range of 10 to 500 ⁇ m, a stable gas barrier property can be obtained, and the resin base material is suitable for conveyance in a roll-to-roll system.
  • the gas barrier layer is not particularly limited, but preferably has at least one inorganic layer on the resin substrate from the viewpoint of controlling the average refractive index in the range of 1.50 to 2.50 for light extraction.
  • the gas barrier layer is preferably a gas barrier layer coated with a coating solution containing a precursor compound and then subjected to a modification treatment by irradiation with vacuum ultraviolet rays.
  • a method for forming the layer modified with silicon oxide the method described in the section of the smooth layer can be used.
  • the method of sealing (laminating) with the transparent sealing substrate 105 is not particularly limited.
  • the organic EL element 100 is subjected to an environment in which oxygen and moisture concentration are constant (for example, oxygen concentration of 10 ppm or less, moisture concentration).
  • the organic EL element is formed by an adhesive layer formed on the transparent sealing substrate 105 by placing it under a reduced pressure (1 ⁇ 10 ⁇ 3 MPa or less) and applying pressure while applying suction. 100 is laminated, and then the adhesive layer is thermally cured by heating with a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, a heat tool, or the like.
  • thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins.
  • an epoxy resin is preferable from the viewpoint of low-temperature curability and adhesiveness.
  • epoxy resin those having an average of two or more epoxy groups per molecule may be used.
  • bisphenol A type epoxy resin biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol type epoxy are used.
  • alicyclic epoxy resin aliphatic chain epoxy resin
  • phenol novolac epoxy resin cresol novolac epoxy resin
  • bisphenol A novolac epoxy resin Epoxy resin having a butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having a dicyclopentadiene structure, diglycidyl ether
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy from the viewpoint of maintaining high heat resistance and low moisture permeability of the resin composition.
  • a resin, an aromatic glycidylamine type epoxy resin, an epoxy resin having a dicyclopentadiene structure, and the like are preferable.
  • the epoxy resin may be liquid, solid, or both liquid and solid.
  • “liquid” and “solid” are states of the epoxy resin at 25 ° C. From the viewpoints of coatability, processability, adhesiveness, and the like, it is preferable that 10% by mass or more of the entire epoxy resin to be used is liquid.
  • the epoxy resin preferably has an epoxy equivalent in the range of 100 to 1000, more preferably in the range of 120 to 1000, from the viewpoint of reactivity.
  • the epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K-7236.
  • the curing agent for the epoxy resin is not particularly limited as long as it has a function of curing the epoxy resin, but from the viewpoint of suppressing thermal deterioration of the element (particularly the organic EL element) during the curing treatment of the resin composition.
  • the curing treatment of the composition is preferably performed at 140 ° C. or lower, more preferably 120 ° C. or lower, and the curing agent preferably has an epoxy resin curing action in such a temperature range.
  • amine adduct-based compounds Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40, Amicure PN-40J, etc. (all Ajinomoto Fine Techno)
  • organic acid dihydrazide Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine Techno Co.)
  • these may be used alone or in combination of two or more.
  • the epoxy resin has extremely good low-temperature curability, and the upper limit of the curing temperature is preferably 140 ° C. or less, more preferably 120 ° C. or less, and even more preferably 110 ° C. or less.
  • the lower limit of the curing temperature is preferably 50 ° C. or higher, and more preferably 55 ° C. or higher.
  • 120 minutes or less is preferable, as for the upper limit of hardening time, 90 minutes or less are more preferable, and 60 minutes or less are still more preferable.
  • the lower limit of the curing time is preferably 20 minutes or more, and more preferably 30 minutes or more. Thereby, the thermal deterioration of the organic EL element can be extremely reduced.
  • the organic EL element of the present invention is a surface light emitter and can be used as various light sources.
  • lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, It can be used as a light source for an optical sensor.
  • the organic EL element of the present invention since the organic EL element of the present invention is characterized by plastic deformation, it may be used as a kind of lamp such as an illumination light source having a curved shape or an exposure light source. Similarly, it may be used as various types of display devices (displays) of a type that directly recognizes still images and moving images. In particular, since the organic EL element of the present invention is a top emission type, when used in the display device, the contrast is high and an excellent display performance can be realized.
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • a color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.
  • Example 1 [Production of Organic EL Element 101] (Production of substrate) The following polysilazane-containing coating solution was applied as a smooth layer onto a non-alkali glass having a thickness of 50 ⁇ m (the arithmetic average roughness Ra of the surface was 0.5 ⁇ m), and then irradiated with vacuum ultraviolet rays to form a polysilazane modified layer (in the table, Described as PHPS). The arithmetic average roughness Ra of the smooth layer surface was 1.0 nm.
  • TDAH 1,6-diaminohexane
  • the coating solution obtained above was formed into a film having a thickness of 300 nm on the glass substrate with a spin coater, allowed to stand for 2 minutes, and then heat-treated for 1 minute on a hot plate at 80 ° C. to obtain polysilazane. A coating film was formed.
  • a smooth layer was formed by applying a vacuum ultraviolet ray irradiation treatment under the condition of an integrated light amount of 6000 mJ / cm 2 .
  • 201 is an apparatus chamber, supplying appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausting from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber.
  • the oxygen concentration can be maintained at a predetermined concentration.
  • Reference numeral 202 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm
  • reference numeral 203 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 204 denotes a sample stage. The sample stage 204 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 201 by a moving means (not shown).
  • the sample stage 204 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 205 denotes a sample on which a polysilazane coating film is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm.
  • Reference numeral 206 denotes a light shielding plate, which prevents the vacuum ultraviolet light from being applied to the coating layer of the sample during the aging of the Xe excimer lamp 202.
  • the energy irradiated on the coating film surface in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using an ultraviolet integrated light meter manufactured by Hamamatsu Photonics Co., Ltd .: C8026 / H8025 UV POWER METER.
  • the sensor head is installed at the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 21 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 24 was moved at a speed of 0.5 m / min (V in FIG. 2) for measurement.
  • an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
  • the moving speed of the sample stage was adjusted to adjust the irradiation energy to 6000 mJ / cm 2 as the integrated light amount.
  • the vacuum ultraviolet irradiation was performed after aging for 10 minutes, similar to the measurement of irradiation energy.
  • PEDOT / PSS polystyrene sulfonate
  • Baytron P AI 4083 manufactured by Bayer
  • ⁇ Drying and heat treatment conditions After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment.
  • the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
  • the following coating solution for forming a white light emitting layer was applied with a spin coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. .
  • the white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
  • ⁇ White luminescent layer forming coating solution> As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, and the coating temperature was 25 ° C.
  • ⁇ Drying and heat treatment conditions After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.
  • the following coating liquid for forming an electron transport layer was applied with a spin coater under the following conditions, and then dried and heated under the following conditions to form an electron transport layer.
  • the coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.
  • the coating process was performed in an atmosphere with a nitrogen gas concentration of 99% or more, and the coating temperature of the electron transport layer forming coating solution was 25 ° C.
  • the electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
  • An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 ⁇ 10 ⁇ 4 Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
  • the extraction electrode is A mask pattern was formed by vapor deposition so that the emission area was 50 mm square, and an upper electrode having a thickness of 150 nm was laminated.
  • each laminated body formed up to the upper electrode was moved again to a nitrogen atmosphere and cut into a prescribed size using an ultraviolet laser to produce an organic EL element.
  • Crimping conditions Crimping was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.
  • the organic EL element 101 was produced using the following PET base material with a gas barrier layer as a transparent sealing base material.
  • a 125 ⁇ m thick polyester film Teijin DuPont Films, Teijin Tetron Film (registered trademark) K was used.
  • Adhesion of the transparent sealing substrate using the PET substrate with the gas barrier layer uses an epoxy thermosetting adhesive (Elephan CS manufactured by Yodogawa Paper Co., Ltd.) as an adhesive, an oxygen concentration of 10 ppm or less, and a moisture concentration of 10 ppm.
  • the PET with the gas barrier layer is directed toward the organic EL element under the conditions of 80 ° C., 0.04 MPa load, reduced pressure (1 ⁇ 10 ⁇ 3 MPa or less) suction 20 seconds, press 20 seconds. It vacuum-pressed so that the gas barrier layer of a base material might become an element side.
  • the adhesive layer was thermally cured by heating on a hot plate at 110 ° C. for 30 minutes.
  • a coating solution containing an inorganic precursor compound a catalyst-free perhydropolysilazane 20 mass% dibutyl ether solution (AZ AMICA NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst containing 5 mass% of a solid content.
  • Hydroamine silazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NAX120-20) is used by mixing, and after adjusting the amine catalyst to 1% by mass of solid content, it is further diluted with dibutyl ether. This was prepared as a 5% by mass dibutyl ether solution.
  • the substrate After coating to a PET substrate so that the film thickness after drying was 300 nm, the substrate was dried with infrared rays at a substrate temperature of 80 ° C., a drying time of 5 minutes, and a dew point of 5 ° C. in a dry atmosphere.
  • the resin substrate was gradually cooled to 25 ° C., and the coating surface was subjected to modification treatment by irradiation with vacuum ultraviolet rays in a vacuum ultraviolet irradiation apparatus.
  • a vacuum ultraviolet irradiation device an Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm was used.
  • Organic EL Element 104 In the production of the organic EL element 101, an organic EL element was similarly obtained except that a polyester film having a thickness of 125 ⁇ m (manufactured by Teijin DuPont Films Ltd., Teijin Tetron Film (registered trademark) K) was used instead of the glass substrate. 104 was produced. The arithmetic average roughness Ra of the surface of the PET substrate was 3 ⁇ m.
  • Organic EL Element 105 In the production of the organic EL element 101, an organic EL element 105 was produced in the same manner except that a SUS substrate having a thickness of 100 ⁇ m was used instead of the glass substrate. The arithmetic average roughness Ra of the surface of the SUS substrate was 18 ⁇ m.
  • Organic EL Element 106 In the production of the organic EL element 105, an organic EL element 106 was produced in the same manner except that the SUS base material was heat-treated in an oven at 240 ° C. for 20 minutes and then gradually cooled and used as a substrate. The arithmetic average roughness Ra of the surface of the SUS substrate was 126 ⁇ m.
  • Organic EL Element 107 In the production of the organic EL element 106, an aluminum (Al) base material having a thickness of 50 ⁇ m was heat-treated in an oven at 200 ° C. for 10 minutes instead of the SUS base material and then slowly cooled and used as a substrate. Thus, an organic EL element 107 was produced.
  • the arithmetic average roughness Ra of the surface of the aluminum (Al) substrate was 73 ⁇ m.
  • Organic EL Element 108 In the production of the organic EL element 107, an organic EL element 108 was produced in the same manner except that an aluminum (Al) substrate having a thickness of 100 ⁇ m was used.
  • Organic EL Element 109 In the production of the organic EL element 107, an organic EL element 109 was produced in the same manner except that an aluminum (Al) substrate having a thickness of 200 ⁇ m was used.
  • Organic EL Element 110 In the production of the organic EL element 105, an organic EL element 110 was produced in the same manner except that an aluminum (Al) base material having a thickness of 100 ⁇ m was used instead of the SUS base material. The arithmetic average roughness Ra of the surface of the aluminum (Al) substrate was 22 ⁇ m.
  • Organic EL Element 111 In the production of the organic EL element 107, a copper (Cu) base material was heated in an oven at 200 ° C. for 10 minutes instead of an aluminum (Al) base material, and then slowly cooled and used as a substrate. An organic EL element 111 was produced. The arithmetic average roughness Ra of the surface of the copper (Cu) substrate was 122 ⁇ m.
  • organic EL element 113 In the production of the organic EL element 111, an organic EL element 113 was produced in the same manner except that a copper (Cu) substrate having a thickness of 200 ⁇ m was used.
  • Organic EL Element 114 In the production of the organic EL element 110, an organic EL element 114 was produced in the same manner except that a copper (Cu) substrate having a thickness of 100 ⁇ m was used instead of the aluminum (Al) substrate. The arithmetic average roughness Ra of the surface of the copper (Cu) substrate was 63 ⁇ m.
  • the internal temperature was kept at 0 ° C. with an ice bath.
  • 30 ml of a 33% THF solution of oligoethylene glycol (10 g, 23 mmol, ethylene glycol units 7-8, manufactured by Laporte Specialties) was added dropwise. After stirring for 30 minutes, the solution was brought to room temperature and stirred for a further 4 hours. After THF was removed under reduced pressure by a rotary evaporator, the residue was dissolved in diethyl ether and transferred to a separatory funnel. Water was added and the ether layer was washed three times, and then the ether layer was dried with MgSO 4 . The ether was distilled off under reduced pressure using a rotary evaporator to obtain 8.2 g (yield 73%) of initiator 1.
  • the structure and molecular weight were measured by 1 H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.
  • the obtained polymer was diluted with water to prepare a 20% solution (abbreviated as P-1).
  • the organic EL element 116 was produced in the same manner except that the smooth layer was applied and dried so as to have a thickness of 300 nm using the following non-conductive polymer-containing coating solution B. did.
  • Polyester resin aqueous dispersion E-1 0.35 g (solid content 70 mg) 0.16 g of dimethyl sulfoxide (DMSO, 1/10 of the mass of the non-conductive polymer solution)
  • DMSO dimethyl sulfoxide
  • SEA sebacic acid
  • 931 g of ethylene glycol (EG) and 1953 g of neopentyl glycol (NPG) as an alcohol component were charged in an autoclave, 250 The esterification reaction was performed by heating at 4 ° C.
  • the temperature of the system was raised to 260 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1 hour. Under this condition, the polycondensation reaction is continued for another 5 hours, the system is brought to atmospheric pressure with nitrogen gas, the temperature of the system is lowered, and when the temperature reaches 255 ° C., 7.2 g of trimellitic anhydride is added, and at 255 ° C. for 2 hours.
  • the depolymerization reaction was carried out with stirring.
  • the system is put under pressure with nitrogen gas, the resin is discharged in a strand shape, and the pellet temperature is reduced by cutting with a pelletizer via a quenching bath having a water temperature of 35 ° C. Obtained.
  • the number average molecular weight of the obtained polyester resin PP-1 was 14000, the acid value was 23, and the glass transition temperature (Tg) was 45.
  • Organic EL Element 117 In the production of the organic EL element 112, the organic EL element 117 was produced in the same manner except that the smooth layer was applied and dried to a thickness of 300 nm using the non-conductive polymer-containing coating solution A. did.
  • Ra Surface roughness (arithmetic mean roughness) Ra
  • Ra Arithmetic mean roughness
  • Ra is an arithmetic mean roughness based on JIS B0601-2001, and uses an AFM (Atomic Force Microscope: manufactured by Digital Instruments), and has a stylus with a minimum tip radius. It was calculated from the cross-sectional curve of the unevenness measured continuously with a vessel, and measured three times in a section having a measurement direction of 30 ⁇ m with a stylus having a minimum tip radius, and obtained from the average roughness regarding the amplitude of the fine unevenness.
  • AFM Automatic Force Microscope
  • a flat substrate having a size of 5 cm ⁇ 5 cm is formed into a semicircular roll having a diameter of 50 mm in an environment of a temperature of 23 ° C. and 55% RH so that the shape of the roll is obtained.
  • a substrate that maintained its shape when stress was unloaded was applied as a substrate that was plastically deformed when a force was applied, and then the substrate that did not have such a shape was indicated as x.
  • Winding 101 to 117 around each roll of ⁇ (diameter) 2 to 10 cm was repeated 10 times, and the floating, peeling and cracking of the electrode were visually evaluated according to the following criteria.
  • organic EL element No. using the plastically deforming substrate according to the present invention was obtained.
  • 107-No. It can be seen that 117 is an organic EL element having a characteristic of plastic deformation and having excellent resistance to floating, peeling, cracking and the like of the electrode even when the shape is changed by being wound around a roll.
  • 101-No. No. 103 was unevaluable because the substrate itself was cracked when it was wound around a roll of ⁇ 6 cm or less to change its shape.
  • Example 2 Organic EL element No. 108, no. 110, no. 112, no. 114, no. 115, no. 116, no. In the production of 117, the organic EL element No. was similarly obtained except that the upper electrode was formed on the silver electrode by the following formation method. 201-No. 207 was produced.
  • Example 1 [Upper electrode: Formation of silver electrode]
  • the substrate after the formation of the electron injection layer was set in a substrate holder, the following compound A was placed in a resistance heating boat made of tantalum, and these substrate holder and heating boat were connected to the first vacuum tank of the vacuum evaporation apparatus. Attached to.
  • the first vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then heated by energizing the heating boat containing Compound A, and the layer thickness was 25 nm on the substrate at a deposition rate of 0.1 nm / second.
  • An underlayer which is a transparent functional layer made of Compound A was provided.
  • the substrate on which the base layer was formed was transferred to the second vacuum chamber in a vacuum, the second vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then a resistance heating boat made of tungsten containing silver (Ag)
  • the lower electrode having a single layer structure made of silver was formed by resistance heating vapor deposition.
  • the layer thickness of the formed lower electrode made of silver (Ag) was 9 nm.
  • Table 2 shows the configuration of the organic EL element and the evaluation results.
  • the organic EL element No. of the present invention 201-No. It can be seen that 207 reproduces Example 1, has the characteristics of plastic deformation, and has excellent resistance to electrode floating, peeling, cracking, and the like. Furthermore, by adopting a thin Ag electrode, it was found that the light emission luminance was improved and the organic EL element was excellent.
  • the organic electroluminescence device of the present invention comprises a plastically deformed substrate, a smooth layer, a lower electrode, an organic light emitting layer, an upper electrode and a transparent sealing substrate in this order, and is usually planar, but physically added.
  • the shape changes to a curved surface due to the applied force, and has the property of maintaining the shape when the stress is unloaded, and thus is suitably used for an image display device and a lighting device having a curved surface shape.

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Abstract

Le problème posé par la présente invention concerne l'obtention d'un élément organique électroluminescent qui est normalement plat, mais dont la forme est modifiée en forme courbe sous l'effet d'une force qui lui est appliquée physiquement, qui conserve ladite forme de surface incurvée quand la contrainte appliquée est supprimée et avec lequel aucun soulèvement ni aucun pelage ne se produit entre un substrat et les électrodes pendant la déformation. La solution de l'invention porte sur un élément organique électroluminescent qui se caractérise par le fait d'être doté d'au moins un substrat qui doit subir une déformation plastique, d'une couche lisse, d'une électrode inférieure, d'une couche organique d'émission lumineuse, d'une électrode supérieure et d'un matériau transparent d'étanchéité de base, dans cet ordre.
PCT/JP2014/068020 2013-07-11 2014-07-07 Elément organique électroluminescent et procédé de production correspondant Ceased WO2015005263A1 (fr)

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