JP5609524B2 - Gas barrier film and organic element device using the same - Google Patents

Description

  The present invention relates to a gas barrier film used for various device elements and an organic element device using the same. More specifically, the present invention relates to a gas barrier film having weather resistance, water resistance, flame retardancy, and light extraction / capture properties that can be sufficiently used in outdoor applications, and various device elements using the same.

  Examples of the gas barrier film substrate for various device elements that can be used in place of the glass plate include polymer materials such as plastic films and sheets. However, the polymer material has the disadvantages of low gas barrier properties and inferior flame retardancy as compared with inorganic materials such as glass.

  For gas barrier films, a thin film of metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic film, and it is widely used for packaging applications to prevent alteration of food, industrial products, pharmaceuticals, etc. It has been. Moreover, it is used with the board | substrate of various devices, such as a liquid crystal display element, a solar cell, and organic electroluminescence (EL), besides the packaging use. As a method for forming such a gas barrier film, a technique for forming a gas barrier layer by a plasma CVD method (Chemical Vapor Deposition method) or a coating liquid containing polysilazane as a main component is applied. Techniques for surface treatment are known (for example, Patent Documents 1 to 3).

  In addition, in solar cells, organic electroluminescence (EL) lighting, etc. used in various environments, the safety of the material itself has been required, and flame retardancy is one of the important functions. It is coming. As countermeasures, flame retardants such as halogen, phosphorus, inorganic and silicon are kneaded with resin and molded into a sheet by melt extrusion, or a kneaded material coated on a film is known. (For example, Patent Document 4).

  Furthermore, when an organic device or the like is used for outdoor applications, weather resistance, water resistance, and the like are required in addition to flame retardancy and gas barrier properties.

  Under the above circumstances, Patent Document 5 is proposed as a flame-retardant solar cell module having UV-cutting properties, and Patent Document 6 is proposed as an element device having a flame-retardant and gas barrier film. However, the above-mentioned technology for imparting weather resistance and flame retardancy to a flame retardant fluororesin on the film surface with an organic UV absorber is not sufficient as a UV cut function with an organic UV absorber, and is not suitable for aging or high humidity. Bleeding out to the surface under the environment, the weather resistance is not sufficient, the gas barrier layer is not described, and the gas barrier property is not sufficient. On the other hand, Patent Document 6 describes that a resin layer containing a UV absorber is provided on a flame retardant film to impart weather resistance and flame retardancy, but such a description is also possible. However, the weather resistance and water resistance are not sufficient, and it is not an invention that sufficiently guarantees light resistance or the like when used in outdoor applications. Further, there is no description of the refractive index of the UV cut layer, and the invention is not an invention from the viewpoint of achieving both UV cut performance and light extraction performance.

JP 2004-66730 A JP 2007-237588 A Special table 2009-503157 JP 52-47891 A JP-A-6-350117 JP 2004-288893 A

  The present invention has been made in view of the above problems and situations, and the solution is to have sufficient flame resistance, high gas barrier performance, UV cutability, and excellent water resistance as a device element film, It is to provide a multifunctional film having light extraction / capturing properties and to provide an organic element device using the same.

  The above object of the present invention can be achieved by the following configuration.

(1)
A gas barrier film having a gas barrier layer formed on one surface of a flame retardant substrate by subjecting a coating film of a polysilazane-containing liquid to irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less, the gas barrier layer and Has a UV cut layer on the opposite surface, and the difference in refractive index between the UV cut layer and the flame retardant substrate is from 0.01 to 0.20.

(2)
The gas barrier film according to (1), wherein the UV cut layer contains an ultraviolet curable resin and an inorganic UV absorber.

(3)
The gas barrier film according to (1) or (2), wherein a layer having a refractive index lower than that of the UV cut layer and made of a fluororesin is laminated on the UV cut layer.

( 4 )
An organic element device using the gas barrier film according to any one of (1) to ( 3 ).

  According to the present invention, it is possible to provide a multi-functional flame-retardant gas barrier film excellent in water resistance and light extraction / capturing property as a film for a device element in addition to flame retardancy, high gas barrier performance, and high UV cut performance. . Moreover, the organic element device using the same can be provided.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  As a result of intensive studies in view of the above problems, the present inventor has a layer having a UV-cut property on one side of the flame-retardant substrate (hereinafter also referred to as a UV-cut layer) and a gas barrier layer on the other side. By controlling the refractive index of the base material and the UV cut layer, it is possible to realize a multifunctional film excellent in water resistance and light extraction / capturing property as a device element film with high gas barrier properties and UV cut properties It is as soon as it has been found and can be achieved.

  The reason why the effect of the present invention can be obtained by the configuration of the present invention is unknown, but the UV coating layer and the gas barrier layer are applied to each layer of the base material on the flame-retardant base material. By sharing the function, it is considered that the bleeding out (water resistance) of the flame retardant of the base material can be suppressed and each function can be sufficiently exhibited. Furthermore, by adopting an inorganic UV absorber for the UV cut layer, it is possible to adjust the refractive index of the UV cut layer, and by controlling the difference in refractive index from a predetermined substrate, the UV cut property and light extraction / It is possible to achieve both uptake properties, and it is considered that the film exhibits a sufficient function as an organic element device film for outdoor use.

  It is not clear why this range is an appropriate region. However, in order to achieve the object of the present invention, the difference in the refractive index between the layer having UV-cutting property and the flame-retardant substrate is required. It needs to be 0.01-0.20.

  In the above, the flame retardancy level in the present invention is preferably VTM-1 or less, particularly preferably VTM-0 or less, in the UL standard 94 vertical test standardized by the United States Fire Insurance Company Association.

In the present invention, the gas barrier property means that the water vapor permeability (60 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10. ⁻³ g / (m ² · 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1.01325 × 10 ⁵ Pa).

  Furthermore, in the said UV cut layer, a UV absorber may be used independently and may be used in combination of 2 or more type. The content in the UV cut layer is not particularly limited as long as the desired UV cut property and refractive index difference can be obtained. From the viewpoint of transparency and smoothness in addition to the above UV cut property and refractive index control, it is 0. The range of 1-50 mass%, preferably 1-20 mass% is preferred.

  The thickness of the UV cut layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. If it is smaller than 1 μm, the effect may be insufficient and may not be preferable.

  The refractive index was measured by the following method.

  Refractive index measurement was performed using an Abbe refractometer-4T (manufactured by Atago Co., Ltd.) using a multi-wavelength light source.

[Gas barrier layer]
At least one surface of the flame-retardant film according to the present invention has a gas barrier layer formed by subjecting a coating film of a polysilazane-containing liquid to a vacuum ultraviolet light having a wavelength of 200 nm or less . The gas barrier layer according to the present invention mainly refers to a layer having a high gas barrier property against water vapor and oxygen. This gas barrier layer is intended to prevent deterioration of the resin base material against high humidity and various functional elements protected by the resin base material.

  As the gas barrier layer, a single layer or a plurality of similar films may be stacked, and by stacking a plurality of layers, the gas barrier property can be further improved.

The gas barrier film of the present invention is a silicon oxide such as silicon dioxide formed by subjecting at least one surface of a base material to a coating film of a polysilazane-containing liquid that is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less. a gas barrier film having a gas barrier layer made of nitride silicon compound.

  The silicon oxide or silicon oxynitride compound for forming the gas barrier layer of silicon oxide or silicon oxynitride compound is supplied as a gas as in a CVD method (Chemical Vapor Deposition). However, it is possible to form a more uniform and smooth gas barrier layer when applied to the surface of the barrier film substrate. It is well known that in the case of a CVD method or the like, a foreign material called unnecessary particles is generated in the gas phase simultaneously with the step of depositing the source material having increased reactivity in the gas phase on the substrate surface. However, it is possible to suppress the generation of these particles by preventing the raw material from being present in the gas phase reaction space.

<Coating film of polysilazane-containing liquid>
The coating film of the polysilazane-containing liquid is preferably applied with a coating liquid containing at least one polysilazane compound on the substrate.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll 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 coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and includes SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _{y made of} Si—N, Si—H, N—H, or the like. Such as a ceramic precursor inorganic polymer.

  In order not to damage the film base material, as shown in JP-A-8-112879, a material represented by the following general formula 1 that is ceramicized at a relatively low temperature and modified to silica is used. Is good.

In the formula, each of R ¹ , R ² , and R ³ independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like.

In the present invention, perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferable from the viewpoint of denseness as a gas barrier film to be obtained.

  On the other hand, 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. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The 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 marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane of the above general formula 1 with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), a glycidol obtained by reacting glycidol Addition polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting metal carboxylate (special Kaihei 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles ( JP-A-7- JP), etc. 96986 can be mentioned.

  As an organic solvent for preparing a liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specific examples include hydrocarbons 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. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  The organic polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, especially a methyl group having the smallest molecular weight, the adhesion to the base material can be improved, and the hard and brittle silica film can be toughened, and even if the film thickness is increased, cracks are not generated. Occurrence is suppressed.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd.

<Polysilazane film formation process>
The coating film of the polysilazane-containing liquid preferably has moisture removed before or during the modification treatment. Therefore, it is preferable to divide into the 1st process for the purpose of removing the solvent in a polysilazane film | membrane, and the 2nd process for the purpose of removing the water | moisture content in the polysilazane film | membrane following it.

  In the first step, the drying conditions for mainly removing the solvent can be appropriately determined by a method such as heat treatment, but the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably high from the viewpoint of rapid treatment, but the temperature and treatment time can be determined in consideration of thermal damage to the resin substrate. For example, when a PET substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and the thermal damage to the substrate is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

  The second step is a step for removing moisture in the polysilazane film, and the method for removing moisture is preferably in a form maintained in a low humidity environment. Since the humidity in the low humidity environment varies depending on the temperature, a preferable form of the relationship between the temperature and the humidity is indicated by the definition of the dew point temperature. A preferable dew point temperature is 4 degrees or less (temperature 25 degrees / humidity 25%), a more preferable dew point temperature is -8 degrees (temperature 25 degrees / humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 degrees / humidity 1%). ) −31 degrees or less, and the maintained time varies depending on the thickness of the polysilazane film. Under the condition of a polysilazane film thickness of 1 μm or less, the preferable dew point temperature is −8 ° C. or less, and the maintained time is 5 minutes or more. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 degrees or less. The treatment time can be selected from 5 minutes to 120 minutes under conditions for removing moisture. The first process and the second process can be distinguished by changing the dew point, and can be classified by changing the dew point of the process environment by 10 degrees or more.

  The polysilazane film is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

<Water content of polysilazane film>
The water content of the polysilazane film can be detected by the following analysis method.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min
The water content in the polysilazane film in the present invention is defined as a value obtained by dividing the water content obtained by the above analytical method by the volume of the polysilazane film, and preferably 0.1% in a state where moisture is removed by the second step. % Or less. A more preferable moisture content is 0.01% or less (below the detection limit).

  This is a preferred mode for promoting the dehydration reaction of the polysilazane film converted to silanol by removing water before or during the modification treatment as in the present invention.

(Modification process)
In the present invention, the modification treatment is a treatment in which a coating film containing polysilazane, which is a ceramic precursor inorganic polymer, is irradiated with vacuum ultraviolet light having a wavelength of 200 nm or less to be converted into a silicon oxide such as silicon dioxide or a silicon oxynitride compound. Say.

(UV irradiation treatment)
In the present invention, as a modification treatment method, treatment by irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less is performed . Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and it is possible to produce silicon oxide films or silicon oxynitride films that have high density and insulation at low temperatures. It is.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  Further, any commonly used ultraviolet ray generator can be used.

  In the present invention, “ultraviolet rays” generally refers to electromagnetic waves having a wavelength of 10 to 400 nm, but in the case of ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described below, preferably 210 to 210. An ultraviolet ray of 350 nm is used.

  In the irradiation with ultraviolet rays, the irradiation intensity and / or the irradiation time should be set within a range where the substrate carrying the coating film to be irradiated is not damaged.

For example, when a plastic film is used as the substrate, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ^2. The distance between the base material and the lamp is set so that the irradiation becomes 0.1 seconds to 10 minutes.

  In general, when the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the substrate is damaged in the case of a plastic film or the like, for example, the substrate is deformed or its strength is deteriorated. However, in the case of a film having high heat resistance such as polyimide or a substrate such as metal, processing at a higher temperature is possible. Therefore, there is no general upper limit to the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generation methods include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. Also, when irradiating the polysilazane coating film with the generated UV light, the UV light from the source is reflected on the reflector and then applied to the coating film in order to achieve uniform irradiation to improve efficiency. Is desirable.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a substrate (eg, silicon wafer) having a polysilazane coating film on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet light source. The ultraviolet baking furnace itself is generally known, and for example, it is possible to use those manufactured by I-Graphics Co., Ltd. In addition, when the substrate having a polysilazane coating film on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in a drying zone having the ultraviolet ray generation source as described above while being conveyed. Can be The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate to be applied and the coating composition.

<Vacuum UV irradiation treatment; Excimer irradiation treatment>
In the present invention, a treatment by vacuum ultraviolet irradiation is performed as a modification treatment method. The treatment with 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 bonds of atoms are only photons called photon processes. 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.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

1. Excimer light is laser light using a rare gas excimer or a hetero excimer as an operating medium. Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded to form no molecule, they are called inert gases. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

  Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric) in a similar very thin discharge called micro discharge, the electric charge accumulates on the dielectric surface, and the micro discharge disappears. This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge can be used in addition to dielectric barrier discharge.

  Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through in order to extract light to the outside in order to discharge in the entire discharge space. Must. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are arranged in close contact, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by connecting both ends of the inner and outer tubes, it is more likely to be damaged during handling and transportation than a thin tube lamp.

  The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As for the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, radical oxygen atomic species and ozone can be generated at a high concentration with a small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, light having a long wavelength that causes a temperature rise due to light is not emitted, and energy is irradiated at a single wavelength in the ultraviolet region, so that the rise in the surface temperature of the object to be fired is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  The film density mentioned here is measured by an X-ray reflectivity measurement method. Specifically, the X-ray generation source is operated at 50 kV-300 mA with copper as a target. X-rays monochromatized with a multilayer mirror and a Ge (111) channel cut monochromator are used. The measurement was performed using the software ATX-Crystal Guide Ver. 6.5.3.4, halved, after alignment adjustment, 2θ / ω = 0 ° to 1 ° from 0.002 ° / step to 0.05 ° / min. Scan with. After measuring the reflectance curve under the above measurement conditions, GXRR Ver. 2.1.0.0 Can be determined using analysis software.

<Surface roughness: smoothness>
The surface roughness (Ra) of the gas barrier layer on the modification treatment side is preferably 2 nm or less, and more preferably 1 nm or less. When the surface roughness is in the above range, when used as a resin base material for organic element devices, the energy conversion efficiency is improved by improving the light transmission efficiency with a smooth film surface with few irregularities and reducing the inter-electrode leakage current. Is preferable. The surface roughness (Ra) of the gas barrier layer can be measured by the following method.

Surface roughness measurement method; AFM measurement:
The surface roughness is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus with a minimum tip radius. This is a roughness related to the amplitude of fine irregularities measured by a stylus many times in a section whose measurement direction is several tens of μm.

[Flame retardant substrate]
The flame retardant substrate of the present invention is a substrate having transparency and flame retardancy. In the present invention, the gas barrier film or the organic element device using the same can be made of a flame retardant substrate, thereby having high flame resistance.

  Examples of the flame retardant substrate used in the present invention include a film made of a flame retardant polymer material, a film kneaded with a flame retardant, and a film bonded with a flame retardant adhesive.

  Resin materials as films made of flame retardant polymer materials include fluororesins (PTFE, ETFE, PCTFE, FEP), polyetherimide, polyamideimide, polyimide, polyphenylene sulfide, polyethersulfone, polyaramid, polysulfone, polysulfone. Examples include ether ether ketone. Even if these are used after being formed into a film alone, or used as a laminated film with a resin material that does not have flame retardancy, they can be used after being kneaded with a resin material that does not have flame retardancy and formed into a film. However, any method may be used as long as flame retardancy is secured.

  A film in which a flame retardant is kneaded can be added by adding and kneading a flame retardant as a masterbatch to a resin during film formation on a non-flame retardant substrate. As flame retardants, phosphorus, phosphorus + halogen, chlorine, bromine, ammonium hydroxide, magnesium hydroxide, antimony, guanidine, zirconium, zinc borate, silicone, nitrogen, low melting glass, There are nanocomposite systems, and one or more of these can be arbitrarily used. Non-flammable substrates include, for example, methacrylate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, polyether ether. Examples of the resin film include ketone, polysulfone, polyethersulfone, polyimide, and polyetherimide, and a resin film obtained by laminating two or more layers of the resin. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.

  A film or the like bonded with a flame retardant adhesive can be produced by bonding the above flame retardant base material with an adhesive having the flame retardant added thereto with a laminator such as heat or vacuum. Adhesives include acrylic, urethane, olefin, cellulose, ethylene-vinyl acetate, epoxy, vinyl chloride, silicone, isocyanate, cyanoacrylate, phenol, polyamide, polyimide, polybutyral System, melamine resin system, and the like, which can be used by adding the flame retardant to them.

  The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  The support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, a transparent gas barrier film can be obtained, and thus a transparent substrate such as an organic EL element can be obtained. It is.

  In addition, the support using the above-described resins or the like may be an unstretched film or a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.

  The support used in the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  In addition, the support used in the present invention may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability. It is preferable that the relaxation treatment is performed in a process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature of 80 to 200 ° C, more preferably a treatment temperature of 100 to 180 ° C. Moreover, it is preferable that the relaxation rate is in the range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is 2 to 6%. The relaxed support is subjected to the following off-line heat treatment to improve heat resistance and further improve dimensional stability. Although it does not specifically limit as a method of off-line heat processing, For example, the method of conveying by the roll conveyance method by a some roll group, the air conveyance etc. which blow an air on a film and levitate | float (one side of a film surface from heating air) Or, a method of spraying on both surfaces), a method of using radiant heat from an infrared heater, a method of hanging the film by its own weight, and a method of conveying such as winding below. The conveyance tension of the heat treatment is made as low as possible to promote thermal shrinkage, thereby providing a support with good dimensional stability. As the processing temperature, a temperature range of Tg + 50 to Tg + 150 ° C. is preferable.

The support of the present invention is preferably coated with an undercoat layer coating solution inline on one side or both sides in the film forming process. In the present invention, undercoating during the film forming process is referred to as in-line undercoating. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating. The coating amount of the undercoat layer is preferably about 0.01 to ² g / m ² (dry state).

  Further, since the support of the present invention is used outdoors, a film having hydrolysis resistance can be used. For example, using the technology for increasing the intrinsic viscosity of a film disclosed in Japanese Patent Application Laid-Open No. 2007-70430 or the technology for suppressing the terminal carboxylic acid of polyester in the film disclosed in Japanese Patent Application Laid-Open No. 2007-204538, the hydrolysis resistance is improved. can do.

[UV cut layer]
In the present invention, the UV cut layer is on the opposite side of the gas barrier layer. Since the above layer is on the opposite side of the gas barrier layer, the gas barrier function and the UV cut function can be efficiently separated, effectively suppressing yellowing due to UV absorption of the substrate and reduction in elastic modulus due to hydrolysis. It is effective as a multifunctional gas barrier film.

  The UV cut layer in the present invention is basically composed of a combination of a resin material and a UV absorber. In particular, from the viewpoint of refractive index control, a combination of an ultraviolet curable resin and an inorganic UV absorber is preferable.

(Refractive index control)
In the present invention, it is necessary that the difference in refractive index between the layer having UV cut property and the flame retardant substrate is 0.01 to 0.20. By making the refractive index difference within the above range, it is possible to suppress internal scattering between layers, and it is easy to emit internal light to the outside (light extraction) at the time of organic device device, or to easily incorporate external light into the light (light Capture).

  As a method for controlling the difference in refractive index, the resin material and configuration of the base material and the UV cut layer are selected, and the filler and additives to be added, particularly in the UV cut layer, are adjusted conveniently by using the following inorganic UV absorbers. I can.

(Resin material)
As the resin material in the present invention, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin can be used. However, since hardness, smoothness, and the like are necessary, the ultraviolet curable resin, the electron beam are used. It is preferable to use a curable resin, and an ultraviolet curable resin is particularly preferable.

  The ultraviolet curable resin can be used without particular limitation as long as it forms a transparent resin composition by curing, and examples thereof include silicone resins, epoxy resins, vinyl ester resins, acrylic resins, and allyl ester resins. . Particularly preferably, an acrylic resin can be used from the viewpoints of hardness, smoothness, and transparency.

  Examples of the acrylic resin composition include acrylate compounds having a radical reactive unsaturated compound, mercapto compounds having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate and the like. What dissolved the polyfunctional acrylate monomer etc. are mentioned. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  As a photoinitiator, a well-known thing can be used and it can be used by 1 type, or 2 or more types of combination.

  From the viewpoint of hardness, smoothness, and transparency, the acrylic resin in the present invention is a reactive silica particle in which a photosensitive group having photopolymerization reactivity is introduced on the surface as described in WO2008-035669 ( In the following, it is preferable to simply include “reactive silica particles”. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. In addition, a polymerizable unsaturated group-modified hydrolyzable silane reacts with a silica particle that forms a silyloxy group and is chemically bonded to the silica particle by a hydrolysis reaction of the hydrolyzable silyl group. Can be used as conductive silica particles. Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle diameter in such a range, transparency, smoothness, and hardness can be satisfied in a well-balanced manner.

  Moreover, a fluorine-containing vinyl monomer can also be used for the acrylic resin of this invention at the point which can adjust a refractive index. Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (trade name) And R-2020 (trade name, manufactured by Daikin) and the like, and fully or partially fluorinated vinyl ethers.

(UV absorber)
As the UV absorber in the present invention, inorganic particles are preferable from the viewpoint of weather resistance.

  Inorganic particles include titanium dioxide, zinc oxide, cerium oxide, hybrid inorganic powder obtained by complexing titanium dioxide fine particles with iron oxide, and hybrid obtained by coating the surface of cerium oxide fine particles with amorphous silica. An inorganic powder etc. are mentioned. The particle size of the UV absorber is preferably 0.1 μm or less from the viewpoint of transparency and smoothness.

  On the other hand, examples of organic UV absorbers include salicylates, benzophenones, benzotriazoles, and substituted acrylonitriles. The organic system is useful because it improves weather resistance when used in combination with a light stabilizer. Examples of the light stabilizer include materials such as hindered amines. The said UV absorber may be used independently and may be used in combination of 2 or more type. Although there is no restriction | limiting in particular as content in a UV cut layer, From the point of transparency and smoothness, 0.1-50 mass%, Preferably the range of 1-20 mass% is preferable.

  The thickness of the UV cut layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. If it is smaller than 1 μm, the hardness is insufficient and is not preferable. On the other hand, if it is larger than 10 μm, the smooth layer, transparency and the like deteriorate, which is not preferable.

  The method for forming the UV cut layer is not particularly limited, but it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  As a method of irradiating ultraviolet rays, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like, or a scanning type or a curtain type are used. It can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from the electron beam accelerator.

  In the formation of the UV cut layer, additives such as an antioxidant, a plasticizer, a matting agent, and a thermoplastic resin can be added to the above-described resin as necessary. Moreover, as a solvent used when forming a smooth layer using the coating liquid which melt | dissolved or disperse | distributed resin in the solvent, a well-known thing can be used.

[Fluorine resin layer]
In the present invention, it is preferable that a layer having a refractive index lower than that of the UV cut layer and made of a fluororesin is laminated on the UV cut layer. With the above configuration, not only the water resistance can be improved, but also the light extraction / capture can be improved.

  Adjustment of the refractive index can be conveniently made with a resin other than fluorine, a filler, an additive, or the like.

  In the present invention, the layer composed of the fluororesin is preferably composed of 50% or more of the fluororesin. Particularly preferably, it is 70% or more. If it is less than 50%, the improvement in the performance by the fluororesin becomes small, which is not preferable. The constitution of the fluororesin may be a coating layer or a sheet.

  Examples of the composition of the fluororesin include ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and polytrifluorochloroethylene. Can be mentioned.

  The thickness of the fluororesin layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. If it is smaller than 1 μm, the hardness is insufficient and is not preferable. On the other hand, when it is larger than 10 μm, the transparency and the like deteriorate, which is not preferable.

[Surface embossing]
In the present invention, in order to improve the light extraction / light capture efficiency, fine unevenness can be provided on the surface of the UV cut layer or the fluororesin layer which is the outermost surface. As a method for providing fine irregularities on the surface, it is preferable to perform uniform embossing with a mold or the like because light scattering efficiency is improved. For example, when coating and forming, solidify while coating the coating film with a mold film having unevenness, or press a molding means such as a molding roll to the formed coating film while heating as necessary. Or a transfer sheet is prepared by applying a UV cut layer or a fluororesin layer on a peelable substrate having unevenness on the release surface, and transferring using the transfer sheet. Preferably, when the UV cut layer or the fluororesin layer is made of metal or the like, it is preferable to use an emboss plate or an emboss roll in terms of production efficiency and uniform abrupt formation.

  The shape of the unevenness may be either a mountain shape or a half moon shape, and the shape can be controlled by combining two or more mountain shapes. As for the degree of surface irregularities, the surface roughness is preferably 0.01 to 1.60 μm, particularly preferably 0.1 to 0.5 μm.

[Organic device]
The gas barrier film of the present invention can be used as a film for organic element devices. Examples of the organic element device include an organic EL element and an organic photoelectric conversion element. The configuration and details of using the gas barrier film of the present invention for an organic EL device and an organic photoelectric conversion device are described below.

(Organic EL)
Subsequently, although embodiment of the organic EL element which is an example of the organic element device of this invention is described in detail, the content described below is a representative example of the embodiment of this invention, and is not limited to these content.

<Organic EL device>
Preferred specific examples of the layer structure of the organic EL layer (hereinafter also referred to as organic EL element) are shown below.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode Here, in order for the light generated in the light emitting layer to be emitted to the outside, it is necessary that at least one of the anode and the cathode is transparent. In the method, it is preferable to use the transparent conductive layer mainly as an anode.

  The light emitting layer preferably contains at least two kinds of light emitting materials having different emission colors, and a single layer or a light emitting layer unit composed of a plurality of light emitting layers may be formed. The hole transport layer also includes a hole injection layer and an electron blocking layer.

(Transparent conductive layer)
As the transparent conductive layer in the organic EL device of the present invention, a material having a work function (4 eV or more) of a metal, an alloy, an electrically conductive compound and a mixture thereof as an electrode material for forming the transparent conductive layer is preferably used. . Specific examples of such electrode substances include metals such as Au, and conductive light-transmitting materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, a material such as IDIXO (In ₂ O ₃ —ZnO) that can form an amorphous light-transmitting conductive film may be used. In the present invention, the transparent conductive layer is preferably used as an anode. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film forming methods, such as a printing system and a coating system, can also be used. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 50 to 200 nm.

  Moreover, a metal nanowire can also be used for this transparent conductive layer. In the case of using metal nanowires, in order to form a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 to 500 μm. It is preferable that it is 3-300 micrometers especially. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  The metal composition of the metal nanowire is not particularly limited, and can be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, Osmium etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity.

  In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire contains two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire may have the same metal composition.

  As a manufacturing method of Ag nanowire, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in water, and since silver has the highest conductivity in metals, it can be preferably applied as a method for producing metal nanowires. it can.

(Light emitting layer)
The light-emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light-emitting portion is the light-emitting layer even in the light-emitting layer. It may be an interface with an adjacent layer.

  As a light emitting layer, if the light emitting material contained satisfies the said requirements, there will be no restriction | limiting in particular in the structure. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. Moreover, it is preferable to have a non-light emitting intermediate | middle layer between each light emitting layer.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably 30 nm or less because a lower driving voltage can be obtained. Note that the total film thickness of the light emitting layer is a film thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers.

  The thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, more preferably adjusted to a range of 1 to 20 nm. There is no particular limitation on the relationship between the film thicknesses of the blue, green and red light emitting layers.

  For the production of the light emitting layer, a light emitting material or a host compound, which will be described later, is formed by forming a film by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, or the like. it can.

  A plurality of light emitting materials may be mixed in each light emitting layer, and a phosphorescent light emitting material and a fluorescent light emitting material may be mixed and used in the same light emitting layer.

  As a structure of the light emitting layer, it is preferable to contain a host compound and a light emitting material (also referred to as a light emitting dopant compound) and emit light from the light emitting material.

  As the host compound contained in the light emitting layer of the organic EL device, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, it becomes possible to mix different light emission by using multiple types of luminescent material mentioned later, and can thereby obtain arbitrary luminescent colors.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

  As the known host compound, 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. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  Specific examples of known host compounds include compounds described in the following documents. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Next, the light emitting material will be described.

  As the light-emitting material, a fluorescent compound or a phosphorescent material (also referred to as a phosphorescent compound or a phosphorescent compound) can be used.

  A phosphorescent material is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0.01 or more at 25 ° C. However, the preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence 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. The phosphorescence quantum yield in a solution can be measured using various solvents. However, when a phosphorescent material is used in the present invention, the phosphorescence quantum yield (0.01 or more) is achieved in any solvent. Just do it.

  There are two types of light emission principles of phosphorescent materials. One is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the host compound, and this energy is transferred to the phosphorescent material. The energy transfer type is to obtain light emission from the phosphorescent light emitting material, and the other is that the phosphorescent light emitting material becomes a carrier trap, and carrier recombination occurs on the phosphorescent light emitting material, and light emission from the phosphorescent light emitting material is obtained. In any case, the excited state energy of the phosphorescent light emitting material is required to be lower than the excited state energy of the host compound.

  The phosphorescent light-emitting material can be appropriately selected from known materials used for the light-emitting layer of the organic EL element, and is preferably a complex compound containing a group 8-10 metal in the periodic table of elements. More preferably, an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.

  A fluorescent substance can also be used for the organic EL element. Representative examples of fluorescent emitters (fluorescent dopants) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes. Examples thereof include dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Conventionally known dopants can also be used in the present invention. For example, WO 00/70655, JP-A 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060, 2001-313178, 2002-302671, 2001-345183, 2002 No. 324679, International Publication No. 02/15645, JP 2002-332291 A, 2002-50484, 2002-332292, 2002-83684, JP 2002-540572 A JP, 2002-11 No. 978, No. 2002-338588, No. 2002-170684, No. 2002-352960, WO 01/93642, JP-A No. 2002-50483, No. 2002-1000047. JP 2002-173674, 2002-359082, 2002-17584, 2002-363552, 2002-184582, 2003-7469, JP 2002-525808, JP 2003-7471 A, JP 2002-525833 A, JP 2003-31366 A, 2002-226495 A, 2002-234894 A, 2002-23076 A, 2002-241751 Gazette, 200 -319779, 2001-319780, 2002-62824, 2002-1000047, 2002-203679, 2002-343572, 2002-203678, and the like. .

  In the present invention, at least one light emitting layer may contain two or more kinds of light emitting materials, and the concentration ratio of the light emitting materials in the light emitting layer may vary in the thickness direction of the light emitting layer.

(Middle layer)
A case where a non-light emitting intermediate layer (also referred to as an undoped region or the like) is provided between the light emitting layers will be described.

  The non-light emitting intermediate layer is a layer provided between the light emitting layers in the case of having a plurality of light emitting layers. The film thickness of the non-light emitting intermediate layer is preferably in the range of 1 to 20 nm, and further in the range of 3 to 10 nm suppresses interaction such as energy transfer between adjacent light emitting layers, and the current of the device This is preferable because a large load is not applied to the voltage characteristics.

  The material used for the non-light emitting intermediate layer may be the same as or different from the host compound of the light emitting layer, but may be the same as the host material of at least one of the adjacent light emitting layers. preferable.

  The non-light-emitting intermediate layer may contain a non-light-emitting layer, a compound common to each light-emitting layer (for example, a host compound), and each common host material (where a common host material is used) In the case where the physicochemical characteristics such as phosphorescence emission energy and glass transition point are the same, or the molecular structure of the host compound is the same, etc.) The barrier is reduced, and the effect of easily maintaining the injection balance of holes and electrons even when the voltage (current) is changed can be obtained. Furthermore, by using a host material having the same physical characteristics or the same molecular structure as the host compound contained in each light-emitting layer in the undoped light-emitting layer, device fabrication, which is a major problem in conventional organic EL device fabrication, is achieved. Complexity can also be eliminated.

  Since the host material is responsible for carrier transportation, a material having carrier transportation ability is preferable. Carrier mobility is used as a physical property representing carrier transport ability, but the carrier mobility of an organic material generally depends on the electric field strength. Since a material having a high electric field strength dependency easily breaks the balance between injection and transport of holes and electrons, it is preferable to use a material having a low electric field strength dependency of mobility for the intermediate layer material and the host material.

  On the other hand, in order to optimally adjust the injection balance of holes and electrons, it is also preferable that the non-light emitting intermediate layer functions as a blocking layer described later, that is, a hole blocking layer and an electron blocking layer. Can be mentioned.

(Injection layer: electron injection layer, hole injection layer)
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

(Blocking layer: hole blocking layer, electron blocking layer)
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has a function of an electron transport layer and is composed of a hole blocking material having a function of transporting electrons and having a remarkably small ability to transport holes, while transporting electrons. By blocking holes, the recombination probability of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer, in a broad sense, has a function of a hole transport layer, and is made of a material having a function of transporting holes while having a remarkably small ability to transport electrons, while transporting holes. By blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transport layer is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer 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. For example, 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.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of 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-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, 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. In addition, 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.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 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 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 ink jet method, or an LB method. Can do. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  It is preferable to use such a hole transport layer having a high p property because an element with lower power consumption can be manufactured.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivative, 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 can also be used as an electron transport material. Furthermore, 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.

In addition, 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., and the central metals of these metal complexes are In, Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as electron transport materials. In addition, 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 electron transporting material. Further, the distyrylpyrazine derivatives exemplified as the material of the light emitting layer can also be used as the electron transport material, and inorganic semiconductors such as n-type-Si and n-type-SiC can be used as well as the hole injection layer and the hole transport layer. It can be used as an electron transport material.

  The electron transport layer can be formed by thinning the electron transport 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. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. 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.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be manufactured.

(Counter electrode)
The counter electrode is an electrode facing the transparent conductive layer. In the present invention, since the transparent conductive layer is mainly used as an anode, the following cathode can be used as the counter electrode. As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal with a film thickness of 1 nm-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing an electroconductive transparent material on it, By applying this, An element in which both the anode and the cathode are transmissive can be manufactured.

[Production method of organic EL]
The organic EL of the present invention can be produced by sequentially forming a light extraction layer, a transparent conductive layer, an organic electroluminescence layer, and a counter electrode on a transparent substrate.

(Formation of transparent conductive layer)
A transparent conductive layer can be formed on a transparent substrate using a desired electrode material. For example, when ITO (indium oxide added with tin) is used as the electrode material, the transparent conductive layer can be formed by a method such as vapor deposition or sputtering. In addition, a transparent conductive layer can be formed from a material containing metal nanowires, a conductive polymer, or a transparent conductive metal oxide by a liquid phase film forming method such as a coating method or a printing method.

  From the viewpoint of improving productivity, improving electrode quality such as smoothness and uniformity, and reducing environmental impact, it is possible to form a transparent conductive layer containing metal nanowires by a liquid phase film-forming method such as a coating method or a printing method. preferable. As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method Etc. can be used. As the 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, and the like can be used. In addition, as necessary, physical surface treatment such as corona discharge treatment or plasma discharge treatment can be applied to the surface of the releasable substrate as a preliminary treatment for improving the adhesion and coating properties.

(Formation of organic electroluminescence layer)
A layer formed between the transparent conductive layer and the cathode, consisting of all or part of the anode buffer layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, and cathode buffer layer is called an organic electroluminescence layer. . As an example of a method for producing this organic electroluminescence layer, a method for producing an organic electroluminescence layer comprising a hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer will be described.

  An organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are constituent materials of the organic EL layer, is formed on the transparent base material on which the transparent conductive layer is formed.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When employing a vapor deposition method for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.

(Formation of cathode)
After forming the organic electroluminescence layer, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm. Is provided.

  Through the above steps, an organic electroluminescence layer is obtained. The organic electroluminescence layer is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor liquid crystal display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

(Organic light conversion element)
Although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to this. There is no restriction | limiting in particular as an organic photoelectric conversion element, The electric power generation layer (The layer which mixed the p-type semiconductor and the n-type semiconductor, the bulk heterojunction layer, and i layer) sandwiched between the anode and the cathode at least 1 is provided. Any element that has more than one layer and generates current when irradiated with light may be used.

The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.
(I) anode / power generation layer / cathode (ii) anode / hole transport layer / power generation layer / cathode (iii) anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first light emitting layer / electron transport layer / intermediate electrode / hole transport layer / second light emitting layer Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, which are substantially two layers and heterojunction. Alternatively, a bulk heterojunction that is in a mixed state in one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like the organic EL element, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer. Therefore, the structure having them ((ii), ( iii)) is preferred. Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (iv). It may be a configuration (also referred to as a pin configuration). Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

  Instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 1 for the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), a hole transport layer 14 and an electron transport layer 16 are respectively formed on a pair of comb-like electrodes. The back contact type organic photoelectric conversion element can be configured such that the photoelectric conversion unit 15 is disposed thereon.

  Furthermore, the preferable aspect of the organic photoelectric conversion element which concerns on detailed this invention is demonstrated below.

  FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element. In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a power generation layer 14 of a bulk heterojunction layer, an electron transport layer 18, and a cathode 13 sequentially stacked on one surface of a substrate 11. Has been.

  The substrate 11 is a member that holds the anode 12, the power generation layer 14, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction organic photoelectric conversion element 10 may be configured by forming the anode 12 and the cathode 13 on both surfaces of the power generation layer 14.

  The power generation layer 14 is a layer that converts light energy into electrical energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  Although not shown in FIG. 1, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.

  As a more preferable configuration, the power generation layer 14 has a so-called p-i-n three-layer configuration (FIG. 2). A normal bulk heterojunction layer is a single i layer in which a p-type semiconductor material and an n-type semiconductor layer are mixed, but is sandwiched between a p-layer composed of a single p-type semiconductor material and an n-layer composed of a single n-type semiconductor material. As a result, the rectification of holes and electrons becomes higher, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

  Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency).

  FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second power generation layer 16, and then the counter electrode 13 are stacked. By stacking, a tandem structure can be obtained. The second power generation layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first power generation layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. Further, both the first power generation layer 14 ′ and the second power generation layer 16 may have the above-described three-layer structure of pin.

  Below, the material which comprises these layers is described.

(Organic photoelectric conversion element material)
<P-type semiconductor material>
Examples of the p-type semiconductor material used for the power generation layer (bulk heterojunction layer) include various condensed polycyclic aromatic low-molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazethrene, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis (ethylenedithio) tetrathiafur Examples include valene (BEDT-TTF) -perchloric acid complex, and derivatives and precursors thereof.

  Examples of the derivative having the above condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216. A pentacene derivative having a substituent described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  Examples of the conjugated polymer include a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, polythiophene-thienothiophene copolymer, WO2008 / 000664, polythiophene-diketopyrrolopyrrole copolymer, Adv Mater, 2007p4160, polythiophene-thiazolothiazole copolymer, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

  In addition, oligomeric materials instead of polymer materials include thiophene hexamer α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable.

  Further, when the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .

  Examples of such a material include materials that can be insolubilized by coating the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or by applying energy such as heat as described in U.S. Patent Application Publication No. 2003/136964 and Japanese Patent Application Laid-Open No. 2008-16834, etc., the soluble substituent reacts to insolubilize (to form a pigment). ) Materials can be mentioned.

<N-type semiconductor material>
The n-type semiconductor material used in the bulk heterojunction layer is not particularly limited. For example, perfluoro compounds in which a hydrogen atom of a p-type semiconductor is substituted with a fluorine atom, such as fullerene and octaazaporphyrin (perfluoropentacene or perfluorophthalocyanine). ), Naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and other aromatic carboxylic acid anhydrides and polymer compounds containing the imidized compounds thereof be able to.

  However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (˜50 fs) and efficiently are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Some are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61-buty Rick acid-isobutyl ester (PCBiB), [6,6] -phenyl C61-butyric acid-n hexyl ester (PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes such as JP-A 2006-199674, metallocene fullerenes such as JP-A 2008-130889, and cyclics such as US Pat. No. 7,329,709. It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as fullerene having an ether group.

<Hole transport layer and electron block layer>
Since the organic photoelectric conversion element 10 according to the present invention can extract the hole transport layer 17 between the bulk heterojunction layer and the anode, and more efficiently take out the charges generated in the bulk heterojunction layer. It is preferable to have a layer.

  As a material constituting these layers, for example, as the hole transport layer 17, PEDOT such as Stark Vitec Co., Ltd., trade name BaytronP, polyaniline and its doped material, cyan compounds described in WO2006019270, etc. Can be used. Note that the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the anode side. It has an electronic block function. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

<Electron transport layer / hole blocking layer>
In the organic photoelectric conversion element 10 according to the present invention, the electron transport layer 18 is formed between the bulk heterojunction layer and the cathode, so that charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have these layers.

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, a p-type semiconductor material used for a bulk heterojunction layer is used. The electron transport layer having a HOMO level deeper than the HOMO level is provided with a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side. Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

<Other layers>
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

<Transparent electrode (first electrode)>
The transparent electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration. Preferably, the transparent electrode is used as an anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires, and carbon nanotubes can be used.

  Also, a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. A functional polymer can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

<Counter electrode (second electrode)>
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The (average) film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  If a metal material is used as the conductive material of the counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and is absorbed again by the photoelectric conversion layer, and more photoelectric conversion efficiency Is preferable.

  Further, the counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. If it is a thing, a transparent and highly conductive counter electrode can be formed with a coating method, and it is preferable.

  In addition, when the counter electrode side is made light-transmitting, for example, a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound is made thin with an average film thickness of about 1 to 20 nm. Thereafter, a light-transmitting counter electrode can be obtained by providing a film of the conductive light-transmitting material mentioned in the description of the transparent electrode.

<Intermediate electrode>
In addition, the material of the intermediate electrode required in the case of the tandem configuration as in the above (v) (or FIG. 3) is preferably a layer using a compound having both transparency and conductivity. (Such as ITO, AZO, FTO, transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, etc., or layers containing nanoparticles / nanowires, PEDOT: PSS, polyaniline, etc. Or the like can be used.

  In addition, among the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by stacking in an appropriate combination. With such a configuration, a step of forming one layer is omitted. Can be preferable.

<Metal nanowires>
As the conductive fibers, organic fibers or inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used. Metal nanowires are preferable.

  In general, the metal nanowire refers to a linear structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a linear structure having a diameter of nm size.

  As a metal nanowire, in order to form a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 to 500 μm. Particularly preferred is 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  The metal composition of the metal nanowire is not particularly limited, and can be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, Osmium etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire includes two or more kinds of metal elements, for example, the metal composition may be different between the surface and the inside of the metal nanowire, or the entire metal nanowire may have the same metal composition.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in water, and since silver has the highest conductivity in metals, it can be preferably applied as a method for producing metal nanowires. it can.

  In the present invention, the metal nanowires come into contact with each other to form a three-dimensional conductive network, exhibiting high conductivity, and allowing light to pass through the window of the conductive network where no metal nanowire exists. In addition, the power generation from the organic power generation layer can be efficiently performed by the scattering effect of the metal nanowires. If a metal nanowire is installed in the 1st electrode at the side close | similar to an organic electric power generation layer part, since this scattering effect can be utilized more effectively, it is more preferable embodiment.

<Optical function layer>
The organic photoelectric conversion element according to the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it is smaller than this, the effect of diffraction is generated and colored.

  Examples of the light scattering layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

(Film forming method / Surface treatment method)
<Method for forming various layers>
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a vapor deposition method and a coating method (including a cast method and a spin coat method). Among these, examples of the method for forming the bulk heterojunction layer include a vapor deposition method and a coating method (including a casting method and a spin coating method). Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. The coating method is also excellent in production speed.

  Although there is no restriction | limiting in the coating method used in this case, For example, a spin coat method, the casting method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

  After coating, it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption longwave due to crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the material is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

<Patterning>
There is no particular limitation on the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like, and known methods can be applied as appropriate.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or etching or lift-off. Alternatively, the pattern may be formed by transferring a pattern formed on another substrate.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

[Example 1]
(Base material (support))
Support 1
A 50 μm-thick polyester film with easy adhesion processing on both sides, manufactured by Teijin DuPont Films Ltd., KDL86W-50μ was used as the support 1.

Support 2
A flame retardant polycarbonate film having a thickness of 100 μm and a flame retardant added thereto, Asahi Glass Co., Ltd., Lexan FR60 was used as the support 2.

Support 3
A flame-retardant polyester film having a thickness of 100 μm was produced as follows.

  Dimethyl terephthalate and ethylene glycol were mixed at an equivalent ratio of 1: 2, and calcium acetate monohydrate (transesterification reaction catalyst) was added at 0.05 mass% based on the mass of the dimethyl terephthalate, and at 200 ° C. for 180 minutes. Reacted. After completion of the transesterification reaction, 2-carboxyethylmethylphosphinic acid is added to the reaction mixture in an amount of 0.2 equivalents based on dimethyl terephthalate, and then trimethyl phosphate (stabilizer) and antimony trioxide (polymerization catalyst) are added. Each was added to the reaction mixture in an amount of 0.05 mass% and 0.04 mass% based on the mass of the dimethyl terephthalate. The mixture was reacted at 280 ° C. for 180 minutes to obtain a polyester resin having an intrinsic viscosity of 0.640 dl / g. 5 parts by mass of polytetrafluoroethylene (PTFE; flame retardant improver) is added to 100 parts by mass of this polyester resin, and mixed at 285 ° C. using a compounder screw having a rotation speed of 300 rpm to produce a master chip. did.

  The polyester resin and master chip were mixed at a mass ratio of 4: 1. The mixture was melt extruded at 280 ° C. with a normal T-die and cooled with a casting roller at 25 ° C. to produce a sheet. A biaxially stretched polyester film having a thickness of 100 μm, which is stretched in the longitudinal direction at 90 ° C. with a stretching ratio of 3.5 and in the lateral direction at 120 ° C. with a stretching ratio of 3.5 and then heat-set at 220 ° C. Got. The support 3 was prepared by coating the both sides of this film with an adhesive layer of K1531 manufactured by Toyobo Co., Ltd. so that the dry film thickness was 0.1 μm.

Support 4
A polyester resin to which 2-carboxyethylmethylphosphinic acid is not added as a support 3 is prepared, and 2-diphenylphosphinyl hydroquinone (trade name: PPQ manufactured by Hokuko Chemical Co., Ltd.) has a phosphorus element content of 4% by mass when a masterbatch is prepared. A support 4 was prepared in the same manner as the support 3 except that the addition was performed.

(Production of gas barrier film)
The gas barrier film was formed so as to have the layer structure shown in Table 1 while transporting the support (substrate) at a speed of 30 m / min. As the formation order, the gas barrier layer was formed after forming the first layer and the second layer on the opposite side of the gas barrier layer side. The configuration and forming method of each layer are shown below.

BA prevention layer On one side of the support, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied, and after coating with a wire bar so that the (average) film thickness after drying was 4 μm, Curing conditions: 1.0 J / cm ² under air, using a high-pressure mercury lamp, drying conditions: Curing was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer.

(Formation of UV-cutting layer (UV cut layer))
UV cut layer 1: TYN80 (UV curable organic / zinc oxide particle-containing hard coat material, adjusting refractive index to 1.80 by adjusting the amount of zinc oxide and acrylic resin) manufactured by Toyo Ink Co., Ltd. It was. After coating and drying, an average film thickness after coating is applied to the above support with a wire bar, and then using a high-pressure mercury lamp from the substrate side in an air atmosphere, curing conditions: 400 mJ / cm ² Curing was performed, followed by drying conditions; 80 ° C., drying for 3 minutes to form a UV cut layer 1 (UV1) on one side of the support or the first layer on the back as shown in Table 1. .

  UV cut layer 2: The coating liquid of UV cut layer 1 is HALS to TYN55 (UV curable organic / zinc oxide particle-containing hard coat material, the refractive index is adjusted to 1.55 by adjusting the amount of zinc oxide and acrylic resin). 2% of Ciba Tinuvin 292 was added as an agent, and UV cut layer 2 (UV2) was formed at the position shown in Table 1 as UV cut coating solution 2 in the same manner as UV cut layer 1.

  UV cut layer 3: Using UV coating layer 1 coating solution, 5% Ciba Tinuvin 477 as an organic UV absorber is added to folceed 461 (UV curable hard coat material) to form UV cutting coating solution 3 (refraction) In the same manner as in the UV cut layer 1, a UV cut layer 3 (UV3) was formed at the position shown in Table 1.

  UV cut layer 4: 50% of Teka ZD019 (methyl oxide ketone (MEK) dispersion of zinc oxide) as an inorganic UV absorber is added to Mitsubishi Rayon Dianal (acrylic resin) as a coating solution for UV cut layer 1 and UV. As the cut coating solution 4, a UV cut layer 4 (UV4) was formed at the position shown in Table 1 in the same manner as the UV cut layer 1.

  UV cut layer 5: TYN55 and TYT55 (UV hardened organic / titanium oxide particle-containing hard coat material was used and the refractive index was adjusted to 1.55) were mixed 1: 1 with the UV cut layer 1 coating solution. Further, 2% of Ciba Tinuvin 292 was added as a HALS agent (polymer light stabilizer), and the UV-cutting coating solution 5 was formed in the same manner as the UV-cutting layer 1, but at the position shown in Table 1, the UV-cutting layer 5 (UV5 ) Was formed.

  UV cut layer x: The UV cut layer 1 coating solution was not added to TYZ55 (UV hardened organic / zirconia particle-containing hard coat material, refractive index adjusted to 1.55), 2% of Ciba Tinuvin 292 was added as a HALS agent, and a UV cut layer x (UV x) was formed at the position shown in Table 1 as a UV cut coating solution x in the same manner as the UV cut layer 1.

(Formation of fluororesin layer)
Fluororesin layer 1 (coating): coated with Kanto Denka Kogyo FG Clear KD200, applied to the support with a wire bar so that the (average) film thickness after drying was 4 μm, and then dried at 80 ° C. for 3 minutes. As shown in Table 1, the substrate is dried, and an embossed plate having chromic properties on the coated surface and fine irregularities on the surface is stacked so as to be in contact with the fine irregularities, and the fluororesin layer 1 (fluorine coating) is shown in Table 1. And formed on the second layer on the back surface.

(Formation of gas barrier layer)
As shown in Table 1, a gas barrier layer is formed on the BA prevention layer or the UV cut layer under the conditions shown below to produce gas barrier films 1 to 19 (Comparative Examples 1 to 10 and Inventions 11 to 19). did.

(Formation of barrier layer 1)
Gas barrier layer coating solution Perhydropolysilazane (PHPS) 20% by mass dibutyl ether solution AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.
With a wireless bar, coating was performed so that the (average) film thickness after drying was 0.30 μm to obtain a coated sample.

(First step; drying treatment)
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.

(Second step; dehumidification treatment)
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

(Modification A)
The sample subjected to the dehumidification treatment was modified under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

(Modification equipment)
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com
The sample fixed on the operation stage was modified under the following conditions.

(Reforming treatment conditions)
Excimer light intensity 130mW / cm ² (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds (formation of barrier layer 2)
Plasma discharge was performed under the following two-layer configuration and conditions to form a barrier layer 2 having a thickness of about 0.3 μm.

<Mixed gas composition>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Film formation conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 90 ° C
(Formation of second ceramic layer)
<Second ceramic layer mixed gas composition>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
<Second ceramic layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10W / cm ²
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 90 ° C
The refractive index was measured using the Abbe refractometer-4T (manufactured by Atago Co., Ltd.) using a multi-wavelength light source.

(Performance evaluation)
<Flame retardance>
Evaluation was performed according to the above-mentioned UL94 vertical combustion test.

<Heat and humidity resistance (bleed out property)>
The sample after the treatment was evaluated by performing an accelerated treatment for 3000 hours in an 85 ° C. and 85% RH environment simulating severe environmental conditions of heat and humidity.

  The sample was cut into a strip shape having a length of 150 mm and a width of 10 mm. The bleed-out evaluation of the treated sample was evaluated according to the following criteria from the surface whitening state.

A: No whitening B: Whitening of fine spots that can be confirmed with a 100 times magnifier is observed (no problem in practical use)
C: Whitening of minute points that can be visually confirmed is observed D: Whitening of 30% or more can be confirmed by area ratio E: Whitening of the entire surface can be confirmed visually

As is clear from the results shown in Table 1, it was found that Samples 11 to 16, 18 and 19 in the present invention were clearly excellent in flame retardancy and heat and humidity resistance (bleed out). On the other hand, Comparative Examples 1 to 9 have a problem in any of the characteristics, and Comparative Example 10 has no gas barrier effect.

[Example 2]
[Production of organic photoelectric conversion element]
Each of the gas barrier films 1 to 19 produced in Example 1 was deposited with an indium tin oxide (ITO) transparent conductive film of 150 nm on the gas barrier layer side (sheet resistance 10 Ω / □). And wet etching were used to perform patterning to a width of 2 mm to form a first electrode. The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, is applied and dried so that the (average) film thickness is 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. A film was formed.

  Thereafter, the substrate was brought into a nitrogen chamber and manufactured in a nitrogen atmosphere.

  First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Co., Ltd .: 6,6-phenyl-C61-butyric acid methyl ester) are added to 3.0% by mass of chlorobenzene. A liquid mixed at 1: 0.8 was prepared so that the film was filtered (filtered) with a filter so that the (average) film thickness was 100 nm, and allowed to dry at room temperature. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin, so that organic photoelectric conversion elements 1 to 19 having a light receiving portion of 2 × 2 mm size were produced.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), an epoxy-based photocuring is used as a sealing material on the surface provided with the gas barrier layer using the gas barrier film comparative examples 1 to 10 and the present inventions 1 to 9 A mold adhesive was applied. Two gas barrier film comparative examples 1 to 10 and the present inventions 1 to 9 coated with the above adhesives were applied to the organic photoelectric conversion elements corresponding to the comparative examples 1 to 10 and the present inventions 1 to 9 obtained by the method described above. Then, the organic photoelectric conversion elements 1 to 19 (Comparative Examples 1 to 10 and Inventions 1 to 9) are cured by irradiating and curing UV light from one side of the substrate. Produced.

<Evaluation of organic photoelectric conversion device>
<Light capture efficiency>
The light capture efficiency is obtained by irradiating a solar simulator (AM1.5G filter) with light of 100 mW / cm ² intensity on the photoelectric conversion element produced above, and overlaying a mask with an effective area of 4.0 mm ² on the light receiving part. By evaluating the IV characteristics, the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%) were measured for each of the four light receiving portions formed on the same element. The four-point average value of energy conversion efficiency PCE (%) obtained according to the following formula 1 was obtained.
(Formula 1) PCE (%) =
[Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as an initial battery characteristic was measured.

  The result was judged based on the quantum efficiency of the obtained organic EL device 1. The larger the value, the better the external light extraction efficiency.

<< Weather resistance of organic photoelectric conversion elements >>
Using a metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.), the sample surface radiation intensity: 2.16 MJ / m ² or less, black panel temperature 63 ° C., relative humidity : Weather resistance test under conditions of 50% and irradiation time of 500 hours, followed by conversion efficiency remaining rate after accelerated test stored at temperature of 85 ° C and humidity of 85% RH for 3000 hours. Evaluated.

Ratio of conversion efficiency / initial conversion efficiency after acceleration test 5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20%, respectively The evaluation results are shown in Table 2.

  As is clear from the results shown in Table 2, it can be seen that the organic photoelectric conversion element produced using the gas barrier film of the present invention has good light capture efficiency and hardly undergoes performance deterioration even in a harsh environment.

Example 3
(Production of organic EL element)
<Formation of ITO conductive layer>
On the gas barrier layer side of the gas barrier film comparative examples 1 to 10 and the present invention 1 to 9 produced in Example 1, ITO (indium tin oxide) was formed and patterned under the condition of a thickness of 100 nm, and the ITO conductive layer Then, the substrate provided with the ITO conductive layer was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

(Formation of hole injection layer)
On this substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, 30 seconds After forming the film by spin coating, the substrate was dried at a substrate surface temperature of 200 ° C. for 1 hour to provide a hole injection layer having a thickness of 30 nm.

(Formation of hole transport layer)
This substrate was transferred to a glove box having a cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm measured by a measurement method according to JIS B 9920 in a nitrogen atmosphere. A coating solution for a hole transport layer was prepared as follows in a glove box, and applied with a spin coater under conditions of 1500 rpm and 30 seconds. This substrate was dried by heating at a substrate surface temperature of 150 ° C. for 30 minutes to provide a hole transport layer. The film thickness was 20 nm when it apply | coated and measured on the conditions with the board | substrate prepared separately.

<Hole transport layer coating solution>
Monochlorobenzene 100g
Poly-N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine (ADS254BE: manufactured by American Die Source)
0.5g
(Formation of light emitting layer)
Subsequently, the light emitting layer coating liquid was prepared as follows, and it apply | coated on 2000 rpm and the conditions for 30 seconds with the spin coater. Furthermore, it heated at the substrate surface temperature of 120 degreeC for 30 minutes, and provided the light emitting layer. When the coating was performed under the same conditions on a separately prepared substrate and measured, the film thickness was 40 nm. In addition, among the following light emitting layer composition, it was HA which showed the lowest Tg, and it was 132 degreeC.

<Coating solution for light emitting layer>
Butyl acetate 100g
H-A 1.0g
DA 0.11g
DB 0.002g
D-C 0.002g
(Formation of electron transport layer)
Subsequently, the coating liquid for electron carrying layers was prepared as follows, and it apply | coated on the conditions of 1500 rpm and 30 seconds with a spin coater. Furthermore, it heated for 30 minutes at the substrate surface temperature of 120 degreeC, and provided the electron carrying layer. The film thickness was 30 nm when it applied and measured on the conditions prepared with the board | substrate prepared separately.

<Coating liquid for electron transport layer>
2,2,3,3-tetrafluoro-1-propanol 100 g
ET-A 0.75g

(Formation of electron injection layer)
Next, the substrate provided up to the electron transport layer was moved to a vapor deposition unit without being exposed to the atmosphere, and the pressure was reduced to 4 × 10 ⁻⁴ Pa. In addition, potassium fluoride and aluminum were each put in a resistance heating boat made of tantalum and attached to a vapor deposition device.

  First, a resistance heating boat containing potassium fluoride was energized and heated to provide 3 nm of an electron injection layer made of potassium fluoride on the substrate.

(Formation of cathode)
Subsequently, a resistance heating boat containing aluminum was heated by energization, and a cathode having a film thickness of 100 nm made of aluminum was provided at a deposition rate of 1 to 2 nm / second. To 9) were produced.

(Performance evaluation)
<Light extraction efficiency>
With respect to the produced organic EL elements 1 to 19, the external extraction quantum efficiency (%) when a constant current of ^2.5 mA / cm ² was passed was measured under an inert gas atmosphere. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used. The relative value when the quantum efficiency of the organic EL element 1 obtained as described above was set to 100 was obtained. The larger the value, the better the external light extraction efficiency.

<Durability-Life>
A metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.) is used for the produced organic EL element, sample surface radiation intensity: 2.16 MJ / m ² or less, black panel temperature 63 ° C., relative humidity: When the weather resistance test was performed under the conditions of 50% and irradiation time of 500 hours, and then stored at a temperature of 85 ° C. and a humidity of 85% RH for 3000 hours, when driven at a constant current of 10 mA / cm ² , the initial brightness was obtained. On the other hand, the weather resistance against light, heat and humidity was evaluated by the residual ratio of luminance after the acceleration test.

Ratio of luminance / initial luminance after acceleration test 5: 70% or more 4: 50% or more, less than 70% 3: 30% or more, less than 50% 2: 10% or more, less than 30% 1: less than 10%

  As is clear from the results shown in Table 3, it can be seen that the organic EL having the structure defined in the present invention has high light extraction efficiency and excellent weather resistance when used outdoors.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode 13 Counter electrode 14 Photoelectric conversion part (bulk hetero junction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion unit 15 charge recombination layer 16 second photoelectric conversion unit 17 hole transport layer 18 electron transport layer

Claims (4)

A gas barrier film having a gas barrier layer formed on one surface of a flame retardant substrate by subjecting a coating film of a polysilazane-containing liquid to irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less, the gas barrier layer and Has a UV cut layer on the opposite surface, and the difference in refractive index between the UV cut layer and the flame retardant substrate is from 0.01 to 0.20.   The gas barrier film according to claim 1, wherein the UV cut layer contains an ultraviolet curable resin and an inorganic UV absorber.   The gas barrier film according to claim 1, wherein a layer made of a fluororesin and having a refractive index lower than that of the UV cut layer is laminated on the UV cut layer. An organic element device using the gas barrier film according to any one of claims 1 to 3 .

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