JP5761030B2 - Barrier film manufacturing method - Google Patents

Description

  The present invention mainly uses a film having a gas barrier property (hereinafter referred to as a barrier film) and a barrier film, which are used for a display material such as a package such as an electronic device, or a plastic substrate such as an organic EL element, a solar cell, and a liquid crystal. The present invention relates to various device resin substrates and various device elements.

  Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging of articles and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

  Aluminum foil is widely used as a packaging material in such fields, but disposal after use has become a problem, and it is basically opaque and the contents can be confirmed from the outside. In addition, the display material is required to have optical transparency and cannot be applied at all.

  In particular, transparent substrates that are being applied to liquid crystal display elements, solar cells, etc., in recent years, are capable of roll-to-roll production, long-term reliability and shape, in addition to demands for weight reduction and size increase. High demands such as high degree of freedom and the ability to display curved surfaces have been added, and film substrates such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken.

  However, a film substrate such as a transparent plastic has a problem that gas barrier properties are inferior to glass. For example, when used as a substrate for an organic photoelectric conversion element, there is a problem that if a substrate with poor gas barrier properties is used, water vapor or air penetrates and the performance is likely to deteriorate with time.

  In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a barrier film substrate. As a barrier film used for a packaging material or a liquid crystal display element, a film obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) or a film obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). Are known. However, the film formation by vapor deposition has a problem that the film production speed is low and a large-scale and expensive apparatus such as a vacuum apparatus is required, so that the production efficiency is extremely low.

  On the other hand, the following techniques are known as techniques for realizing high gas barrier properties.

Instead of vapor deposition, a method is known in which a gas barrier layer is formed by applying a surface treatment after applying a coating liquid containing polysilazane as a main component (see, for example, Patent Documents 3 and 4). These are techniques for applying a vacuum plasma treatment to a single polysilazane film, but none of these techniques are sufficient for those requiring a high gas barrier layer such as organic photoelectric conversion elements and organic EL elements. Yes, for example, a water vapor transmission rate of 1 × 10 ⁻² g / m ² · day or more is required.

  As a technique for providing a barrier layer with flexibility, the technique of Patent Document 5 is known. In this method, an organic film is inserted between a substrate made of a polymer and a barrier layer made of an inorganic oxide film to form a laminated structure, thereby giving the organic layer stress relaxation ability. However, in this configuration, since the organic layer serving as the stress relaxation layer has a low gas barrier property, the gas barrier property of the entire film did not reach the above target. Further, in order to achieve the above target, a plurality of laminated structures must be constructed, and the productivity is extremely low.

  Further, in this case, a plurality of low affinity interfaces of the organic film and the inorganic film are overlapped, and there is a problem that the strength against bending is low.

  There has been disclosed a method of forming a substrate film that is difficult to crack and has a high gas barrier property by conversion treatment such as vacuum ultraviolet irradiation using polysilazane (see Patent Documents 6 and 7). In Patent Document 6, polysilazane is applied to the surface of a resin film, converted, and a plurality of formed films are laminated. On the other hand, in Patent Document 7, the catalyst is applied to polysilazane and converted. Discloses a method for forming a glass-like transparent coating, and performing these treatments multiple times.

  In any case, a conversion process is performed every time each layer is formed, and a method of repeatedly laminating the same layer is disclosed, but it still does not have sufficient gas barrier properties and durability.

JP-A-2-251429 JP-A-6-124785 JP 2007-237588 A JP 2000-246830 A JP 2009-28949 A JP 2009-255040 A Special table 2009-503157

Accordingly, an object of the present invention is to a child provide extremely high barrier performance can be achieved, and manufacturing method of the barrier fill beam to withstand bending.

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

1. A method for producing a barrier film having a gas barrier layer having a lower layer containing at least one layer of a catalyst and a silicon compound and an upper layer containing at least one layer of SiO ₂ on the substrate, the method comprising: Including a step of forming a lower layer containing at least a polysilazane compound and a catalyst, a step of forming an upper layer containing at least a silicon compound, and a conversion treatment step in this order,
The said conversion process process is performed only after the process of forming an upper layer, The manufacturing method of the barrier film characterized by the above-mentioned.

2. The method for producing a barrier film according to claim 1, wherein the lower layer contains SiO ₂ .

3. The method for producing a barrier film according to claim 1, wherein the catalyst is an amine compound or a palladium compound.

4 . The said conversion process process is an ultraviolet irradiation excimer method, The manufacturing method of the barrier film as described in any one of said 1-3 characterized by the above-mentioned.

  According to the present invention, it is possible to obtain a barrier film having excellent production stability and handleability and having high barrier performance. By using the barrier film as a resin substrate for an organic photoelectric conversion element, an organic photoelectric converter having excellent durability can be obtained. A conversion element could be obtained.

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. It is a figure which shows the structure of an optical sensor array.

  The barrier film according to the present invention will be described.

The present invention forms a lower layer containing at least one layer of a catalyst and a silicon compound on a substrate, and a layer containing at least one layer of SiO ₂ on the substrate, thereby providing high gas barrier properties, flexibility and durability. A barrier film is provided.

Hereinafter, in the present invention, the lower layer containing the silicon compound and a catalyst for modifying the silicon compound and the upper layer containing SiO ₂ are referred to as a gas barrier layer.

In the present invention, with such a gas barrier layer, the water vapor transmission rate measured according to the JISK7129B method is 10 ⁻⁴ g / m ² / day or less, preferably 10 ⁻⁵ g / m ² / day or less, and the oxygen transmission rate There 0.01ml ^/ m 2 ^/ day or less, and preferably provides a superior barrier film gas barrier properties or less 0.001ml ^/ m 2 ^/ day.

[Lower layer containing catalyst and silicon compound]
In the present invention, a lower layer containing a catalyst and a silicon compound is formed on a substrate.

  The silicon compound in the present invention refers to a compound containing a silicon atom in a molecule and capable of performing a hydrolysis reaction or an oxidation reaction with oxygen or moisture in the air in the presence of a catalyst.

In the present invention, it is preferable to form the lower layer using the following silicon compound as a raw material. A flexible film can be formed by including a raw material of a silicon compound, a catalyst, and a substance in which a part thereof is changed to a SiOH group. Further, the contained catalyst has a function of accelerating the conversion of the silicon compound raw material to SiO _2. Typical examples of the catalyst include acids, alkalis, amine compounds and palladium compounds. Thereby, the lower layer forms a film softer than SiO ₂ as a whole, and the upper layer containing strong SiO ₂ can be prevented from coming into direct contact with the substrate.

(Silicon compound)
The silicon compound that can be used in the present invention is preferably perhydropolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, Methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, Dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3, , 3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane , Methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxy Silane, butyldimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane, phenyl Trimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycyl Sidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethoxyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxyp Propylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenyl Silane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxy Propylmethylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane Diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3 3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetra Methyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethyl Cyclotrisiloxane, octamethylcyclotetrasilo Sun, 1,3,5,7 tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, etc., or they may include compounds which are formed as a raw material.

  The silsesquioxane, Mayaterials manufactured by Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3-ethyl- 3-oxetylyl) methyoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octalyloxetanes sesquioxane, Octa [(3-Propylglycidylether) Dim thylsiloxy] Silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane Octakis (dimethylvinylsyloxy) octasilsesquioxane, Octakis [(3-hydroxypropyl) dimethylsyloxy] octasilsesquioxane, Octa [(metha ryloylpropyl) dimethylsilyloxy] silsesquioxane Octakis [(3-methacryloxypropyl) dimethylsiloxy] octasilsesquioxane and the like.

  Of these, silicon compounds that are liquid at room temperature are preferable, and perhydropolysilazane, silsesquioxane, and the like are more preferably used.

(catalyst)
Examples of the catalyst used in the present invention include metal fine particles described in JP-A Nos. 7-196986 and 11-105187, for example, metal fine particles such as Au, Ag, Pd, and Al, and JP-A No. 6-299118. Metal carboxylates described, for example, carboxylates containing Ni, Pt, Ti, etc., metal complexes described in JP-A-6-306329, for example, acetylacetonate complexes such as Pd, Ni, Pt, etc. Amine compounds and / or acids described in Kaihei 9-157544, 9-31333, etc., for example, heterocyclic amines such as primary to tertiary alkylamines, arylamines, pyridines, etc., aliphatic carboxylic acids, inorganic acids Etc.

  Of these, primary to tertiary alkylamines are preferred. As the catalyst function, even if the reaction rate is too fast, the smoothness and denseness of the coating film cannot be maintained. Therefore, a tertiary alkylamine that exhibits a suitable catalyst function is more preferably used.

  Furthermore, when these catalysts are vaporized after film formation, pores are formed in the barrier layer, and there is a possibility that the barrier property cannot be expressed. For these reasons, adjustment of the boiling point of the catalyst is also important. Specifically, 1,4-diaminobutane having a boiling point of 50 ° C. or higher and good compatibility with dibutyl ether used as a solvent for the polysilazane solution, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6 -Amines such as diaminohexane are preferred. Of these, N, N, N ′, N′-tetramethyl-1,6-diaminohexane is preferably used.

  As a function of these catalysts, Si—N—O—M or Si—N—O—C—M (M represents a metal or an amine), by mixing the silicon compound and the catalyst. Bond formation of Si—O— can be promoted.

  Catalysts particularly preferably used in the present invention are metallic palladium, palladium compounds and amines.

  The content of the catalyst is 0.0001% by mass to 50% by mass, preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass with respect to the silicon compound.

  As the silicon compound most preferably used in the present invention, perhydropolysilazane can be mentioned. Specifically, as non-catalyzed perhydropolysilazane, AZ Electronic Materials Co., Ltd. Aquamica NN110, NN310, NN320, etc., amine Examples of the perhydropolysilazane containing a catalyst include AZ Electronic Materials Co., Ltd. Aquamica NAX120-20, NP110, NP140, SP140, and the like, NL110A, NL120A, NL150A, etc. containing a palladium catalyst. When these silicon compounds are applied, it is preferable to use a solvent that does not easily contain water, such as xylene, dibutyl ether, solvesso, and terpenes, in order to suppress the reaction between the coating solution components and the water.

  When laminating a coating film containing a catalyst and a silicon compound, the content of the catalyst is preferably large in the layer on the base material side and small in the upper layer. Such a tendency of the composition is reflected in the bending resistance of the barrier film, and the barrier film produced by the method of the present application has little performance deterioration against bending.

  In the perhydropolysilazane used in the present invention, after the coating solution is applied, the layer obtained by simply drying the coating solution solvent hardly undergoes conversion to the silicon compound. Conversion process is required. By this conversion treatment, a dense gas barrier layer containing no impurities can be formed.

  On the other hand, in the case of a layer obtained by applying a liquid in which the catalyst is mixed with perhydropolysilazane and then drying the solvent of the coating liquid, a part of the perhydropolysilazane proceeds to a silicon compound due to the effect of the catalyst. Furthermore, when the layer containing this catalyst is allowed to stand naturally, the conversion of unreacted perhydropolysilazane to a silicon compound proceeds gradually due to the effect of the catalyst.

  When such a layer is used for the lower layer, since it has resistance to the solvent, the upper layer can be satisfactorily laminated by coating and drying, but conversely, a solution that does not add the catalyst to perhydropolysilazane. After coating, when a layer in which the coating solution solvent is dried is used as the lower layer, it becomes difficult to form a dried film. Therefore, when the upper layer is laminated and coated, it forms a good upper and lower layer such as dissolving in the upper layer coating solution solvent. Is difficult.

[Upper layer containing SiO ₂ ]
Next, the layer containing SiO ₂ formed in the upper layer will be described.

  As a method for forming a barrier film having a gas barrier layer comprising at least upper and lower layers according to the present invention, first, a coating solution containing at least one layer of a catalyst and a silicon compound is applied on a substrate to form a lower layer. It is presumed that after coating, the silicon compound is gradually oxidized or hydrolyzed by the action of the catalyst to form various mixtures, thereby forming a flexible film.

Further, an upper layer containing SiO ₂ is formed thereon to form a gas barrier layer composed of upper and lower layers.

The upper layer of the forming method containing SiO _2, (1) by coating a coating solution containing at least a silicon compound, by conversion processing in an oxidizing gas atmosphere, a method of forming a top layer containing SiO ₂ (2) A method in which a gas containing a silicon compound is subjected to a conversion treatment and an upper layer containing SiO ₂ is formed by a vapor phase method.

  Here, as the silicon compound used for the upper layer, the same silicon compound used for forming the lower layer can be used. Further, the catalyst used for the lower layer and the formation of the upper layer may contain a trace amount that does not inhibit the effect of the present invention, but it is more preferable that the catalyst is not substantially contained.

<Formation method by coating>
Any coating method can be used as a method for forming these upper and lower layers by coating. 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 of the lower layer and the upper layer can be set, for example, such 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.

(UV treatment)
As a means preferably used for the modification treatment of the production method of the present invention, there is ultraviolet irradiation. In order to dissociate the molecular bond of the inorganic compound by the energy of ultraviolet light and recombine with the inorganic layer having a high barrier property, it is important that the light is absorbed by the compound and its energy is higher than the molecular bond energy.

(Conversion process)
The conversion treatment step in the present invention refers to a so-called ceramic conversion treatment step for converting a silicon compound into SiO ₂ .

Examples of the conversion treatment for converting the silicon compound into SiO ₂ after the upper layer is formed by the coating method (1) include heat treatment, UV ozone treatment, plasma treatment, and ultraviolet irradiation treatment. Among them, ultraviolet irradiation treatment, particularly conversion treatment by excimer light irradiation is preferable in the present invention because of high conversion efficiency.

<Ultraviolet irradiation treatment>
The ultraviolet irradiation treatment preferably used in the present invention will be described. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and a silicon oxide film having high density and insulation can be produced at low temperature.

This UV irradiation heats the substrate and excites and activates O ₂ and H ₂ O, which contribute to SiO ₂ conversion (ceramic conversion), UV absorbers, and polysilazane itself. Also, the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the method according to the present invention, any commonly used ultraviolet ray generator can be used.

  In the present invention, “ultraviolet rays” specifically refers to ultraviolet rays (UV light) having a wavelength of 400 nm or less, radiation rays including X-rays and electron beams, and vacuum ultraviolet rays (10 to 200 nm described later). In the case of ultraviolet irradiation treatment other than the treatment, preferably 210 to 350 nm ultraviolet rays are used.

  Irradiation with ultraviolet rays can set irradiation intensity and / or irradiation time within a range in which the substrate carrying the film to be irradiated is not damaged.

Taking the case of using a plastic film as the substrate, for example, a lamp of 2 kW (80 W / cm × 25 cm) is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ² . Thus, the distance between the substrate and the lamp can be set, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the substrate may be damaged in the case of a plastic film or the like, for example, the substrate may be deformed or its strength may be deteriorated. However, in the case of a film substrate having high heat resistance such as polyimide, 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.

  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.

  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 having a polysilazane coating film on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. 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 on the surface is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. can do. 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 ultraviolet irradiation treatment>
In the present invention, a more preferable conversion treatment method includes treatment by vacuum ultraviolet irradiation. The treatment by vacuum ultraviolet irradiation uses light energy of 10 to 200 nm, which is larger than the interatomic bonding force in the silazane compound, and oxidation by active oxygen or ozone while directly cutting the bonds of the atoms by the action of only photons called photon processes. By allowing the reaction to proceed, an upper layer containing SiO ₂ can be formed at a relatively low temperature.

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

1. Excimer light emission is called an inert gas because atoms of rare gases such as Xe, Kr, Ar, and Ne do not form a molecule by chemically bonding. 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 → Xe ^*
Xe ^* + 2Xe → 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 lamp outer surface. 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, it can generate radical oxygen atom species and ozone at a high concentration with a very 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.

<Irradiation intensity of vacuum ultraviolet light>
If the irradiation intensity is high, the probability that the photons and chemical bonds in the polysilazane collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification).

  However, if the irradiation time is too long, the flatness may be deteriorated and other materials of the barrier film may be damaged. In general, the progress of the reaction is considered by the integrated light amount represented by the product of the irradiation intensity and the irradiation time, but the absolute value of the irradiation intensity may be important.

Therefore, in the present invention, in the VUV irradiation process, at least 1 is selected from the viewpoint of suppressing both damage to the base material and damage to the members of the lamp and the lamp unit, increasing the reforming efficiency, and improving the barrier performance. times, it is preferable to carry out the reforming process which gives the maximum irradiation intensity of ^{50mW / cm 2 ~200mW / cm 2} .

(Vacuum ultraviolet (VUV) irradiation time)
The irradiation time for irradiation with vacuum ultraviolet light (VUV) can be arbitrarily set, but from the viewpoint of substrate damage and film defect generation and productivity, the irradiation time in the light irradiation process is 0.1 second to One minute is preferable, and more preferably 0.5 seconds to 0.5 minutes.

(Oxygen concentration during irradiation with vacuum ultraviolet light (VUV))
The oxygen concentration at the time of irradiation with vacuum ultraviolet light (VUV) is preferably 300 ppm to 10000 ppm (1%), more preferably 500 ppm to 5000 ppm.

  By adjusting the oxygen concentration within the above range, it is possible to prevent the generation of an excessive oxygen barrier film and to prevent the deterioration of the barrier property.

  A gas other than oxygen is preferably a dry inert gas upon irradiation with vacuum ultraviolet light (VUV), and dry nitrogen gas is particularly preferred from the viewpoint of cost.

  The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

<Plasma treatment>
In the plasma treatment used in the present invention, plasma discharge treatment is performed while supplying a discharge gas that tends to be in a plasma state without supplying raw materials in the case of a plasma CVD method described later.

  By supplying oxygen having an oxidizing property as the reaction gas, the oxidation reaction can be advanced. As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

<< Formation of upper layer containing SiO ₂ by vapor phase process >>
As a method for forming the barrier film of the present invention, the method for forming the upper layer by the vapor phase method (2) will be described.

  As the vapor phase method, it is preferable to apply a sputtering method, an ion assist method, a plasma CVD method, a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, and the method using atmospheric pressure plasma CVD is particularly preferable. And the like, and a high-speed film formation method that is highly productive is preferable.

  The sputtering method, ion assist method, and plasma CVD method can form a film having a high barrier property. On the other hand, fine particles called particles are generated in the film forming process, and are easily attached to or on the surface of the gas barrier layer. There are drawbacks.

  Even if such a defect occurs, the barrier film of the present invention can suppress gas permeation from the defective part due to the presence of the lower layer having the catalyst and the silicon compound, and can realize higher gas barrier properties. It is.

<Plasma CVD method>
The upper layer containing SiO ₂ obtained by the plasma CVD method, or the plasma CVD method under atmospheric pressure or near atmospheric pressure is a raw material (also referred to as raw material) silicon compound, decomposition gas, decomposition temperature, input power, etc. It can be formed by selecting the conditions.

  As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

In the upper layer containing SiO _{2 according} to the present invention, the inorganic compound is SiO _x C _y (x = 1.5 to 2.0, y = 0 to 0.5), SiO _x , SiN _y or SiO _x. N _y (x = 1 to 2, y = 0 to 1) is preferable, and SiO _x is preferable from the viewpoint of light transmittance and suitability for atmospheric pressure plasma CVD described later.

  The inorganic compound contained in the layer having a silicon compound according to the present invention includes, for example, a combination of oxygen gas and nitrogen gas in a predetermined ratio with the above organic silicon compound, and at least one of an O atom and an N atom, an Si atom, Can be obtained.

  As described above, various inorganic thin films can be formed by using the source gas as described above together with the discharge gas.

Next, the atmospheric pressure plasma CVD method that can be suitably used for forming the layer having SiO ₂ in the method for producing a barrier film of the present invention will be described in more detail.

  In the atmospheric pressure plasma CVD method preferably used in the present invention, an electric field is applied to a space in the vicinity of a support to generate a space (plasma space) in which a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is formed. After being introduced into this plasma space and undergoing a decomposition reaction, it is sprayed onto the support to form an inorganic thin film. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support on which the inorganic material is formed and can sufficiently form the film on the resin film support.

Further, according to this method, a thin film having a dense film density and a stable performance can be obtained when the upper layer containing SiO ₂ is formed on the resin film substrate.

  In the plasma discharge treatment apparatus, the source gas containing the silicon compound and the decomposition gas are appropriately selected from the gas supply means, and the discharge gas that is likely to be in a plasma state is mixed with these reactive gases. The layer can be obtained by feeding a gas into the plasma discharge generator.

  As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as described above. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an atmospheric pressure plasma discharge treatment apparatus applicable to the present invention, for example, atmospheric pressure plasma discharge treatment described in JP-A-2004-68143, 2003-49272, International Patent No. 02/48428, etc. An apparatus can be mentioned.

  The conversion treatment step of the present invention may be performed for both the lower layer and the upper layer, but the lower layer conversion treatment step can be omitted because the lower layer of the present invention contains the aforementioned catalyst. By omitting the lower layer conversion process, it is possible to reduce the manufacturing cost by shortening the manufacturing time and simplifying the production equipment. At the same time, the upper layer is continuously added to the lower layer maintaining flexibility. By laminating, the bending resistance of the gas barrier film is increased by relaxing the interlaminar adhesion of the upper and lower layers and the film shrinkage stress in the conversion process of the perhydropolysilazane layer, and further the durability of the photoelectric conversion element using this Can increase the sex. In this case, the conversion process step for reforming is efficient because the upper and lower layers can be converted once after the upper layer is laminated.

In the barrier film of the present invention, as a method for forming the upper layer containing SiO ₂ , the coating method (1) is more advantageous in terms of adhesion, surface properties, productivity, etc. than the gas phase method (2). To preferred.

<Annealing>
Next, after the gas barrier layer formed by coating, conversion, or vapor phase method is formed, an embodiment in which annealing is further performed in the present invention is preferable. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 2 hours. By performing annealing in such a range, a part of polysilazane reacts to immobilize molecules, and a barrier film having good characteristics can be obtained. The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30% RH to 90% RH, more preferably 40% RH to 80% RH.

<substrate>
Next, the board | substrate used for the barrier film of this invention is demonstrated.

  The substrate is not particularly limited. For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride. (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and other resin films, Heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin Door can be.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like can be preferably used. The thickness of the substrate is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  Moreover, it is preferable that the board | substrate of the barrier film which concerns on this invention is transparent. Since the substrate is transparent and the layer formed on the substrate is also transparent, a transparent barrier film can be obtained. Therefore, a transparent substrate such as an organic EL element or a photoelectric conversion element can be obtained. Because.

  Further, the substrate using the above-described resin or the like may be an unstretched film or a stretched film.

  In addition, in the substrate according to the present invention, the substrate surface may be subjected to activation treatment such as corona discharge treatment, plasma treatment, UV ozone treatment, and excimer treatment before forming the gas barrier layer of the present invention.

  Furthermore, the substrate surface according to the present invention may have various functional layers shown below.

<Easily adhesive layer>
An easy-adhesion layer may be formed for the purpose of improving the adhesion with the gas barrier layer formed on the substrate. Examples of the anchor coating agent used for the easy adhesion layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One or two or more can be used in combination. Conventionally known additives can be added to these anchor coating agents. And the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc. can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

<Smooth layer>
For the purpose of improving the flatness of the gas barrier layer formed on the substrate, it is preferable to provide a smooth layer on the substrate surface.

  The smooth layer is used to flatten the rough surface of the transparent resin film substrate where protrusions and the like are present, or to fill the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the transparent resin film substrate. Provided. Such a smooth layer is basically formed by curing a photosensitive resin.

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. 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.

  The method for forming the smooth layer is not particularly limited, but 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.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

<Bleed-out prevention layer>
The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that, when a film substrate having a smooth layer is heated, unreacted oligomers migrate from the film substrate to the surface and contaminate the contact surface. Provided on the opposite side of the substrate having a layer.

  The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

  As other additives, a matting agent or the like may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than mass parts, more preferably not more than 16 mass parts.

  The bleed-out preventing layer as described above is prepared as a coating solution by mixing a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the film surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having 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 are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

[Use]
The barrier film of the present invention can be used as various sealing materials and sealing films.

  In the present invention, the gas barrier layer is preferably transparent. As the light transmittance of the barrier film, for example, when the wavelength of the test light is 550 nm, the transmittance is preferably 80% or more, and more preferably 90% or more.

  When using the barrier film of this invention for an organic photoelectric conversion element, for example, it can comprise so that sunlight may be received from this support body side using this barrier film as a support body. That is, on this barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for organic photoelectric conversion elements. Then, an ITO transparent conductive film provided on the support is used as an anode, a porous semiconductor layer is provided thereon, a cathode made of a metal film is further formed to form an organic photoelectric conversion element, and another seal is formed thereon. The organic photoelectric conversion element can be sealed by stacking a stopper material (which may be the barrier film of the present invention), adhering the barrier film substrate and the periphery, and encapsulating the element. The influence of the gas such as oxygen on the device can be sealed.

  As a method for sealing the two films, for example, a generally used impulse sealer heat-fusible resin layer is laminated, fused with an impulse sealer, and sealed. In this case, when the film thickness exceeds 300 μm, the barrier films are sealed with a film thickness of 300 μm or less because the film handleability at the time of sealing work is deteriorated and heat fusion with an impulse sealer or the like becomes difficult. desirable.

  As a method for forming a transparent conductive film on the barrier film of the present invention, it is manufactured by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin. it can.

  As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 nm to 1000 nm is preferable.

<< Configuration of Organic Photoelectric Conversion Element and Solar Cell >>
Next, as a preferred application of the barrier film of the present invention, an example in which a transparent conductive film is formed on the film and used as a resin substrate for an organic photoelectric conversion element will be described.

  First, each layer (component layer) of the organic photoelectric conversion element material constituting the organic photoelectric conversion element will be described.

  Although the preferable aspect of an organic photoelectric conversion element is demonstrated, this invention is not limited to these. There is no restriction | limiting in particular as an organic photoelectric conversion element, A power generation layer (a layer in which a p-type semiconductor and an n-type semiconductor are mixed, a bulk heterojunction layer, or an i layer) sandwiched between the anode and the cathode is at least one layer. Any element that 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 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.

  By sandwiching the power generation layer between the hole transport layer and the electron transport layer, the efficiency of taking out holes and electrons to the anode / cathode can be increased, so the configuration 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.

  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, 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.

  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.

  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 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).

  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 made of a single p-type semiconductor material and an n-layer made 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.

  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.

  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) of the present invention 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 heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above-mentioned condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A. 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. Am. 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.

  As the conjugated polymer, for example, 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, a polythiophene-thienothiophene copolymer described in WO2008000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, 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, oligomer materials instead of polymer materials include thiophene hexamer α-seccithiophene, α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis ( Oligomers such as 3-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 materials include materials that can be insolubilized by polymerizing 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. Alternatively, a soluble substituent reacts and becomes insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834. Materials etc. can be mentioned.

(N-type semiconductor material)
The n-type semiconductor material used for the bulk heterojunction layer of the present invention is not particularly limited. For example, a perfluoro compound (perfluoropentacene or the like) in which a hydrogen atom of a p-type semiconductor such as fullerene or octaazaporphyrin is substituted with a fluorine atom. Perfluorophthalocyanine), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized compounds thereof as a skeleton Etc.

  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), and the like. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, 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 / electron block layer)
The organic photoelectric conversion device of the present invention has a hole transport layer between the bulk heterojunction layer and the anode, and the charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable.

  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)
Since the organic photoelectric conversion element of the present invention can extract charges generated in the bulk heterojunction layer more efficiently by forming an electron transport layer between the bulk heterojunction layer and the cathode, these It is preferable to have a layer.

  As the electron transport layer, octaazaporphyrin and p-type semiconductor perfluoro (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, HOMO of p-type semiconductor material used for the bulk heterojunction layer. The electron transport layer having a HOMO level deeper than the level is given 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))
In the transparent electrode of the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element structure, but preferably the transparent electrode is used as the 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 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.

  The counter electrode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. A dispersion is preferable because a transparent and highly conductive counter electrode can be formed by a coating method.

  Moreover, when making the counter electrode side light-transmitting, for example, after forming a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound in a thin film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

(Intermediate electrode)
In addition, the material of the intermediate electrode required in the case of the tandem configuration as in (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) Or the like can be used.

  In addition, in 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 appropriately combining and laminating, and with such a configuration, the process of forming one layer This is preferable because it can be omitted.

(Metal nanowires)
As the conductive fiber of the present invention, an organic fiber or inorganic fiber coated with a metal, a conductive metal oxide fiber, a metal nanowire, a carbon fiber, a carbon nanotube, or the like can be used, and a metal nanowire is 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.

  The metal nanowire according to the present invention preferably has an average length of 3 μm or more in order to form a long conductive path with one metal nanowire, and to express an appropriate light scattering property. Furthermore, 3-500 micrometers is preferable, and it is especially preferable that it is 3-300 micrometers. 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.

  There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element or a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium) Iridium, ruthenium, osmium, and the like) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin, and more preferably at least silver 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 according to the present invention includes 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 has the same metal composition. You may have.

  In the present invention, there are no particular limitations on the means for producing the metal nanowire, 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 manufacturing method of Ag nanowire, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc., as a method for producing Au nanowires, such as JP 2006-233252A, etc., as a method for producing Cu nanowires, JP 2002-266007 A, etc. For example, Japanese Patent Application Laid-Open No. 2004-149871 can be referred to. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in an aqueous system, and since the conductivity of silver is the highest among metals, the production of metal nanowires according to the present invention is possible. It can be preferably applied as a method.

  In the present invention, the metal nanowires contact each other to form a three-dimensional conductive network, exhibit high conductivity, and light passes through the window of the conductive network where the metal nanowire does not exist. 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 of 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 particles 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)
The method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.

  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.

(Sealing member)
The organic photoelectric conversion element formed as described above is usually sealed and sealed from the outside by sealing with a sealing member.

  The blocking and sealing from the outside is performed by bonding the barrier films facing the barrier film to each other through a substantially frame-shaped sealing material provided on the periphery of the photoelectric conversion element by a coating method or a transfer method. Is called.

  The barrier film of the present invention is preferably used as this barrier film.

  The sealing material is made of a thermosetting epoxy resin, an ultraviolet curable epoxy resin, or a room temperature curable epoxy resin whose reaction starts by microencapsulating and pressurizing a reaction initiator. In this case, an air escape opening or the like is provided at a predetermined position of the sealing material to complete the sealing. The air escape opening is sealed with one of the above curable epoxy resins, ultraviolet curable resin, or the like in a vacuum atmosphere or a nitrogen gas or inert gas atmosphere in a vacuum apparatus.

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

Example 1
(substrate)
A 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films Co., Ltd.) that had been subjected to easy adhesion processing on both sides was annealed and heated at 170 ° C. for 30 minutes.

(Preparation of a film having a smooth layer and a bleed-out prevention layer)
By the following forming method, a bleed-out prevention layer was formed on one side, and a smooth layer was formed on the opposite side to obtain a barrier film substrate.

(Formation of bleed-out prevention layer)
On one side of the substrate, UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation was applied, applied with a wire bar so that the film thickness after drying was 4 μm, and then drying conditions: 80 ° C., 3 After drying in minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 1.0 J / cm ² curing was performed to form a bleedout prevention layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite surface of the substrate, applied with a wire bar so that the film thickness after drying is 4 μm, and then drying conditions; 80 After drying at 3 ° C. for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing conditions: 1.0 J / cm ² curing was performed to form a smooth layer.

  The maximum cross-sectional height Rt (p) at this time was 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

(Preparation of barrier film sample)
<Formation of gas barrier layer>
Next, a gas barrier layer was formed on the substrate provided with the smooth layer and the bleed-out prevention layer under the following conditions.

<Lower layer deposition>
(Lower layer coating solution)
20% by weight dibutyl ether solution of perhydropolysilazane (PHPS) containing 5% amine catalyst (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20)
The coating solution was applied with a wireless bar so that the (average) film thickness after drying was 0.25 μm to obtain a coated sample. 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. 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.

(Conversion processing A)
The dehumidified sample was converted under the following conditions to form a gas barrier lower layer. The dew point temperature during the conversion treatment was -8 ° C.

(Conversion processing equipment)
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com Co., Ltd., wavelength: 172 nm, lamp gas: Xe
The sample fixed on the operation stage was converted under the following conditions.

(Conversion processing conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 10 seconds Integrated light intensity per layer 4000 mJ / cm ²
<Upper layer deposition>
(Upper layer coating solution)
Non-catalytic perhydropolysilazane (PHPS) 20% by mass dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied with a spin coater so that the (average) film thickness after drying was 0.1 μm, and a coated sample was obtained. 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. 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.

(Conversion processing B)
The sample subjected to the dehumidification treatment was converted under the following conditions to form a gas barrier layer. The dew point temperature during the conversion treatment was -8 ° C.

(Conversion processing equipment)
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com Co., Ltd., wavelength: 172 nm, lamp gas: Xe
The sample fixed on the operation stage was converted under the following conditions.

(Conversion processing conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 10 seconds Integrated light intensity per layer 4000 mJ / cm ²
The content ratio of SiO _{2 in} the gas barrier layer of the present invention can be quantified by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), or the like, using a sputtering method. Usually, XPS is preferably used. A solid X-ray surface is irradiated with soft X-rays and the kinetic energy of photoelectrons emitted from the surface is measured by the photoelectric effect. Since the escape depth of the photoelectrons is several nm, information on atoms and molecules constituting a layer close to the outermost surface of the solid can be obtained. By using sputtering by ion (Ar, Xe) irradiation in combination, information such as composition from the surface in the depth direction and changes in the bonding state can be obtained. In the measurement of the depth direction of the barrier layer, the composition is analyzed by performing sputtering at regular intervals from the outermost surface in a state where no dirt or foreign matter is attached to the thickness depth up to the surface contacting the barrier layer and the substrate side. The measurement interval is 1 nm interval or more and 50 nm or less, and preferably 2 nm or more and 30 nm or less. When the thickness of the barrier layer is different from an integral multiple of the measurement interval, the nearest integer multiple of the measurement location that is equal to or less than the barrier layer thickness is taken as the end point of the composition comparison.

From the above analysis, it was confirmed that both the upper layer and the lower layer of Example 1 contained a SiO ₂ component.

Example 2
In Example 1, the lower layer was formed by changing to the following method.

(Lower layer coating solution)
Non-catalytic perhydropolysilazane (PHPS) in 20% by weight dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied with a wireless bar so that the (average) film thickness after drying was 0.25 μm to obtain a coated sample. On this membrane, a 10% aqueous solution of polystyrene sulfonic acid was applied as an acid catalyst and allowed to stand for 1 minute, and then the aqueous solution was removed.

  The subsequent steps were processed in the same manner as in Example 1 to obtain a two-layer gas barrier layer.

Example 3
In Example 1, the lower layer of the gas barrier layer was formed by the following method.

(Lower layer coating solution)
Non-catalytic perhydropolysilazane (PHPS) in 20% by weight dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied with a wireless bar so that the (average) film thickness after drying was 0.25 μm to obtain a coated sample. A 10% aqueous solution of 1,8-diazabicyclo- [5,4,0] -7-undecene as an alkali catalyst was applied onto the film and allowed to stand for 1 minute, and then the aqueous solution was removed.

  The subsequent steps were processed in the same manner as in Example 1 to obtain a two-layer gas barrier layer.

Example 4
In Example 1, the lower layer was formed by changing to the following method.

(Lower layer coating solution)
20% by mass dibutyl ether solution of perhydropolysilazane (PHPS) containing 5% palladium catalyst (Aquamica NP120-20, manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied with a wireless bar so that the (average) film thickness after drying was 0.25 μm to obtain a coated sample. The subsequent steps were processed in the same manner as in Example 1 to obtain a two-layer gas barrier layer.

Example 5
In Example 1, the excimer treatment immediately after forming the lower layer was omitted, and the excimer treatment was performed after the upper layer was applied.

Example 6
In Example 5, the excimer process was changed to the following process.

A UVO ₃ cleaning apparatus, Samco UV-1 was used, the substrate temperature was set to 150 ° C., and a UV lamp was irradiated for 10 minutes while flowing ozone gas into the chamber.

Example 7
In Example 5, the excimer process was changed to the following atmospheric pressure plasma (AGP) process described below.

<Atmospheric pressure plasma treatment>
The sample after being left for 30 minutes in an atmosphere of temperature 85 ° C. and humidity 55% RH was subjected to atmospheric pressure plasma treatment under the following conditions to form a gas barrier layer.

  The support holding temperature during atmospheric pressure plasma treatment was 120 ° C.

  It processed using the roll electrode type discharge processing apparatus. A plurality of rod-shaped electrodes opposed to the roll electrode were installed in parallel to the film transport direction, and power was applied to each electrode portion to plasma-treat the coated surface as follows.

  As the power source used here, a high frequency power source (80 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

<Dual frequency AGP>
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ²
High frequency side power supply power: 13.56 MHz at 9 W / cm ²
The maximum cross-sectional height Rt (p) after the atmospheric pressure plasma treatment was 12 nm.

Example 8
In Example 5, the film formation of the barrier film was changed to the following formulation.

(Lower layer 1 coating solution)
20% by weight dibutyl ether solution of perhydropolysilazane (PHPS) containing 5% amine catalyst (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20)
The coating solution was applied and dried with a wireless bar so that the film thickness after drying was 0.25 μm.

(Lower layer 2 coating solution)
Next, a 20% by mass dibutyl ether solution of perhydropolysilazane (PHPS) containing 5% of an amine catalyst (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) and 20% by mass of uncatalyzed perhydropolysilazane (PHPS). A butyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed to prepare an amine catalyst of 1%.

  The coating solution was applied and dried with a wireless bar so that the film thickness after drying was 0.1 μm.

(Upper layer coating solution)
Furthermore, 20 mass% dibutyl ether solution of non-catalytic perhydropolysilazane (PHPS) (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied and dried with a wireless bar so that the film thickness after drying was 0.1 μm.

  Thus, the laminated film which consists of three layers was formed, and the conversion process was performed by the method similar to Example 5. FIG.

Comparative Example 1
In Example 1, gas barrier layer formation was carried out by changing to the following method.

(Gas barrier layer coating solution)
Non-catalytic perhydropolysilazane (PHPS) 20% by mass dibutyl ether solution (Aquamica NN120-20, manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied and dried with a wireless bar so that the film thickness after drying was 0.3 μm.

  The conversion process was performed under the same conditions as in Example 5.

Comparative Example 2
In Comparative Example 1, everything was carried out in the same manner as Comparative Example 1 except that the gas barrier layer formation was changed to the following method.

(Gas barrier layer coating solution)
20% by mass dibutyl ether solution of perhydropolysilazane (PHPS) containing 5% amine catalyst (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.)
The coating solution was applied and dried with a wireless bar so that the film thickness after drying was 0.3 μm.

Comparative Example 3
In Example 5, everything was carried out in the same manner as in Example 5 except that the formation of the lower layer of the gas barrier layer was changed to the following method.

(Lower layer coating solution)
10% by mass solution of polystyrene dissolved in dichlorobenzene The above coating solution was applied using a wire bar so as to have a film thickness of 1 μm. Dried for 2 hours at room temperature. The film thickness was about 300 nm.

Comparative Example 4
In Example 1, a gas barrier layer having a two-layer structure in which the lower layer and the upper layer were interchanged was prepared.

Comparative Example 5
In Example 1, the upper layer was changed to the method described below, and everything was carried out in the same manner as in Example 1 except that the conversion treatment was not performed.

(Upper layer coating solution)
10% by mass solution of polystyrene dissolved in dichlorobenzene The above coating solution was applied using a wire bar so as to have a film thickness of 1 μm. Dried for 2 hours at room temperature. The film thickness was about 300 nm.

Comparative Example 6
The upper layer in Example 1 was implemented in the same manner as in Example 1 except that the lower layer film formation and the conversion process in Example 1 were repeated to laminate the same structure.

Comparative Example 7
The gas barrier layer in Comparative Example 1 was repeated twice, and the same procedure as in Comparative Example 1 was performed except that the lower layer and the upper layer having the same configuration were desired.

Comparative Example 8
The same operation as in Comparative Example 6 was performed except that the lower layer conversion treatment in Comparative Example 6 was omitted.

Comparative Example 9
The conversion process in Comparative Example 7 was performed in the same manner as Comparative Example 7 except that the conversion treatment was not performed after the lower layer film formation, but only after the upper layer film formation.

(Evaluation)
The barrier film samples (Examples 1 to 8 and Comparative Examples 1 to 9) obtained as described above were previously bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. The samples that were not bent were evaluated as follows.

<< Evaluation of water vapor permeability >>
The following measurement methods were used for evaluation.

<apparatus>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments
<Vapor deposition material>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
<Production of water vapor barrier property evaluation cell>
Metal calcium was vapor-deposited on the gas barrier layer surface of each barrier film sample by the vacuum vapor deposition apparatus. After that, the vacuum state is released, and in a dry nitrogen gas atmosphere, it is bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays. An evaluation cell was produced.

  The sealed sample thus obtained was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of corrosion of metallic calcium was measured based on the method described in Japanese Patent Application Laid-Open No. 2005-283561. The amount of water that permeated into the water was calculated.

<Evaluation rank>
The following ranks 1-5 were evaluated.

Less than 5: 1 × 10 ⁻⁵ g / m ² / day 4: 1 × 10 ⁻⁵ g / m ² / day or more, less than 1 × 10 ⁻⁴ g / m ² / day 3: 1 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g ^/ m 2 / day or more.

  The following organic photoelectric conversion element was produced using the barrier film sample subjected to the bending test as described above as a substrate, and further the sealing treatment was performed using the same barrier film, and the characteristics were evaluated.

<Preparation of organic photoelectric conversion element>
On the barrier layer surface of each barrier film, an indium tin oxide (ITO) transparent conductive film deposited with a thickness of 150 nm (sheet resistance 10 Ω / □) is patterned to a width of 2 mm using ordinary photolithography technology and wet etching. A first electrode was formed. 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, was applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer.

  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 in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and 3.0 wt% Then, a liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at room temperature and dried. Subsequently, heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate is moved into a vacuum deposition apparatus chamber, the pressure inside the vacuum deposition apparatus is reduced to 1 × 10 ⁻⁴ Pa or less, and then 0.6 nm of lithium fluoride is laminated at a deposition rate of 0.01 nm / second. Subsequently, a second electrode is formed by laminating 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask having a width of 2 mm (vaporization is performed so that the light receiving portion is 2 × 2 mm), An organic photoelectric conversion element having a light receiving portion with a size of 2 × 2 mm was produced.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), the surface of the two barrier film samples (bending test completed) on which the gas barrier layer is provided is the inner side, and an epoxy photocurable adhesive is used as a sealing material for the gas barrier. An organic photoelectric conversion element applied on the layer and formed using the same barrier film sample as a substrate was sandwiched between the barrier films and adhered, and then cured by irradiating UV light from one side of the substrate. In this way, the organic photoelectric conversion element sample sealed on both sides was obtained.

  Each photoelectric conversion element thus obtained was evaluated by the following method.

<Evaluation of durability of organic photoelectric conversion device>
The organic photoelectric conversion element produced above was irradiated with light of 100 mW / cm ² of solar simulator (AM1.5G filter), and a mask with an effective area of 4.0 mm ² was superimposed on the light receiving part to evaluate IV characteristics. By measuring the four light receiving portions formed on the same element, the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%) are measured according to the following formula 1. A four-point average value of the obtained energy conversion efficiency PCE (%) was estimated.
(Formula 1) PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial battery characteristics was measured, and the degree of deterioration with time in the performance was stored at a temperature of 60 ° C. and a humidity of 90% RH for 1000 hours. It was evaluated with 1-5.

Conversion efficiency remaining rate (%) = ratio of conversion efficiency after acceleration test / initial conversion efficiency × 100
5: Conversion efficiency remaining rate is 90% or more 4: Conversion efficiency remaining rate 70% or more, less than 90% 3: Conversion efficiency remaining rate 40% or more, less than 70% 2: Conversion efficiency remaining rate 20% or more, less than 40% 1 : Conversion efficiency remaining rate of less than 20% Each evaluation result is shown in Table 1.

  As is clear from Table 1, the barrier film of the present invention has excellent bending resistance and low water vapor transmission rate. Further, the organic photoelectric conversion element produced using the barrier film of the present invention as a substrate and a sealing member is It can be seen that performance degradation is unlikely to occur in harsh environments.

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 20 photosensor array 21 substrate 22 transparent electrode 23 counter electrode 24 photoelectric conversion part 24a buffer layer 24b photoelectric conversion layer

Claims (4)

A method for producing a barrier film having a gas barrier layer having a lower layer containing at least one layer of a catalyst and a silicon compound and an upper layer containing at least one layer of SiO ₂ on the substrate, the method comprising: Including a step of forming a lower layer containing at least a polysilazane compound and a catalyst, a step of forming an upper layer containing at least a silicon compound, and a conversion treatment step in this order,
The said conversion process process is performed only after the process of forming an upper layer, The manufacturing method of the barrier film characterized by the above-mentioned. The method for producing a barrier film according to claim 1, wherein the lower layer contains SiO ₂ . The method for producing a barrier film according to claim 1, wherein the catalyst is an amine compound or a palladium compound. The said conversion process process is an ultraviolet irradiation excimer method, The manufacturing method of the barrier film as described in any one of Claims 1-3 characterized by the above-mentioned.