JP5636646B2 - Barrier film manufacturing method, barrier film and organic photoelectric conversion device manufacturing method - Google Patents

Description

  The present invention mainly relates to a barrier film used for a display material such as a package of an electronic device or the like, or a plastic substrate such as an organic EL element, a solar cell, or a liquid crystal, and a resin substrate for various devices using the barrier film, and various device elements About.

  Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging goods 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 etc. are widely used as packaging materials in such fields, but disposal after use is a problem, and it is basically opaque and the contents should be confirmed from the outside. In addition, since display materials are required to be transparent, they cannot be applied at all.

  In particular, transparent substrates that are being applied to liquid crystal display elements, solar cells, etc. have recently been able to be produced in roll-to-roll, in addition to demands for weight reduction and size increase, long-term reliability and High demands such as high degree of freedom of shape and display of curved surfaces are added, and film base materials such as transparent plastics are beginning to be used instead of glass substrates that are heavy and easily broken. For example, an example using a polymer film as a substrate of an organic electroluminescence element is disclosed (for example, refer to Patent Documents 1 and 2). When a film having a relatively high oxygen permeability such as polyethylene terephthalate (hereinafter abbreviated as “PET”) is used as the transparent resin film, the film base material such as transparent plastic is inferior in barrier properties to glass. There's a problem. For example, when used as a substrate of an organic photoelectric conversion element, there is a problem that if a base material 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. Known barrier films used for packaging materials and liquid crystal display elements include those obtained by depositing silicon oxide on a plastic film (for example, see Patent Document 1) and those obtained by depositing aluminum oxide (for example, see Patent Document 2). ing.

  Moreover, the method of forming a barrier layer by the method of surface-treating after apply | coating the coating liquid which has polysilazane as a main component instead of a vapor deposition method is known (patent document 3, 4). A barrier layer formed by forming a film of silicon nitride and / or silicon oxynitride and performing a discharge treatment with an oxidizing gas, a laminate with a barrier film in which a resin layer and the barrier layer are alternately formed, and a method for forming the same are also known. There is also a description of atmospheric pressure plasma treatment as the discharge treatment method (Patent Document 5).

However, any of these techniques has an insufficient function as a barrier layer of an organic photoelectric conversion element or the like, and has a water vapor transmission rate exceeding 1 × 10 ⁻² g / (m ² · 24 h). There was a need for improved sex.

  As a technique for further improving the barrier property, a technique using the polysilazane layer in combination with a plasma CVD method is also known (see Patent Document 6). The point of this technology is to heat-treat after applying a liquid containing polysilazane, but in order to obtain a barrier property, a heat treatment for a long time at a relatively high temperature is necessary. For example, a base having high heat resistance such as PES. This material is difficult to apply to PET and the like having high versatility, has poor productivity, and even in this technology, the above barrier performance target has not been achieved.

  There is known a method for forming a dense functional body having a release property, scratch resistance, luminance life, transmittance, and light shielding property using a plasma chemical vapor deposition method using a silazane compound as a source gas (for example, Patent Document 7). . The functional body fabricated using this technology has a good function, but it is a problem unique to the plasma CVD method, which is called a particle in the plasma space between the opposing electrodes, which is a problem unique to the plasma CVD method. There are cases where product particles are generated and these particles adhere to the surface of the deposited film to prevent uniform film formation, and there is a concern that the portion may become a defect and deteriorate the quality of the organic photoelectric conversion element. It was.

JP-A-2-251429 JP-A-6-124785 JP 2007-237588 A JP 2000-246830 A JP 2004-114645 A Japanese Patent Laid-Open No. 8-281186 JP 2004-84027 A

  Accordingly, an object of the present invention is to provide a film capable of achieving extremely high barrier performance, to use the film as a resin substrate for an organic photoelectric conversion element, and to the resin substrate for an organic photoelectric conversion element. It is to obtain a device such as a highly permeable organic photoelectric conversion element using the above.

  The above object of the present invention is achieved by the following means.

1. A liquid containing at least one silicon compound is applied to at least one surface on the substrate.
After forming a thin film by coating and drying at 0 ° C. to 100 ° C., at least one organosilicon compound and a base material on which the thin film is applied and formed without performing a heat treatment at 140 ° C. or higher. A method for producing a barrier film, comprising laminating a silicon oxide thin film by a plasma CVD method using a reactive gas containing oxygen.
2. 2. The method for producing a barrier film according to 1 above, wherein the liquid containing the at least one silicon compound is applied and dried at 20 to 80 ° C.

3. 3. The method for producing a barrier film according to 1 or 2, wherein the liquid containing the silicon compound is a liquid containing at least polysilazane.
4). For thin film obtained by the coating and drying, in IR measurement, attributed to Si-O absorption attributed to the (asymmetric) stretching vibration absorption attributed to Si-N stretching vibration (1080 cm ^-1) (960 cm ^-1) The ratio to (Si—O) ¹⁰⁸⁰ / (Si—N) ⁹⁶⁰ is 0.1 or more and 3 or less, the method for producing a barrier film as described in any one of 1 to 3 above.

5. 5. The method for producing a barrier film according to any one of 1 to 4, wherein the silicon oxide thin film is formed by a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure.

6). 6. The method for producing a barrier film according to any one of 1 to 5 , wherein the plasma CVD method is performed under two or more kinds of high-frequency electric fields.
7). 7. The method for producing a barrier film according to any one of 1 to 6, wherein a smooth layer is provided between the substrate and the thin film.

  According to the present invention, it is possible to obtain a barrier film that is excellent in production stability and handleability and that can achieve high barrier performance, and a barrier film that is useful as a resin base material for organic photoelectric conversion elements excellent in gas barrier properties can be obtained. Moreover, an organic photoelectric conversion element can be obtained using the manufacturing method and the substrate.

It is a figure which shows an example of IR absorption when heat-processing to a polysilazane film | membrane. 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 which is a bulk heterojunction type and the electric power generation layer becomes a three-layer structure of pin. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer.

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

  The barrier film of the present invention has at least two ceramic layers on a resin film support such as polyethylene terephthalate. That is, a thin film was formed by plasma discharge treatment using a reactive gas containing at least one organic silicon compound and oxygen (hereinafter referred to as plasma CVD). It is described that it is formed) It has at least two ceramic layers made of silicon oxide layers. In the barrier film of the present invention, three or more such ceramic layers may be laminated.

<Gas barrier layer (hereinafter referred to as barrier layer)>
The barrier layer in the present invention is a film containing silicon atoms and oxygen atoms and blocking the permeation of oxygen and water vapor. Specifically, the constituent material is preferably an inorganic oxide containing silicon, such as silicon oxide, oxynitridation. A ceramic layer such as silicon can be mentioned.

With such a barrier layer, the water vapor transmission rate measured according to the JIS K7129B method is 10 ⁻⁴ g / (m ² · 24 h) or less, preferably 10 ⁻⁵ g / (m ² · 24 h) or less, and oxygen transmission A film having a support with a resin film having an excellent barrier property with a rate of 0.01 ml / (m ² · 24 h · atm) or less, preferably 0.001 ml / (m ² · 24 h · atm) or less is obtained.

  The water vapor permeability of the barrier film of the present invention is negligible when used for applications requiring high water vapor barrier properties such as organic EL displays and high-definition color liquid crystal displays, especially for organic EL display applications. However, since a growing dark spot may occur and the display life of the display may become extremely short, the water vapor permeability measured according to the JISK7129B method is preferably not more than the above value.

  In order to achieve such barrier properties, the surface roughness of the barrier layer surface is 10 nm or more and 30 nm or less with the maximum cross-sectional height Rt (p) of the roughness curve obtained according to JIS B0601: 2001. Preferably there is. The barrier film of the present invention is further smoothed by applying a silicon compound on the smooth layer, and a smoother barrier layer is formed by laminating a silicon oxide layer thereon by plasma CVD to form a ceramic layer. Can be obtained.

<Method for forming barrier layer>
In the method for producing a barrier film of the present invention, a liquid containing at least one silicon compound is applied to at least one surface on a film substrate at 20 ° C. to 120 ° C. and dried to form a silicon compound thin film. Without performing a heat treatment at 140 ° C. or higher on the thin film, a plasma CVD method using a reactive gas containing at least one organic silicon compound and oxygen on a substrate on which the thin film is applied and formed. A thin film of silicon oxide is laminated.

When a barrier layer made of silicon oxide is laminated by plasma CVD after heat treatment (for example, heat treatment at 160 ° C. for 1 hour) after applying polysilazane as in the prior art (for example, described in JP-A-8-281661) ,
1. Since the silicon compound coating layer has already been converted so as to have a hard film quality of silicon oxide, it has a high curvature when passing through a roll during transportation in the lamination process of the silicon oxide thin film by plasma CVD. There is a possibility that a crack may occur due to the curvature, thereby causing a decrease in barrier properties.

  2. Also, an interface between a silicon oxide formed from a silicon compound coating layer formed by coating and a barrier layer made of silicon oxide formed by plasma CVD using a reactive gas containing an organic silicon compound and oxygen. As a result, the adhesiveness is liable to be lowered, and there is a concern that the barrier property is similarly lowered.

  On the other hand, in the production method of the present invention, after the formed coating film is newly dried, the silicon compound in the layer is not subjected to a heat treatment at 140 ° C. or higher which causes a substantial conversion to silicon oxide. By laminating a thin film of silicon oxide by the plasma CVD method described later, a barrier film having desired barrier properties and adhesion, and flexibility as a barrier film can be obtained. Although the mechanism is not clear, if the processing temperature is less than 140 ° C., the silicon compound is not substantially converted to silicon oxide, and the silicon compound in the precursor state is substantially present. Furthermore, by performing plasma CVD, polysilazane (silicon compound) in the vicinity of the coating film surface by plasma energy is converted into silicon oxide, and part of silanol groups are formed, and silicon oxide is simultaneously formed by CVD. Thus, the reaction at the interface between the two layers is also promoted, and it is presumed that a flexible barrier film layer having a dense and good adhesion can be obtained. Furthermore, if the processing temperature is 120 ° C. or lower, a barrier layer with better performance can be obtained.

  Therefore, the present invention does not use a heat treatment at 140 ° C. or higher, and laminates a silicon oxide thin film by plasma CVD before the silicon compound layer formed by coating is sufficiently converted to silicon oxide. For example, in the case of polysilazane represented by the following general formula, the degree of conversion to silicon oxide can be known by measuring IR absorption of a silicon compound (polysilazane) thin film.

As polysilazane is converted to silicon oxide, the absorption attributed to Si—N stretching vibration of polysilazane is attenuated. Therefore, the absorption attributed to (asymmetric) stretching vibration attributable to Si—O, which also has silicon oxide ( know the degree of Si-N stretching ratio absorption (960 cm ^-1) attributed to a vibration ^{(Si-O) 1080 / (} Si-N) 960 to take if conversion to silicon oxide of the silicon compound of 1080 cm ^-1) be able to.

In FIG. 1 (1), as an example of polysilazane, a thin film (film thickness 300 nm) formed from AQUAMICA NAX120-20 manufactured by AZ Electronic Materials Co., Ltd., 30 minutes at 60 ° C., 80 ° C., 120 ° C., 150 ° C. IR absorption curves of those subjected to the heat treatment are shown. The peak represented by a is absorption (1080 cm ⁻¹ ) attributed to (asymmetric) stretching vibration attributable to Si—O, and the peak represented by b is attributable to Si—N stretching vibration. Absorption (960 cm ⁻¹ ).

When the heating time is about 30 minutes, the peak intensity ratio a / b is 4 or less at temperatures of 60 ° C. and 80 ° C., but is about 5 at 120 ° C., and is expressed by b when the heating condition is 150 ° C. The absorption (960 cm ⁻¹ ) attributed to the Si—N stretching vibration is almost absent (a / b = 10 or more), and it is considered that the silicon oxide is converted to silicon oxide as a result of the thermal reaction. Incidentally, when fully baked (for example, heating conditions at 150 ° C. for one day), a / b is 20 or more.

  FIG. 1 (2) also shows 60 minutes and 180 minutes heating data at each temperature.

The present invention is characterized in that the silicon oxide layer is formed by plasma CVD while the conversion to silicon oxide does not proceed substantially, that is, without performing a heat treatment at 140 ° C. or higher after the silicon compound layer is formed by coating. And When polysilazane is used, the ratio (Si-O) of absorption (1080 cm- ¹ ) attributed to (asymmetric) stretching vibration attributed to Si-O to absorption (960 cm- ¹ ) attributed to Si-N stretching vibration (Si-O). ) ¹⁰⁸⁰ / (Si—N) ⁹⁶⁰ (= a / b) conversion into this silicon oxide shows that if a / b is 0.1 or more and 5 or less, the silicon compound remains sufficiently. Therefore, it can be determined that the conversion to silicon oxide has not substantially progressed. Preferably, when a / b is 0.1 or more and 5 or less, a silicon oxide film can be stacked by plasma CVD. . If a / b is within this range, the silicon compound remains sufficiently, and the conversion to silicon oxide has not substantially progressed. It is more preferable that a / b is 3 or less, and more preferable is 0.3 or more and 1 or less.

Therefore, in another preferred embodiment of the present invention, a liquid containing at least one silicon compound is applied to at least one surface on a substrate, and is coated and dried at 20 ° C. to 120 ° C. to form a thin film. in the thin film, thin film, in IR measurement, attributed to Si-O absorption attributed to the (asymmetric) stretching vibration absorption attributed to Si-N stretching vibration (1080 cm ^-1) (960 cm ^-1) When the ratio to (Si—O) ¹⁰⁸⁰ / (Si—N) ⁹⁶⁰ is 0.1 or more and 5 or less, the substrate on which the thin film is applied and formed contains at least one organosilicon compound and oxygen It can be said that the method for producing a barrier film is characterized in that a silicon oxide thin film is laminated by a plasma CVD method using a reactive gas.

  In the silicon compound coating, some silanol groups are also formed by plasma energy, and this simultaneously with the formation of silicon oxide by CVD promotes the reaction at the interface between the two layers, and it is dense and flexible with good adhesion. It is presumed that a barrier layer having a characteristic film quality can be obtained.

  In addition, the above-mentioned measurement by IR absorption is performed by separately forming a silicon compound thin film (dry film thickness of 300 nm) on a BaF plate (without IR absorption) with a spin coater or the like, and heat-treating it under various conditions. Can be done. As the IR measuring apparatus, FT-IR Nexus870 manufactured by Thermo Fisher Scientific Co., Ltd. can be used.

  Any appropriate method can be adopted as a method for applying the liquid containing the silicon compound on the substrate. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 5 nm to 2 μm, more preferably about 10 nm to 1 μm, and most preferably about 30 nm to 0.5 μm.

<Silicon compound coating layer formed by coating and drying>
Preferred examples of the silicon compound that can be used for the silicon compound coating layer formed by coating and drying of the present invention include polysilazane, silsesquioxane, 1,1,3,3-tetramethyldisilazane, 2,2, 4,4,6,6-hexamethylcyclotrisilazane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetra Ethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane , Dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylamino Trimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3- Aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropylene Trimethoxysilane, diaryldimethoxysilane, butyldimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltri Methoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane , Dimethylethyoxyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethyl Phenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane, octyloxy Limethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethyl Silane, 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) tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, , 3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3 Examples include 5,7-tetramethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

  Of these, polysilazane, silsesquioxane and the like are more preferably used.

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

  In order not to damage the film base material, as described in JP-A-8-112879, it is preferable that the material be ceramicized at a relatively low temperature to be modified to silica. It can be preferably used.

  However, each of R 1, R 2 and R 3 in the formula is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, etc., and is obtained in the present invention. Perhydropolysilazane in which all of R 1, R 2, and R 3 are hydrogen atoms is particularly preferred because of its denseness as a barrier film.

  On the other hand, organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base material is improved and the ceramic made of polysilazane which is hard and brittle The film can be tough, and there is an advantage that the occurrence of cracks can be suppressed even when the film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with polysilazane of the above chemical formula 1 (Japanese Patent Laid-Open No. 5-238827), glycidol addition obtained by reacting glycidol Polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting a metal carboxylate 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (specialty) Kaihei 7-19 986 JP), and the like.

  As an organic solvent for preparing a liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

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

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

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

  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) methoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octalyloxetanes sesquioxane, Octa [(3-Propylglycidyletherer) D methylsiloxy] Silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane Octakis (dimethylvinylsilyloxy) octasilsesquioxane, Octakis [(3-hydroxypropylo) dimethylsiloxyxy, octasilsequioxane, Octa [( methacryloylpropyl) dimethylsilyloxy] silsesquioxane octakis [(3-methacryloxypropyl) dimethylsiloxy] octasylsequioxane, and compounds of the following structural formula.

  The drying temperature after applying the liquid containing the silicon compound in the present invention is usually 20 ° C. to 120 ° C., preferably 40 ° C. to 100 ° C. The solvent evaporates depending on the drying temperature and the coating film thickness. It is sufficient if a layer containing a silicon compound can be formed, which is approximately several seconds to several minutes. Drying at a higher temperature may cause substantial conversion of the silicon compound to silicon oxide, and depending on the plastic substrate used, coating film thickness, etc., curl to the coating film side may increase. In some cases, cracks may occur in the coating film. Conversely, if the temperature is lower than this, the adhesion may be lowered.

  In addition, the coating layer of the present invention may be a single layer or a plurality of similar layers, and a combination unit with plasma CVD described later may be one time or two or more times, and may be cracked. The barrier property can be further improved by performing the treatment a plurality of times within a range where no adverse effects such as occurrence occur.

<Silicon oxide layer by plasma CVD>
Next, in the present invention, a silicon oxide layer is further laminated on the above-described coating layer by a plasma CVD method using a reactive gas containing at least one organic silicon compound and oxygen.

  In the present invention, after the coating layer (film) formed as described above is dried, a silicon oxide thin film is further laminated by a plasma CVD method to be described later without substantially performing a heat treatment for converting the coating layer to silica. As a result, the formation of a silicon oxide thin film by the plasma CVD method and the conversion of the coating layer to silica can be caused simultaneously, and a barrier film having a desired barrier property and excellent flexibility can be obtained. .

  As described above, the mechanism is not clear, but the conversion of polysilazane near the coating film surface to silicon oxide by plasma energy and the formation of some silanol groups also occur, and this leads to the formation of silicon oxide by CVD. It is presumed that the reaction at the interface between the two layers occurs at the same time, and a flexible and flexible barrier layer with good adhesion is obtained.

(Plasma CVD)
In general, vacuum deposition, sputtering, plasma CVD, which will be described later, and the like are known as methods for forming a silicon oxide layer, but the above-described sufficiently excellent barrier properties cannot be obtained by vacuum deposition or sputtering. .

  On the other hand, in the plasma CVD method, a film having a high barrier property can be formed, but in the film forming process, there is a defect that fine particles called particles are generated and a defect attached to or on the surface of the barrier layer is likely to occur.

  Even if such a defect occurs, the barrier film of the present invention can suppress gas permeation from the defective portion due to the presence of the layer having the above-described silicon compound, and can realize higher barrier properties. .

  The thickness of the thin film (layer) having these silicon compounds in the present invention is appropriately selected depending on the type and configuration of the material used, and is preferably in the range of 5 to 2000 nm.

  When the thickness of the layer containing a silicon compound is thinner than the above range, a uniform film with many film defects cannot be obtained, and it is difficult to improve the barrier property against gas. In addition, when the thickness of the layer having a silicon compound is thicker than the above range, the moisture resistance is theoretically high, but the internal stress becomes unnecessarily large, and the film is bent during film formation or after film formation. In some cases, a favorable barrier property may not be obtained due to the possibility of cracking due to external factors such as pulling.

  Further, in the present invention, it is preferable that a silicon oxide thin film formed by plasma CVD on the silicon compound layer is transparent. It is because it becomes possible to make a barrier film transparent by being transparent, and it can also be used for uses, such as a transparent substrate of an EL element. 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.

  Plasma CVD method, plasma CVD method under atmospheric pressure or near atmospheric pressure, metal carbide by selecting conditions such as organometallic compound, decomposition gas, decomposition temperature, input power etc. which are raw materials (also called raw materials) It is preferable because a ceramic layer of metal nitride, metal oxide, metal sulfide, etc., and a mixture with these metal oxynitrides, metal nitride carbides, etc. can be formed separately.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  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.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  In the present invention, a silicon compound is used as a source gas containing a metal element. Examples of the silicon compound include alkyl silanes such as dimethylsilane, tetramethylsilane, and tetraethylsilane; tetramethoxysilane, tetraethoxysilane (TEOS). Organic silicon compounds such as silicon alkoxides such as tetrapropoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and tetramethoxydisiloxane (TMDSO); silicon hydrogen compounds such as monosilane and disilane; dichlorosilane and trichlorosilane And halogenated silicon compounds such as tetrachlorosilane; and other organosilanes, and any of these can be preferably used. Moreover, these can be used in combination as appropriate. From the viewpoint of handling, the above silicon compounds are preferably silicon alkoxides, alkyl silanes, and silicon hydrogen compounds, and are not corrosive, do not generate harmful gases, and have little contamination in the process. preferable.

  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 silicon oxide thin film according to the present invention, the inorganic compound contained is SiOxCy (x = 1.5 to 2.0, y = 0 to 0.5), SiOx, SiNy or SiOxNy (x = 1 to 2, y = 0.1-1), and from the viewpoint of light transmittance and suitability for atmospheric pressure plasma CVD described later, SiOx is preferable.

  Next, the atmospheric pressure plasma CVD method that can be suitably used for forming the silicon oxide thin film according to the present invention in the barrier film manufacturing method of the present invention will be described in more detail.

  In CVD (chemical vapor deposition), volatilized and sublimated organometallic compounds adhere to the surface of a high-temperature support, causing a thermal decomposition reaction to produce a thermally stable inorganic thin film. In such a normal CVD method (also referred to as a thermal CVD method), since a substrate temperature of 500 ° C. or higher is usually required, it is difficult to use for forming a film on a plastic support. In the CVD method, an electric field is applied to the space in the vicinity of the support to generate a space (plasma space) in which a gas is present (plasma space). Volatilized and sublimated organometallic compounds are introduced into the plasma space and decomposed. After the occurrence of this, 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 performance and a stable performance can be obtained when the silicon oxide thin film is formed on the resin film.

  Next, an example of a method for laminating the above-described silicon oxide thin film using the plasma CVD method at or near atmospheric pressure will be described.

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

  In the present invention, the plasma discharge treatment is performed under atmospheric pressure or a pressure in the vicinity thereof, and the atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and in order to obtain a good effect described in the present invention. Is preferably 93 kPa to 104 kPa.

The discharge condition in the present invention is such that the first high-frequency electric field and the second high-frequency electric field are superimposed on the discharge space, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, The relationship between the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge start electric field strength IV is as follows.
V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied,
The output density of the second high frequency electric field is 1 W / cm ² or more.

  High frequency refers to one having a frequency of at least 40 kHz.

  When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

  In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (such as electrode configuration) and reaction conditions (such as gas conditions) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

  Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one of them may be a continuous wave and the other may be a pulse wave. Further, it may have a third electric field.

  As a specific method of applying the high-frequency electric field of the present invention to the same discharge space, the first high-frequency electric field having the frequency ω1 and the electric field strength V1 is applied to the first electrode constituting the counter electrode. It is to use an atmospheric pressure plasma discharge treatment apparatus in which a power source is connected and a second power source for applying a second high frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode.

  The atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a reactive gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher frequency electric field strength than the second power source.

  Here, the high frequency electric field strength (applied electric field strength) and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of high-frequency electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode section, and the output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the high frequency electric field strength measurement.

  By adopting the discharge conditions specified in the present invention, even a discharge gas having a high discharge starting electric field strength, such as nitrogen gas, can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. It can be done.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first high frequency electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 40 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. It is an important point of the present invention that the plasma density can be increased by the high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated.

  In the atmospheric pressure plasma discharge processing apparatus used in the present invention, the first filter facilitates passage of the current of the first high-frequency electric field from the first power source to the first electrode, and grounds the current of the second high-frequency electric field. Thus, it is difficult to pass the current of the second high-frequency electric field from the second power source to the first power source. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. The current of the first high-frequency electric field to the power supply is made difficult to pass. In the present invention, any filter having such properties can be used without limitation.

  For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

Supply power higher well, the first power source is preferably 1W / cm ² or more, 2W / cm ² or more is more preferable, 5W / cm ² or more is more preferable. The second power source is preferably 1 W / cm ² or more, more preferably 5 W / cm ² or more, and even more preferably 11 W / cm ² or more.

  Further, as the discharge gas, nitrogen gas and / or an 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 reactive gas is not limited as long as the silicon compound can be changed to silicon oxide, but oxygen and water are preferable.

  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.

  Moreover, as a power supply installed in the atmospheric pressure plasma discharge treatment apparatus, Shinko Electric SPG50-4500 (frequency 50 kHz), Hayden Laboratory PHF-6k (100 kHz), Pearl Industry CF-2000-200k (200 kHz), CF-2000- 400k (400kHz), CF-2000-800k (800kHz), CF-2000-2M (2MHz), CF-2000-13M (13.56MHz), CF-2000-27M (27MHz), CF-2000-150M (150MHz) ) And the like, and any of them can be preferably used.

  Next, the present invention will be described in more detail.

  Next, the resin film support used as a substrate in the barrier film according to the present invention will be described.

  The resin film support as a substrate is not particularly limited as long as it is formed of an organic material capable of holding the above-described barrier layer.

  For example, acrylic ester, methacrylate 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, silsesquioxane having an organic-inorganic hybrid structure And a heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin film formed by laminating two or more layers of the resin. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  The resin film support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.

  Moreover, the unstretched film may be sufficient as the resin film support body using the resin etc. which were mentioned above, and a stretched film may be sufficient as it.

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

  In the present invention, the resin film support may be subjected to corona discharge treatment before the barrier film is formed.

Furthermore, an anchor coat agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion to the vapor deposition film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(Smooth layer)
In the present invention, a smooth layer is preferably provided on the base resin film.

  The smooth layer of the present invention flattens the rough surface of the transparent resin film support with protrusions or the like, or fills the irregularities and pinholes generated in the transparent inorganic compound layer with the protrusions present on the transparent resin film support. Provided for flattening. 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.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, mihi -Ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, Examples include a combination of a photoreducible dye such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  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.

  Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  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. If the value is smaller than this range, the coatability is impaired when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or wireless bar at the stage of coating a silicon compound described later. There is a case. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

  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.

(Additive to smooth layer)
One preferred embodiment includes reactive silica particles (hereinafter, also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the above-described photosensitive resin. Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By making the average particle diameter in such a range, by using it in combination with a matting agent composed of inorganic particles having an average particle diameter of 1 to 10 μm, which will be described later, optical properties satisfying a good balance between antiglare property and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent, or cracks may occur when heat treatment is performed, or optical properties such as transparency and refractive index of the gas barrier film may be affected.

  In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  The thickness of the smooth 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 smoothness as a film having a smooth layer 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 has a high transparency. When the film is provided only on one surface of the molecular film, curling of the smooth film can be easily suppressed.

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

  Examples of polyunsaturated organic compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropante La (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxy) Ethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent 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 part by mass, more preferably not more than 16 parts by mass.

  The bleed-out preventing layer of the present invention may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicone resin etc. are mentioned.

  Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) Examples include -1-propane, α-acyloxime ester, and thioxanthone.

  The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure. 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.

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

  The gas barrier film of this invention can be used for an organic photoelectric conversion element, for example. Since the gas barrier film of the present invention is transparent when used in an organic photoelectric conversion element, it can be configured to receive sunlight from this side using the gas barrier film as a support. That is, on this gas 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 same), adhering the gas barrier film support and the periphery, and encapsulating the element. Can seal the impact on

  The resin support for organic photoelectric conversion elements is obtained by forming a transparent conductive film on the ceramic layer of the gas barrier film thus formed.

  The transparent conductive film can be formed 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.

  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.

  Subsequently, the organic photoelectric conversion element using these gas barrier films and the resin support body for organic photoelectric conversion elements in which the transparent conductive film was formed is demonstrated.

[Sealing film and manufacturing method thereof]
The present invention is characterized in that a barrier film having the ceramic layer is used as a substrate.

  In the gas barrier film having the ceramic layer, a transparent conductive film is further formed on the ceramic layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated thereon using the transparent conductive film as an anode. Furthermore, another gas barrier film (sealing material) can be used as a sealing film to be sealed by overlapping.

  As another gas barrier film (sealing material) to be used, a barrier film having a ceramic layer having the dense structure according to the present invention can be used. Also, for example, known barrier films used for packaging materials, such as plastic films deposited with silicon oxide or aluminum oxide, dense ceramic layers, and flexible impact relaxation polymer layers are laminated alternately A barrier film having the structure described above can be used as the sealing film. In particular, a resin-laminated (polymer film) metal foil cannot be used as a barrier film on the light extraction side, but it is a low-cost and further low-moisture-permeable sealing material and does not intend to extract light (with transparency). When not required), it is preferable as a sealing film.

  In the present invention, the metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .

  As metal foil, there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil. Among these various metal foils, a particularly preferred metal foil is an Al foil.

  The thickness of the metal foil is preferably 6 to 50 μm. If the thickness is less than 6 μm, depending on the material used for the metal foil, pinholes may be vacant during use, and required barrier properties (moisture permeability, oxygen permeability) may not be obtained. If it exceeds 50 μm, the cost may increase depending on the material used for the metal foil, and the merit of the film may be reduced because the organic photoelectric conversion element becomes thick.

  As a resin film in a metal foil laminated with a resin film (polymer film), various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin , Polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, vinylidene chloride Based resins and the like. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. In addition, a polyethylene resin having a low density or a high density can be used.

  As will be described later, as a method for sealing the two films, for example, a method of laminating a commonly used impulse sealer heat-fusible resin layer, fusing with an impulse sealer, and sealing is preferable. In the sealing between barrier films, if the film thickness exceeds 300 μm, the handling of the film during the sealing operation deteriorates, and it becomes difficult to heat-seal with an impulse sealer or the like, so the film thickness is 300 μm or less. desirable.

(Sealing of organic photoelectric conversion elements)
In this invention, after forming a transparent conductive film on the resin film (barrier film) which has the said ceramic layer concerning this invention, and also forming each layer which comprises an organic photoelectric conversion element, it uses the said sealing film. The organic photoelectric conversion element can be sealed by covering the cathode surface with the sealing film in an environment purged with an inert gas.

As the inert gas, a rare gas such as He and Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 99.99. It is preferably 9% by volume. Preservability is improved by sealing in an environment purged with an inert gas.

  In addition, when sealing the organic photoelectric conversion element using the metal foil laminated with the resin film (polymer film), a ceramic layer is formed on the metal foil instead of the laminated resin film surface, The ceramic layer surface is preferably bonded to the cathode of the organic photoelectric conversion element. When the polymer film surface of the sealing film is bonded to the cathode of the organic photoelectric conversion element, conduction may occur partially.

  As a sealing method for bonding the sealing film to the cathode of the organic photoelectric conversion element, a resin film that can be fused with a commonly used impulse sealer, for example, ethylene vinyl acetate copolymer (EVA), polypropylene (PP) film, polyethylene ( There is a method in which a heat-fusible film such as a PE) film is laminated and fused and sealed with an impulse sealer.

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm. However, when the coating amount of the adhesive is too large, tunneling, oozing, crimping, etc. may occur, so the amount of the adhesive is preferably adjusted to 3 to 5 μm in dry film thickness. It is preferable.

  Hot melt lamination is a method in which a hot melt adhesive is melted and an adhesive layer is applied to a support, and the thickness of the adhesive layer is generally a method that can be set in a wide range of 1 to 50 μm. Commonly used base resins for hot melt adhesives include EVA, EEA, polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. as tackifiers, wax etc. It is added as an agent.

  The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 to 50 μm.

  In general, LDPE, EVA, PP or the like is used as the resin used for the extrusion laminate.

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

(Configuration of organic photoelectric conversion element and solar cell)
Although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to this. There is no restriction | limiting in particular as an organic photoelectric conversion element, 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 power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation 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.

  As with organic EL devices, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer. , (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). A configuration (also referred to as a pin configuration) may be used. 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.

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

  FIG. 2 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element. In FIG. 2, the bulk heterojunction type organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a power generation layer 14 of a bulk heterojunction layer, an electron transport layer 18, and a cathode 13 sequentially stacked on one surface of a substrate 11. Has been.

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

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

  In FIG. 2, the light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  Although not shown in FIG. 2, 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.

  Instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 2 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. It is possible to form a back-contact type organic photoelectric conversion element structure in which the photoelectric conversion unit 15 is disposed thereon.

  As a more preferable configuration, the power generation layer 14 has a so-called p-i-n three-layer configuration (FIG. 3). 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. In FIG. 3, the power generation layer has a structure in which a bulk heterojunction layer 14i is sandwiched between a p-type semiconductor layer 14p and an n-type semiconductor layer 14n.

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

  Below, the material which comprises these layers is described.

  Hereinafter, elements constituting the organic photoelectric conversion element will be described.

(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, circobiphenyl, 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. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  Examples of the conjugated polymer include a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, 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, oligomeric materials instead of polymer materials include thiophene hexamer α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

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

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

  Examples of such a material include materials that can be insolubilized by polymerizing and crosslinking 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 C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₄ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed fullerene, fullerene nanotube, multi-wall nanotube, single-wall nanotube, nanohorn (cone Type), etc., and some of these are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, The fullerene derivative substituted by the amino group, the silyl group, etc. can be mentioned.

  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)
In the organic photoelectric conversion element 10 of the present invention, the hole transport layer 17 can be taken out between the bulk heterojunction layer and the anode, and charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have.

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

(Electron transport layer / hole blocking layer)
In the organic photoelectric conversion element 10 of the present invention, by forming the electron transport layer 18 between the bulk heterojunction layer and the cathode, it becomes possible to more efficiently take out the charges generated in the bulk heterojunction layer. It is preferable to have these layers.

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

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

(Transparent electrode (first electrode))
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.

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

  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, as a material of the intermediate electrode constituting the charge recombination layer 15 required in the case of the tandem configuration as in the above (v) (or FIG. 4), a layer using a compound having both transparency and conductivity is used. Preferably, the material used for the transparent electrode (ITO, AZO, FTO, transparent metal oxide such as titanium oxide, Ag, Al, Au, etc., or a very thin metal layer or metal nanoparticle / metal nanowire) A layer containing the conductive polymer material such as PEDOT: PSS or polyaniline).

  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)
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 a single metal nanowire and to exhibit appropriate light scattering properties. 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 and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire 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. May be.

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

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

(Functional 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. .

  Moreover, you may coat an easily bonding layer etc. as another functional layer.

  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 preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced. 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 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.

(Methods 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.

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

Example 1
(Support)
As a thermoplastic resin support, a substrate of a 125 μm thick polyester film (Tetoron O3, manufactured by Teijin DuPont Films Ltd.) that was easily bonded on both sides was annealed at 170 ° C. for 30 minutes and used.

  The barrier film was produced by adhering an adhesive protective film after forming a bleed-out prevention layer on one side and a smooth layer on the opposite side by the following forming method while transporting the support at a speed of 20 m / min. A roll-shaped barrier film was obtained.

<Production of film having smooth layer and bleed-out preventing layer>
(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the support, and the film was coated with a wire bar so that the film thickness after drying was 4 μm, followed by curing conditions: 500 mJ / cm Under high pressure using a high-pressure mercury lamp in ² air, curing was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the support, and the film was dried with a wire bar so that the film thickness after drying was 4 μm, and then drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 500 mJ / cm ² curing was performed to form a smooth layer.

  The maximum cross-sectional height Rt (p) at this time was 21 nm.

  The maximum cross-sectional height Rt (p) 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. This is the average roughness of the amplitude of fine irregularities measured many times in a section with a measurement direction of 30 μm.

<Preparation of barrier film>
(Formation of barrier layer)
(Formation of silicon compound coating layer)
Next, the silicon compound coating layer of the present invention was formed on the smooth layer of the sample provided with the smooth layer and the bleed-out prevention layer under the following conditions.

Silicon compound layer coating solution Perhydroxypolysilazane (PHPS) 20% by weight dibutyl ether solution (Aquamica NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.)
Adjust the wireless bar count and the perhydroxypolysilazane solution by diluting with dehydrated dibutyl ether so that the film thickness after drying is as shown in Table 1. After coating in a 23 ° C 50% RH environment, 80 ° C for 1 minute A dried sample was obtained (Sample A).

(Formation of silicon oxide thin film by atmospheric pressure plasma CVD)
A thin film was formed on the sample A under the following conditions by atmospheric pressure plasma CVD using an organic silicon compound and oxygen as raw materials. The film thickness is 30 nm. Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes opposed to the roll electrode were installed in parallel to the film transport direction, and raw materials and electric power were supplied to each electrode part to form a thin film as follows.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used. Sample 1 was prepared under the following conditions.

<Plasma CVD layer>
Discharge gas: N ₂ gas Reactive gas 1: Oxygen gas 8% of total gas
Reaction gas 2: TEOS is 0.1% of the total gas
Low frequency side power supply power: 100 kHz, 8 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ²
Samples 2 to 19 were produced in the same manner.

  For samples 2 to 6, the film thickness of the silicon compound layer and the coating / drying temperature were changed as shown in Table 1, and the atmospheric pressure plasma CVD was performed under the condition of no heat treatment after the formation of the silicon compound coated layer. Was performed under the same conditions as Sample 1.

  Regarding Samples 7 to 19, the silicon compound layer thickness, coating drying temperature, heat treatment after formation of the silicon compound coating layer, and silicon compounds used in atmospheric pressure plasma CVD are shown in Table 1, respectively. Went so.

  However, samples 11 and 12 were samples except that 20% by mass dibutyl ether solution of octa (hydroxymethyl) silsesquioxane and hexamethyldisilazane was used instead of Aquamica NAX120-20 (perhydroxypolysilazane (PHPS)), respectively. 1 was prepared.

  Sample 13 was formed by vaporizing a silicon oxide thin film by atmospheric pressure plasma CVD at 40 ° C. using vacuum plasma CVD in the same manner as in Examples 1 to 3 of JP-A-8-281861 instead of TEOS. TMDSO (tetramethoxydisiloxane) was introduced into a vacuum chamber at a flow rate ratio of 0.5% with respect to oxygen, and a 13.56 MHz high frequency parallel plate electrode was maintained while maintaining a vacuum of 13.3 Pa. The sample was produced in the same manner as Sample 1 except that plasma was discharged and the film was formed for a certain period of time so that the film thickness was 30 nm.

  Sample 14 was the same as Sample 11, except that octa (hydroxymethyl) silsesquioxane was applied and dried instead of Aquamica NAX120-20 (PHPS), and then vacuum plasma CVD was performed in the same manner as Sample 13. 1 was prepared.

  Further, Sample 19 was manufactured by repeating the coating and plasma CVD processes twice under the conditions of Sample 1.

  As a comparative example, Sample 7 (Comparative Example 1) was obtained by setting the coating and drying temperature to 140 ° C., and Samples 8 and 9 (Comparative Examples 2 and 3) were subjected to the conditions shown in Table 1 before the plasma CVD of the organosilicon compound. And heat treated. In Sample 10 (Comparative Example 4), the coating and drying temperature was set to 15 ° C. Sample 15 (Comparative Example 5) is reactive gas 1 instead of oxygen gas 8%, hydrogen gas 1%, Sample 16 (Comparative Example 6) is only reactive gas 1, and Sample 17 (Comparative Example 7) is silicon oxide by plasma CVD. No physical layer was formed, and Sample 18 (Comparative Example 8) was directly subjected to plasma CVD on the smooth layer without applying a silicon compound layer.

  Table 1 shows the results of measuring the peak intensity ratio a / b by IR absorption of the coating film before the atmospheric pressure plasma CVD and before drying the silicon compound layer for any sample.

  As described above, barrier film sample No. 1-19 were made.

(Creation of organic photoelectric conversion element)
In advance, the barrier film sample No. 1 was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. 1-19 and the barrier film sample No. which was not bent. 1 to 19 were prepared by depositing a 150 nm thick indium tin oxide (ITO) transparent conductive film (sheet resistance: 10 Ω / □) and patterning it to a width of 2 mm using a normal photolithography technique and wet etching. The 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 prepared in a nitrogen atmosphere.

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

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and the deposition rate is 0.01 nm / second. A second electrode was formed by laminating 0.6 nm of lithium fluoride and then laminating 100 nm of Al metal at a deposition rate of 0.2 nm / second through a shadow mask having a width of 2 mm. Vapor deposition perpendicular to the first electrode pattern to be 2 mm). Organic photoelectric conversion elements SC-101 to 119 were prepared.

  Each obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), an epoxy-based photo-curing adhesive is used as a sealing material with the gas barrier layer side of the same two gas barrier films used for the substrate facing inside. It apply | coated to the gas barrier layer, and the said organic photoelectric conversion element was pinched | interposed between gas barrier films, and was made to adhere | attach, Then, it irradiated with UV light from the one side of the substrate side, and was hardened. Thus, the organic photoelectric conversion element sample No. 1-19 were obtained.

(Evaluation)
<Evaluation of water vapor transmission rate (WVTR)>
The following measurement methods were used for evaluation.

Device vapor deposition device: JEE-400, a vacuum vapor deposition device 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.

Metal that corrodes by reacting with raw material moisture: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
In advance, the barrier film sample No. 1 was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. Using the vacuum deposition device (JEOL-made vacuum deposition device JEE-400) on the ceramic layer surfaces 1 to 19, except for the portion (12 mm × 12 mm 9 locations) of the barrier film sample before attaching the transparent conductive film Masked and vapor deposited metallic calcium. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the barrier property before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the barrier film that was not subjected to the bending treatment.

  The obtained sample with both sides sealed is stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the amount of moisture permeated into the cell from the corrosion amount of metallic calcium Was calculated.

  In addition, in order to confirm that there is no permeation of water vapor other than from the barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm, The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no metallic calcium corrosion occurred even after 1000 hours.

  The following evaluation rank was followed.

Less than 5: 1 × 10 ⁻⁵ g / (m ² · 24 h) 4: 1 × 10 ⁻⁵ g / (m ² · 24 h) or more and less than 1 × 10 ⁻⁴ g / (m ² · 24 h) 3: 1 × 10 ⁻⁴ g / (m ² · 24 h) or more, less than 1 × 10 ⁻³ g / (m ² · 24 h) 2: 1 × 10 ⁻³ g / (m ² · 24 h) or more, 1 × 10 ⁻² Less than g / (m ² · 24 h) 1: 1 × 10 ⁻² g / (m ² · 24 h) or more.

<Evaluation of durability of organic photoelectric conversion device>
<Evaluation of energy conversion efficiency>
About the produced photoelectric conversion element, the light of the intensity of 100 mW / cm ² of a solar simulator (AM1.5G filter) is irradiated, a mask having an effective area of 4.0 mm ² is overlaid on the light receiving portion, and the IV characteristics are obtained. By evaluating the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%), four light receiving portions formed on the same element were measured, respectively, and the following formula 1 The four-point average value of the energy conversion efficiency PCE (%) obtained according to the above 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 over time was evaluated by the conversion efficiency remaining rate after the acceleration test stored for 1000 hours in a temperature 60 ° C., humidity 90% RH environment.

The ratio of conversion efficiency / initial conversion efficiency after accelerated test is
5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20%. In addition, the organic photoelectric conversion element using the barrier film samples 1-19 which repeated bending was evaluated.

<Peel test>
Gas barrier film sample No. A cross-cut test based on JIS K5400 was performed using 1-19. On the surface of the formed thin film, a single-edged razor blade was cut at an angle of 90 ° with respect to the surface, and 11 cuts were made vertically and horizontally at intervals of 1 mm to produce 100 1 mm square grids. A commercially available cellophane tape is affixed on this, and one end is held by hand, and it is pulled and peeled off strongly by force. The ratio of the area where the thin film is peeled to the tape area affixed from the score line is shown as follows: A: Not peeled at all B : The peeled area ratio is less than 10%. C: The peeled area ratio is ranked in 3 ranks of 10% or more, and the results are shown in Table 1.

  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. Furthermore, the organic photoelectric conversion element produced using the barrier film of the present invention is capable of being used in harsh environments. Performance degradation is unlikely to occur. Sample No. in which coating and plasma film formation were repeated twice. No. 19 is less susceptible to performance degradation.

Example 2
Regarding the formation of the silicon oxide layer by atmospheric pressure plasma CVD, the examples except that the atmospheric pressure plasma CVD was performed under the conditions shown in Table 2 for the frequency, power density, and film thickness of the first electric field and the second electric field. 1 was prepared and evaluated in the same manner as Sample 1. The results are shown in Table 2.

  However, the samples 24 and 25 were formed by using a high-frequency power source only by using argon (Ar) instead of nitrogen as a discharge gas for forming the silicon oxide layer by atmospheric pressure plasma CVD.

  Sample 25 was formed by applying and drying octa (hydroxymethyl) silsesquioxane in the same manner as Sample 11 of Example 1 for forming a silicon compound coating layer, and then performing atmospheric pressure plasma CVD.

  Evaluation was performed in the same manner as in Example 1.

  As is apparent from Table 2, the barrier film of the present invention has excellent bending resistance, low water vapor transmission rate (WVTR), and the organic photoelectric conversion device produced using the barrier film of the present invention has a harsh environment. Under performance degradation is unlikely to occur.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Anode 13 Cathode 14 Power generation layer (bulk heterojunction layer)
14p p-type semiconductor layer 14i bulk hetero junction layer 14n n-type semiconductor layer 14 'first power generation layer 15 charge recombination layer 16 second power generation layer 17 hole transport layer 18 electron transport layer

Claims (7)

  After forming a thin film by applying and drying a liquid containing at least one silicon compound at 20 ° C. to 100 ° C. on at least one surface of the substrate, the thin film is subjected to a heat treatment at 140 ° C. or higher. And a thin film of silicon oxide is laminated on the substrate on which the thin film has been applied by plasma CVD using a reactive gas containing at least one organic silicon compound and oxygen. A method for producing a film.   The method for producing a barrier film according to claim 1, wherein the liquid containing the at least one silicon compound is applied and dried at 20 ° C. to 80 ° C.   The method for producing a barrier film according to claim 1 or 2, wherein the liquid containing the silicon compound is a liquid containing at least polysilazane. For thin film obtained by the coating and drying, in IR measurement, attributed to Si-O absorption attributed to the (asymmetric) stretching vibration absorption attributed to Si-N stretching vibration (1080 cm ^-1) (960 cm ^-1) The method for producing a barrier film according to claim 1, wherein the ratio (Si—O) ¹⁰⁸⁰ / (Si—N) ^{960 to} is 0.1 or more and 3 or less.   The method for producing a barrier film according to any one of claims 1 to 4, wherein the silicon oxide thin film is formed by a plasma CVD method under an atmospheric pressure or a pressure in the vicinity of atmospheric pressure.   The said plasma CVD method is performed under a 2 or more types of high frequency electric field, The manufacturing method of the barrier film of any one of Claims 1-5 characterized by the above-mentioned.   The barrier film according to any one of claims 1 to 6, comprising a step of applying and drying the liquid on an exposed surface of a smooth layer provided on at least one surface of the substrate. Production method.

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