JP2011073417A - Barrier film, method of producing barrier film, and organic photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film that can attain extremely high barrier performance, that has transparency and applicability to roll-to-roll, and that thereby possesses required adaptability to production such as bending resistance, scratch resistance, etc., as well as low cost, to provide a method of manufacturing the barrier film, and also to provide an organic photoelectric conversion element using the barrier film as a substrate. <P>SOLUTION: The barrier film has, on a base material, a barrier layer containing at least one layer of silicon atoms and oxygen atoms and an overcoat layer on top of the barrier layer. The barrier film is characterized in that the barrier layer is the layer formed by processing a layer composed of polysilazane and that the overcoat layer is provided with inorganic nanoparticles having a number average particle size of 1-200 nm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a barrier film used for a package such as an electronic device, or a material such as a plastic substrate such as an organic EL element, a solar cell, or a liquid crystal, a manufacturing method thereof, and an organic photoelectric conversion element. The present invention relates to a barrier film excellent in productivity.

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

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

  In particular, transparent substrates, which are applied to display elements such as organic electroluminescence and liquid crystal, and solar cells, have recently achieved high productivity with the aim of lowering the price in addition to demands for weight reduction and size increase. High demands such as the ability to produce roll-to-roll, high long-term reliability and high degree of freedom, and the ability to display curved surfaces are added, making it difficult to increase the area with heavy cracks. Instead of glass substrates, film substrates such as transparent plastics have begun to be adopted. For example, an example using a polymer film as a substrate is disclosed (see Patent Document 1).

As the transparent resin film, for example, since a film having a relatively high water and oxygen permeability such as polyethylene terephthalate (hereinafter abbreviated as “PET”) is inexpensive because it is general-purpose, the film substrate such as transparent plastic is made of glass. However, there is a problem that the gas barrier property is inferior. For example, when used as a substrate of an organic photoelectric conversion element, there is a problem that when a base material with poor gas barrier properties is used, water vapor, air, or oxygen penetrates and the performance is likely to deteriorate with time. It has been found that the water vapor transmission rate at this time is about 1 × 10 ⁻² g / m ² · day.

  Here, it supplements about the high productivity in a roll-to-roll. As a method for forming a barrier layer having a high gas barrier property, it is usual to use a vapor deposition method. However, a general vacuum film-forming system in the vapor deposition method is a batch process and is difficult to cope with roll-to-roll. In addition, the vapor deposition method is extremely low in terms of film formation regardless of vacuum or atmospheric pressure.

  On the other hand, the coating method is easy to roll-to-roll and has high productivity, but a material for forming a barrier layer forming method (film formation) with high gas barrier properties is a problem.

  In view of this, there has been proposed a method of forming a gas barrier layer by a method of applying a coating liquid containing polysilazane as a main component and then performing a heat treatment instead of the vapor deposition method which is a vapor deposition method. Polysilazane is known to be converted to silica at 400-500 ° C, but unlike glass substrates and silicon wafers, it is applicable from the viewpoint of heat resistance in film substrates such as the above-mentioned roll-to-roll produced transparent plastics. I could not. In order to improve this point, various types of catalysts for lowering the conversion temperature have been studied. However, the catalyst remaining in the coating film has a problem that gas barrier properties and transparency are lowered. On the other hand, even when low-temperature treatment is possible, a new problem in production aptitude has been generated in which the treatment (conversion) time is increased accordingly.

  As a surface treatment instead of the heat treatment, a one-frequency plasma treatment technique using discharge is known (see Patent Document 2). These have the advantage of lowering the treatment temperature for silica conversion, however, none of these techniques has a sufficient function as a barrier layer. This is due to incomplete conversion to silica, residual impurities in the barrier layer, generation of voids due to volatilization of volatile substances, material composition that is insufficiently flexible, and inappropriate production methods (heat load is For example, a crack (crack) of the barrier layer caused by a large size).

Accordingly, there has been a demand for further improvement in gas barrier properties such that the water vapor transmission rate is significantly lower than 1 × 10 ⁻² g / m ² · day.

  In addition, in order to perform roll-to-roll production that achieves high productivity, in addition to having flexibility, it is necessary to provide advanced bending resistance and winding resistance (scratch resistance). It is essential. For example, when used as a substrate for an organic photoelectric conversion element, the life of the product is significantly reduced even with a minute scratch. However, a technique for imparting such high bending resistance and scratch resistance to the polysilazane coating layer has not been known.

JP-A-2-251429 JP 2007-237588 A

  The object of the present invention is to achieve extremely high barrier performance, have transparency, and can be applied to roll-to-roll, so it is inexpensive and has necessary production suitability such as bending resistance and scratch resistance. It is in providing a barrier film and its manufacturing method, and also in providing the organic photoelectric conversion element which used this barrier film as a board | substrate.

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

  1. A barrier film having a barrier layer containing at least one silicon atom and oxygen atom on a substrate and an overcoat layer on the barrier layer, wherein the barrier layer is made of polysilazane. A barrier film, wherein the overcoat layer has inorganic nanoparticles having a number average particle diameter of 1 to 200 nm.

  2. 10. The barrier film as described in 1 above, wherein the surface of the barrier layer has a ten-point average roughness Rzjis of 10 nm to 90 nm.

  3. 10. The barrier film as described in 1 above, wherein a ten-point average roughness Rzjis of the surface of the barrier layer is 10 nm to 30 nm.

  4). The organic photoelectric conversion element produced using the barrier film of any one of said 1-3.

  5. 4. The method for producing a barrier film according to any one of 1 to 3, wherein after applying a coating liquid containing polysilazane on a substrate, the polysilazane is converted into silicon by plasma treatment of at least two frequencies in a discharge gas atmosphere. The manufacturing method of the barrier film characterized by forming a barrier layer by converting into an oxide.

  According to the present invention, it is possible to obtain a barrier film that is excellent in production stability and handleability, has transparency and roll-to-roll suitability, and can achieve high barrier performance. Furthermore, it is possible to provide a barrier film useful for a resin substrate for an organic photoelectric conversion element having excellent barrier properties, a production method thereof, and an organic photoelectric conversion element using the substrate.

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

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

  The barrier film of the present invention will be described. The barrier film of the present invention has a barrier layer made of polysilazane on a resin film substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and further an OC layer (overcoat layer). Moreover, the barrier film of this invention may laminate | stack two or more barrier layers.

(Barrier layer)
The barrier layer is formed by applying polysilazane and then performing oxidation treatment to convert the layer into a layer containing silicon atoms and oxygen atoms. In particular, as the oxidation treatment, plasma treatment of at least two frequencies or more can be converted to a film having a dense average surface density of the barrier layer at a low temperature, and in addition, the visible light transmittance (transparency) is improved. It is preferable in that it can be increased.

Specifically, the compound constituting the barrier layer is preferably an inorganic oxide containing silicon, and includes a ceramic layer such as silicon oxide or silicon oxynitride. With such a barrier layer, the water vapor transmission rate measured according to the JISK7129B method is 10 ⁻⁴ g / m ² / day or less, preferably 10 ⁻⁵ g / m ² / day or less, and the oxygen transmission rate is 0.00. 01ml ^/ m 2 ^/ day or less, preferably the film is obtained as a base material excellent resin film barrier property or less 0.001ml ^/ m 2 ^/ day.

  The organic photoelectric conversion element using the barrier film having the water vapor transmission rate as a substrate does not have a deterioration in performance over time due to the ingress of water vapor.

  In addition, when used in applications requiring high water vapor barrier properties such as organic EL displays and high-definition color liquid crystal displays, particularly in the case of organic EL display applications, there is no occurrence of dark spots and the display life of the display can be extended. I can do it.

When the composition ratio of oxygen atoms to silicon atoms is a value close to 2.0, the composition approaches that of SiO ₂ . If SiO ₂ average density (g / cm ³⁾ becomes 2.2. If a composition close to SiO ₂ is formed, a dense structure can be formed and a sufficient barrier property is expected.

  By providing the barrier layer by coating, the surface smoothness is high (the ten-point average roughness Rzjis (JIS B 0601: 2001) of the barrier layer surface is small) and the film thickness is converted to a uniform barrier layer. Therefore, it is possible to reduce the stress concentration at the time of bending, increase the bending resistance, and enable roll-to-roll production.

  In order to exhibit such characteristics, the 10-point average roughness Rzjis of the barrier layer surface layer is preferably 10 nm to 90 nm. Further, Rzjis is more preferably 10 nm to 30 nm.

  In order to improve the smoothness of the barrier layer, a method of applying a liquid is preferable to chemical vapor deposition of the barrier layer, and further, preparation in an environment with a low degree of foreign matter and a high cleanliness is required. Specifically, it is necessary that the cleanliness is higher than that of class 1000.

(Method for forming barrier layer)
As a method for forming the barrier layer of the present invention, a method in which a barrier layer containing silicon oxide is formed by applying a coating solution containing at least one polysilazane on a substrate and then performing plasma treatment is preferable.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 20 nm to 100 μm, more preferably about 20 nm to 10 μm, and most preferably about 20 nm to 1 μm.

  Next, it is preferable to anneal the applied film. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 2 hours. By performing annealing in such a range, a part of polysilazane reacts to immobilize molecules, and a barrier film having good characteristics can be obtained. Specifically, it is assumed that molecules are immobilized by the following mechanism. The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30% RH to 90% RH, more preferably 40% RH to 80% RH.

  The silicon compound for forming the barrier layer of silicon oxide is higher in film-formability when applied to the surface of the barrier film substrate than when supplied as a gas as in CVD (vapor phase growth method). Therefore, it is possible to form a barrier layer with high productivity, more uniform and smooth. It is well known that in the case of a CVD method or the like, a foreign material called unnecessary particles is generated in the gas phase simultaneously with the step of depositing the source material having increased reactivity in the gas phase on the substrate surface. By preventing the raw material from being present in the plasma reaction space, the generation of these particles can be suppressed. This is superior in improving the bending resistance described above.

  The silicon compound contained in the coating solution is polysilazane. A typical example is perhydropolysilazane, but a part of hydrogen may be substituted with an organic group such as a methyl group. Alternatively, an organic group may be introduced into the mother skeleton.

  Specifically, commercially available products of polysilazane, including non-catalytic ones, are manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. When these are applied, in order to suppress the reaction between the coating liquid and moisture, it is preferable to use a solvent that does not easily contain moisture, such as xylene, dibutyl ether, solvesso, turpentine, or a dehydrating solvent.

  As another method other than the above-described plasma treatment for converting polysilazane to a silicon oxide compound, for example, heat treatment (400 to 500 ° C.) is known. Unlike glass substrates and silicon wafers, the roll-to-roll method of the present invention is used. In the case of a film substrate such as a transparent plastic capable of roll production, plasma treatment is preferable from the viewpoint of heat resistance. It may be applicable to some special engineering plastic films, but these are more expensive than general-purpose plastic films, and there are problems such as the inability to obtain colorlessness / transparency. It was. The reason why it is difficult to obtain colorlessness / transparency of such a heat-resistant plastic is generally attributed to the fact that a double bond conjugated system represented by an aromatic bond has visible light absorption. A typical example of such a film is polyimide (PI).

  In order to improve this point, various catalysts for lowering the conversion temperature have been studied. However, the catalyst remaining in the coating film has a disadvantage that the barrier property and transparency are lowered.

Moreover, the function as a barrier layer did not reach the plasma treatment, and the barrier property such that the water vapor transmission rate was significantly lower than 1 × 10 ⁻³ g / m ² · day could not be obtained.

  The barrier layer of the present invention may be a single layer or a plurality of similar layers, and the barrier properties can be further improved by a plurality of layers.

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

  By supplying oxygen having an oxidizing property as the reaction gas, the oxidation reaction can be advanced. As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost. Specifically, it is described in International Publication No. 2007/026545 pamphlet and the like.

  The electric field applied to generate plasma is obtained by applying two or more electric fields having different frequencies to the discharge space, and in particular, applying an electric field in which the first high-frequency electric field and the second high-frequency electric field are superimposed is a barrier property. It is preferable in terms of improvement.

The frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field are:
ω1 <ω2
And the relationship between the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge starting electric field strength IV is:
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By taking such a discharge condition, for example, a discharge gas having a high discharge start 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. I can do it.

  When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field intensity IV is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field intensity is V1 ≧ 3.7 kV / mm. By applying it as mm, the nitrogen gas can be excited and brought into 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 1 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. In addition, it is possible to increase the plasma density by a high power density and form a dense and high-quality thin film.

  In order to be incorporated into the final form of an organic photoelectric change element or the like, it is required to be transparent. That is, in order to obtain a barrier film having a high barrier property characterized by having a visible light transmittance of 400 to 800 nm of 70% or more and 90% or less, a dense barrier layer convertible layer at a low temperature on a transparent plastic film. The two-frequency AGP process using the first and second high-frequency electric fields is excellent as the processing (conversion) method.

  AGP is atmospheric pressure plasma, and AGP treatment is a surface treatment by irradiating atmospheric pressure plasma, and means surface modification by application of energy of atmospheric pressure plasma, that is, conversion treatment to a barrier layer in the present application. To do.

(Overcoat layer)
An overcoat layer (hereinafter referred to as an OC layer) is provided on the barrier layer. The OC layer preferably contains inorganic nanoparticles having a number average particle diameter of 1 to 200 nm, and additionally contains a polymer as a main component.

  The polymer is preferably a resin cured using the following photosensitive resin and photopolymerization initiator.

  Examples of the photosensitive resin include 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, and polyester acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyether acrylate, polyethylene glycol acrylate, and 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 the reactive monomer 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, 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, di Cyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, Dil 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, tripropyl 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- Trimethyl-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 OC layer is blended with the inorganic nanoparticles and, if necessary, other components such as the polymer, and prepared as a coating solution with a diluting solvent used as necessary, and the coating solution is conventionally applied to the substrate surface. After coating by a known coating method, it can be formed by irradiating with ionizing radiation and curing. As a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The thickness of the OC layer (overcoat layer) in the present invention is 0.5 to 10 μm, preferably 2 to 7 μm. By making it 0.5 μm or more, it becomes easy to make the winding resistance (scratch resistance) sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties, and the OC layer is made of a transparent polymer film. When it is provided on one side, curling of the barrier film can be easily suppressed.

(Inorganic nanoparticles)
The inorganic nanoparticles are inorganic particles having a number average particle diameter of 1 to 200 nm, and a wide variety of materials such as metals, metal oxides, and nonmetals are candidates, but metal oxides are particularly preferable from the viewpoint of transparency. .

_{There is} no particular restriction as the metal _{oxide, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, ZnO, SnO 2, In 2 O 3, BaO, SrO, CaO, MgO, VO 2, V 2 O 5, _{CrO 2, MoO 2, MoO 3} , MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO 4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In2O 5, Cd 2 Examples thereof include SnO ₄ , CdIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , Zn ₂ In ₂ O _{5 and the} like. These may be used alone or in combination of two or more.

  In order to obtain a dispersion of inorganic nanoparticles, adjustments may be made in accordance with recent academic papers. However, using commercially available nanodispersions results in inorganic nanoparticles having a uniform particle size and a good dispersion state. There is excellent.

  Specifically, there are dispersions (dispersions) of various metal oxides such as NANOBYK series manufactured by Big Chemie Japan Co., Ltd. and NanoDur manufactured by Nanophase Technologies, etc., dispersions in solvents, UV curable dispersions, etc. There is.

(Number average particle size)
The inorganic nanoparticles were photographed with an electron microscope, and the diameter of the circumscribed circle of each particle on the image was measured to obtain the particle size of each particle. The number average particle size is determined from the particle size of arbitrary 100 particles. If the number average particle size is 200 nm or less, the OC layer is excellent in flexibility, and therefore the scratch resistance and the barrier property of the bent barrier film are excellent. If it is 50 nm or less, it is more suitable from the viewpoint of transparency and haze. The smaller the particle size, the better. However, a particle size of 1 nm or more is used from the viewpoint of production load and cost load.

  Also, the above particle diameter is suitable for achieving both the flexibility of the OC layer and the adhesiveness to the barrier layer, and within this range, it is appropriately used in consideration of the original transparency of the inorganic nanoparticle material.

  The amount of inorganic nanoparticles added to the OC layer is preferably 1 to 70% by mass with respect to the polymer component. If it is 1% by mass or more, the adhesiveness to the barrier layer is good, and if it is 70% by mass or less, transparency and flexibility including haze are excellent. Is used as appropriate in consideration of the transparency and particle size of the material.

  In order to further improve the barrier property, a layer having a silicon compound may be further provided on the OC layer. Hereinafter, layers other than the barrier layer and the OC layer will be described.

(Base material)
Next, the base material used in the barrier film of the present invention will be described. The substrate of the present invention is preferably a film substrate having a smooth layer, but is not particularly limited as long as it is formed of an organic material capable of holding a barrier layer having a barrier property described later. .

  Specifically, acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), Silsesquioki having an organic-inorganic hybrid structure such as polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films. A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having Sun as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin can be used. 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. As for the thickness of a base material, about 5-500 micrometers is preferable, More preferably, it is 25-250 micrometers.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as a photoelectric conversion element. is there.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate 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. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, in the resin film base material which concerns on this invention, you may corona-treat before forming a barrier layer.

(Anchor coating agent layer)
Furthermore, an anchor coat agent layer may be formed on the surface of the substrate according to the present invention for the purpose of improving the adhesion with the barrier layer. 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 a substrate 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)
The base material of the present invention is preferably provided with a smooth layer. The smooth layer according to the present invention flattens the rough surface of the transparent resin film substrate on which protrusions and the like exist, or fills irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the transparent resin film substrate. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive composition containing a photosensitive resin and a photopolymerization initiator.

  In addition, regarding the bending resistance to be improved in the present application, it is desirable that the barrier layer has a uniform film thickness. This is to relieve stress concentration during bending. From this viewpoint, it is preferable to provide a smooth layer.

  As the photosensitive resin and polymerization initiator for the smooth layer, the tourism resin and polymerization initiator used for the OC layer can be preferably used.

  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 defined by JIS B 0601, and the ten-point average roughness Rzjis is preferably 10 nm or more and 30 nm or less. If Rzjis is 10 nm or more, the coating property is good when the coating means is in contact with the smooth layer surface by a coating method such as a wire bar or a wireless bar at the stage of coating a silicon compound described later. Moreover, if it is 30 nm or less, it is easy 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.

(Addition of reactive silica particles to the 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 setting the average particle size in such a range, the anti-glare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and 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. By adding 20% or more, adhesion with the barrier layer is improved. On the other hand, if it exceeds 60%, the film may be bent or cracked when heat-treated, or the optical properties such as transparency and refractive index of the 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 on only one surface of the molecular film, curling of the smooth film can be easily suppressed.

(Bleed-out prevention layer)
The barrier film of the present invention, when heating a film having a smooth layer, for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film substrate to the surface and contaminate the contacting surface. It is preferable to provide a bleed-out prevention layer on the opposite surface of the substrate having a smooth layer.

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

  The bleed-out prevention layer can contain an unsaturated compound having a polymerizable unsaturated group as a hard coat agent. As the unsaturated organic compound having a polymerizable unsaturated group, 2 Examples thereof include polyunsaturated organic compounds having the above polymerizable unsaturated groups, unitary unsaturated organic compounds having one polymerizable unsaturated group in the molecule, and the like.

  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 bleedout prevention layer 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 prepared as a coating solution by mixing a hard coat agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the material surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

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

(Layer with silicon compound)
The barrier film of the present invention is formed by applying a silicon compound on the OC layer by applying a sputtering method, an ion assist method, a plasma CVD method described later, a plasma CVD method under atmospheric pressure or a pressure close to atmospheric pressure described later, and the like. The layer which has it may be formed by laminating | stacking.

  Even if a defect occurs in the barrier layer and the OC layer, gas permeation from the defect portion can be suppressed by the presence of the layer having the silicon compound, and higher barrier properties can be realized.

  The thickness of the layer having these silicon compounds in the present invention is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 1 to 2000 nm. This is because when the thickness of the layer having a silicon compound is smaller than the above range, a uniform film cannot be obtained, and it is difficult to improve the gas barrier property. In addition, when the thickness of the layer having a silicon compound is thicker than the above range, it is difficult to maintain the flexibility of the barrier film. This is because cracks may occur.

  If the thickness is less than this, there are many film defects, and further improvement in moisture resistance cannot be obtained. The larger the thickness, the higher the moisture resistance theoretically. However, when the thickness is too large, the internal stress becomes unnecessarily large, and it is easy to break, so that the moisture resistance cannot be improved.

  In the present invention, the layer having the silicon compound is preferably 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.

  As a method for forming a layer having a silicon compound, atmospheric pressure plasma CVD does not require a decompression chamber or the like among the above methods, and high-speed film formation is possible and has high productivity.

  A layer having a silicon compound obtained by a plasma CVD method or a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure is composed of an organic metal compound, decomposition gas, decomposition temperature, input power, etc. that are raw materials (also referred to as raw materials). By selecting the conditions, ceramic layers such as metal carbides, metal nitrides, metal oxides, metal sulfides, etc., and mixtures thereof (metal oxynitrides, metal nitride carbides, etc.) can be formed separately, which is preferable.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the 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.

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

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

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

(Organic photoelectric conversion element)
The barrier film can be used as various sealing materials and films.

  This barrier film can be used for an organic photoelectric conversion element, for example. Since the barrier film is transparent when used in an organic photoelectric conversion element, it can be configured to receive sunlight from this side using the barrier film as a main part of the substrate. That is, on the barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the substrate is used as an anode, a porous semiconductor layer is provided thereon, a cathode made of a metal film is formed to form an organic photoelectric conversion element, and another sealing is formed thereon. The organic photoelectric conversion element can be sealed by stacking the material (may be the same as the barrier film) and adhering the substrate and the surrounding by the barrier film and encapsulating the element, thereby allowing moisture such as outside air or oxygen The influence of the gas on the device can be sealed.

  The resin substrate for organic photoelectric conversion elements is obtained by forming a transparent conductive film on the OC layer of the barrier film. 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 the resin substrate for organic photoelectric conversion elements in which the transparent conductive film was formed on these barrier films is demonstrated.

(Sealing film)
One feature of the present invention is that a barrier film having the barrier layer is used as a substrate.

  In the barrier film having the barrier layer, a transparent conductive film is further formed on the barrier layer. Using this as an anode, a layer constituting the organic photoelectric conversion element and a layer serving as a cathode are laminated thereon. Further, another barrier film is used as a sealing film to be sealed by overlapping.

  As another example of the sealing film, a metal foil laminated with a resin film is used. Although this cannot be used as a barrier film on the light extraction side, it is a sealing material having a low cost and a low moisture permeability, and is preferable as a sealing film when light extraction is not intended (transparency is not required).

  A preferred metal foil is an Al foil.

  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 is 300 μm or less, the film is easy to handle at the time of sealing work, and heat fusion with an impulse sealer or the like is easy, so the film thickness is 300 μm or less. desirable.

[Encapsulation of organic photoelectric conversion elements]
In this invention, after forming a transparent conductive film on the resin film (barrier film) which has the said barrier layer based on this invention, and forming each layer of an organic photoelectric conversion element on the produced resin substrate for organic photoelectric conversion elements, Using the 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.

  Further, when sealing the organic photoelectric conversion element using the metal foil laminated with the resin film, a barrier layer is formed on the metal foil instead of the laminated resin film surface. It is preferable to bond to the cathode of the organic photoelectric conversion element. When the resin 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 substrate, and the thickness of the adhesive layer is generally set within 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 substrate with a die, and the thickness of the resin layer can be generally 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, The anode and the cathode, and the electric power generation layer (a layer in which p-type semiconductor and n-type semiconductor are mixed, a bulk heterojunction layer, i layer) sandwiched between them are 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.

(A) Anode / power generation layer / cathode (B) Anode / hole transport layer / power generation layer / cathode (C) Anode / hole transport layer / power generation layer / electron transport layer / cathode (D) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (E) Anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

  The above (A) to (E) are examples of preferable material layer configurations. For example, the hole transport layer and the electron transport layer of (E) may be omitted by selecting a suitable material. For example, instead of the electron transport layer / intermediate electrode / hole transport layer of (E), a charge recombination layer serving as an intermediate electrode and a hole transport layer or an electron transport layer may be used. Although omission of such a layer is highly difficult as a material technology, it is suitable for the manufacturing process.

  In the above (A) to (E), 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. A junction may be formed, or a bulk heterojunction mixed in one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like the organic EL element, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer, so that the configuration having them ((B), ( C)) is preferred.

  In addition, the power generation layer itself also increases the rectification of holes and electrons (selection of carrier extraction), so that the power generation layer is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (D). A configuration (also referred to as a pin configuration) may be used. Moreover, in order to improve the utilization efficiency of sunlight, a tandem configuration (configuration (E)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

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

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

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

  The substrate 11 is a barrier film, and is a member that holds the anode 12, the power generation layer 14, and the cathode 13 that are sequentially laminated on the barrier layer side. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member.

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

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

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

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

  Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency). FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second power generation layer 16, and then the counter electrode 13 are stacked. By stacking, a tandem structure can be obtained. The charge recombination layer 15 has both functions of an intermediate electrode and a hole transport layer or an electron transport layer.

  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.

(P-type semiconductor material)
Examples of the p-type semiconductor material used in the power generation layer (bulk heterojunction layer) of the organic photoelectric conversion device according to 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, zeslen, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above-mentioned condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A. A pentacene derivative having a substituent described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. 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.

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO 2008/000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO 2008/000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007 p4160, 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, not polymer materials, include thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, 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 materials include materials that can be insolubilized by polymerizing the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Alternatively, a soluble substituent reacts and becomes insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834. Materials etc. can be mentioned.

(N-type semiconductor material)
The n-type semiconductor material used for the bulk heterojunction layer of the organic photoelectric conversion device according to the present invention is not particularly limited. For example, perfluorocarbons such as fullerene, octaazaporphyrin, etc., in which hydrogen atoms of a p-type semiconductor are substituted with fluorine atoms. (Perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized products thereof Examples thereof include a polymer compound contained as a skeleton.

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

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

(Hole transport layer)
The organic photoelectric conversion element 10 of the present invention has a hole transport layer 17 in the middle of the bulk heterojunction layer and the anode in order to more efficiently extract charges generated in the bulk heterojunction layer. Preferably it is.

  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 compounds described in WO2006 / 019270, etc. 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)
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 given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side. Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

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

(Transparent electrode (first electrode))
The cathode and anode of the transparent electrode of the organic photoelectric conversion device according to the present invention are not particularly limited and can be selected depending on the device configuration, 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 of the organic photoelectric conversion element according to the present invention may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

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

  The counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), inorganic nanoparticles made of carbon, nanowires, or nanostructures. A wire dispersion is preferred because a transparent and highly conductive counter electrode can be formed by a coating method.

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

(Intermediate electrode)
Further, the material of the intermediate electrode required in the case of the tandem structure as in (E) (or FIG. 3) is preferably a layer using a compound having both transparency and conductivity. (Such as ITO, AZO, FTO, transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, etc., or layers containing inorganic nanoparticles / nanowires, PEDOT: PSS, For example, a conductive polymer material such as polyaniline) can be used.

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating, and with such a configuration, the process of forming one layer This is preferable because it can be omitted.

(Metal nanowires)
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 said metal nanowire, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, it is a noble metal (For example, gold | metal | money, platinum, silver, palladium, rhodium, iridium, ruthenium) , Osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin, and more preferably at least silver from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

  There is no restriction | limiting in particular in the manufacturing means of the said metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-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.

(Optical function layer)
The organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight. Examples of the optical functional layer include an antireflection film, a condensing layer such as a microlens array, and a light diffusion layer that can scatter light reflected by the cathode and re-enter the power generation layer. You may provide in the base material side.

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

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

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

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

(Film forming method / Surface treatment method)
Formation method of various layers Bulk heterojunction layer in which electron acceptor and electron donor are mixed, and formation method of transport layer / electrode include vapor deposition method, coating method (including cast method and spin coat method), etc. It can be illustrated. 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 evaporation at the time of 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
(Production of Sample 1-1 (Comparative Example))
(Base material)
As a base material for the thermoplastic resin, a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was annealed and heated at 170 ° C. for 30 minutes.

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

(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7535) manufactured by JSR Corporation is applied to one side of the base material, applied with a wire bar so that the film thickness after drying is 4 μm, and then curing conditions: 1 Curing was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer under a pressure of 0.0 J / cm ^{2 and} using a high-pressure mercury lamp.

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

  The ten-point average roughness Rzjis at this time was 16 nm.

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

(Formation of barrier layer)
Next, the barrier layer was formed on the smooth layer of the base material provided with the smooth layer and the bleed-out preventing layer under the conditions shown below.

(Barrier layer coating)
A 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN120-20) was applied with a wireless bar so that the film thickness after drying was 0.3 μm. A sample was obtained after drying. The applied film was annealed by treatment for 30 minutes in an atmosphere at a temperature of 80 ° C. and a humidity of 40% RH.

(Heat treatment)
Further, a barrier layer was formed by treatment at 450 ° C. for 1 hour in an oven. 1-1 was obtained. Sample No. 1-1 cracked the barrier layer.

(Preparation of barrier film sample Nos. 1-2 to 4-2)
The base material of Sample 1-1 is changed to that shown in Tables 1 to 4, and further, a method for forming a barrier layer material (coating, vapor deposition method, AGP barrier, magnetron sputtering), treatment method (temperature and time of heat treatment) , AGP treatment conditions, temperature / time during AGP barrier film formation, temperature / time during vacuum deposition, temperature / time during magnetron sputtering), a combination of two layers obtained by laminating the film and the barrier layer formed by the treatment Sample 1-1, except that (barrier layer 2 layer configuration only) and OC layer (thickness, resin, inorganic nanoparticle material, content, number average particle diameter) are as shown in Tables 1 to 4 In the same manner as in Sample No. 1-2 to 4-2 was obtained.

  In addition, (1) base material, (2) barrier layer material film forming method, (3) barrier layer treatment / film forming conditions, and (4) OC layer in Tables 1 to 4 are described below.

(1) Base material The base material of Sample 2-1 was annealed at 170 ° C. for 30 minutes with 125 μm-thick PEN (polyethylene naphthalate, manufactured by Teijin DuPont Films, Inc., manufactured by Teonex Q83). What was done was used.

  Furthermore, as for the film thickness difference of PET, 75 μm thickness is 38 μm thickness using a base material obtained by annealing heat treatment at 170 ° C. for 30 minutes at 170 ° C. on a polyester film (Teijin DuPont Films Co., Ltd., Tetoron O3) that is easily bonded on both sides Used a base material obtained by annealing heat treatment at 170 ° C. for 30 minutes on a polyester film (Tetron HS, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides.

(2) Barrier layer material film forming method (Coating)
As shown in Tables 1 and 3, a barrier layer coating solution (polysilazane or a mixture of polysilazane and catalyst shown below) was applied.

(Barrier layer coating solution)
The coating solution is mainly composed of perhydropolysilazane (also referred to as PHPS), and the following catalysts are added as shown in Tables 1 to 4. Perhydropolysilazane was selected from Aquamica NL120A-20, Aquamica NAX-120-20, Aquamica NN320-20, and Aquamica NN-120-20CL as shown in Tables 1 to 4. All are manufactured by AZ Electronic Materials.

  As the amine catalysts described in Tables 1 and 3, NAXCAT-10DB manufactured by Nease Performance Chemicals was used.

  As the Pd catalysts described in Tables 1 and 3, palladium propionate was used.

(2 frequency AGP barrier)
An AGP barrier using plasma generated by simultaneously applying a low-frequency and high-frequency electric field at the temperatures and times described in Tables 1 and 3. (AGP barrier is a method in which a reactive gas introduced into atmospheric pressure plasma reacts and deposits on a substrate to form a barrier layer.) The temperatures in Tables 1 to 4 are all The temperature of the substrate is shown.

  Other conditions are shown below.

Discharge gas: N ₂ gas Reaction gas 1: 8% of oxygen gas with respect to the total gas
Reaction gas 2: TEOS (tetraethoxysilane) is 0.1% of the total gas
Low frequency side power supply power: 100 kHz 2 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ² .

  The discharge gas and the reaction gas are mixed and at normal pressure, and the amount (%) of the reaction gas indicates a mole fraction.

(Al ₂ O ₃ vacuum deposition)
On the smooth layer, aluminum oxide was formed to a thickness of 50 nm by vacuum deposition at the temperature and time described in Tables 1 to 4.

(ITO magnetron sputtering)
On the smooth layer, ITO (indium tin oxide) was formed to a thickness of 100 nm by magnetron sputtering at the temperature and time described in Tables 1 to 4.

(Construction of two barrier layers)
As shown in Tables 1 to 4, Samples 3-1 to 4-2 are examples in which two layers are laminated by combining various barrier layers. Below, the structure which laminated | stacked the barrier layer formed by the said film forming and a process in two layers is shown. When providing the OC layer, the OC layer is applied after the two barrier layers are stacked.

(Coating + 2 frequency AGP barrier)
In Sample 3-1, a barrier layer was laminated by applying a 2-frequency AGP barrier at 120 ° C. for 12 minutes on a layer that had been subjected to heat treatment (120 ° C. for 6 minutes) by applying polysilazane.

  In Sample 4-1, after applying polysilazane, a barrier layer was laminated by a dual frequency oxygen AGP barrier for 12 minutes at 120 ° C. on a barrier layer formed by performing a double frequency oxygen AGP treatment (6 minutes in a 120 ° C. environment). did.

(Lamination of coating)
For sample 3-2, polysilazane coating and 1-frequency oxygen AGP treatment 2 (6 minutes in a 120 ° C. environment) were repeated twice.

  For Sample 4-2, polysilazane coating and dual-frequency oxygen AGP treatment (6 minutes in a 120 ° C. environment) were repeated twice in the same manner, so that the barrier layer was formed as a laminate of two layers.

(Lamination of ITO magnetron sputtering)
In Sample 3-3, the ITO magnetron sputtering (80 ° C., 30 minutes) was repeated twice to laminate an ITO barrier layer.

(Barrier layer treatment)
After coating, the polysilazane coating solution is subjected to heat treatment or the following AGP treatment as shown in Tables 1 and 3 to form a barrier layer.

(AGP treatment (atmospheric pressure plasma treatment))
After applying the polysilazane as described above, the AGP treatment (atmospheric pressure plasma treatment) specified in Tables 1 and 3 is converted to silicon oxide to form a barrier layer. Performed at time conditions.

(AGP processing conditions)
(Plasma processing equipment)
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 portion, and the coated surface was plasma-treated as follows.

  Here, the roll electrode and the rod-like electrode used were a metal base material coated with 1 mm of alumina (dielectric) by ceramic spraying. 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. The power source used here was a high-frequency power source (80, 100 kHz) manufactured by Applied Electronics, or a high-frequency power source (13.56 MHz) manufactured by Pearl Industry.

  Further, the conditions for the AGP treatment among the barrier layer treatments shown in Tables 1 and 3 are described below. The discharge gas and the reaction gas are mixed and at normal pressure, and the amount (%) of the reaction gas indicates a mole fraction.

(Dual frequency oxygen AGP treatment)
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ²
High frequency side power supply power: 13.56 MHz at 9 W / cm ² .

(Single-frequency oxygen AGP treatment 1)
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ² .

(Single-frequency oxygen AGP treatment 2)
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
High frequency side power supply power: 13.56 MHz at 9 W / cm ² .

(Measurement method of 10-point average roughness Rzjis of barrier layer)
The sample coated with polysilazane was measured for 10-point average roughness Rzjis after the barrier layer was formed after the treatment. Rzjis is calculated from an uneven cross-sectional curve continuously measured by a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope), and the measurement direction is within a 30 μm interval with a stylus with a minimum tip radius. Is a ten-point average roughness with respect to the amplitude of fine irregularities.

(Visual observation of sample after formation of barrier layer)
The state of the sample was visually observed at the stage after the treatment of Samples 1-1 to 4-2 (the sample that was not treated was the stage of forming the barrier layer). The results are shown in Table 5.

(Preparation of OC layer forming composition and OC layer formation)
As the UV curable resin 1 in Tables 2 and 4, OC layer formation prepared by mixing a solvent dispersion solution of inorganic nanoparticles shown in Tables 2 and 4 with DIC Corporation UV curable coating agent Unidic V-9510 The composition for coating is applied on each barrier layer by the gravure roll method so that the OC layer thickness is as shown in Table 2 and Table 4, followed by drying conditions; drying at 80 ° C. for 3 minutes, and nitrogen atmosphere Under the high pressure mercury lamp, it was cured by irradiation with 1.0 J / cm ² to form an OC layer.

  In addition, the numerical value of the item of inorganic nanoparticle (mass%) of Table 2 and Table 4 is the content rate (mass%) with respect to a coating liquid.

(Measurement and evaluation of light transmittance (%) of barrier film)
In this example, the light transmittance (400 to 800 nm) was measured according to JIS-R-3106.

  In addition, Hitachi spectrophotometer U-4100 made by Hitachi High-Technologies Corporation was used as the measuring device, and the light transmittance (400 to 800 nm) was classified as follows and listed in Table 5.

○: 80% or more and less than 99% Δ: 80% or more and less than 80% ×: less than 70% The results obtained are shown in Table 5.

(Flexibility)
Judgment was made by whether or not it bends when it is held in the hand and force is applied in the bending direction.

○: Turned ×: Not bent Table 5 shows the results.

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

Equipment Vapor deposition equipment: Vacuum vapor deposition equipment JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments.

Raw material Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Preparation of cell for evaluating water vapor barrier property In advance, a barrier film sample No. 1 was subjected to a bending test (bending 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm). A portion (12 mm × 12 mm) to be deposited on the barrier film sample before applying the transparent conductive film on the barrier layer surface of 1-1 to 4-2 using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400). The portion other than the portion was masked, and metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was evaporated from another metal evaporation source on the entire surface of the sheet having the barrier layer. 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. Since Sample 1-2 was low in flexibility and was damaged by the bending test, the subsequent evaluation was not performed.

  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 the water vapor transmission rate is calculated from the corrosion amount of metallic calcium based on the calculation method of the water vapor transmission rate below. It was evaluated according to the evaluation criteria.

  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.

(Calculation method of water vapor transmission rate)
The water vapor permeability calculating means 5 takes an image of the evaluation cell after storage, extracts the area where the corrosive metal (calcium) is corroded by image processing, and the amount of water vapor required for the corroded area to corrode. Is calculated to calculate the water vapor permeability of the water vapor barrier film. As shown in Equation 1, 1 mol of calcium reacts with 2 mol of water to produce 1 mol of calcium hydroxide.

Ca + 2H ₂ O → Ca (OH) ₂ + H ₂ (Formula 1)
Therefore, the water vapor transmission rate required for the corrosion of the evaluation cell is the time of storage under high temperature and high humidity, the calcium area and corrosion area of the test piece, the thickness of the calcium layer, the thickness correction coefficient after corrosion of calcium, It can be determined from the density of calcium hydroxide.

Molar amount of calcium hydroxide after storage under high temperature and high humidity (X):
X = (δ × t × α × d ₂ ) / M ₂ (Formula 2)
Water vapor transmission rate (g / m ² / day) = X × 18 × 2 × (10 ⁴ / A) * (24 / T) (Formula 3)
Storage time under high temperature and high humidity: T (hour)
Area of corrosive metal: A (cm ² )
Corrosive metal thickness: t (cm)
Thickness correction factor after corrosion of corrosive metal: α
Corroded metal area: δ (cm ² )
Corrosive metal molecular weight: M ₁
Metal hydroxide molecular weight after corrosion: M ₂
Density of corrosive metal: d ₁ (g / cm ³ )
Metal hydroxide density after corrosion: d ₂ (g / cm ³ ).

(Evaluation criteria)
Less than 5: 1 × 10 ⁻⁵ g / m ² / day 4: 1 × 10 ⁻⁵ g / m ² / day or more, less than 1 × 10 ⁻⁴ g / m ² / day 3: 1 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more The results obtained are shown in the column of water vapor transmission rate in Table 5.

(Evaluation of scratch resistance (rolling resistance))
(Preparation of base material)
The above-mentioned polyester film (Teijin DuPont Films Co., Ltd., Tetron O3) 18 cm wide and 125 μm thick, which is easily bonded to both sides, has a smooth layer and a back surface: about 100 m long film having a bleed-out preventing layer. In the same manner, coating, drying, and UV curing were performed in a test plant.

  Next, this long film is cut in the middle, each barrier film sample is bonded and connected with a splicing tape, and winding / unwinding is performed 10 times on a cylindrical stainless steel roll having a diameter of 15 cm at a tension of 60 N / 18 cm. Repeatedly, the presence or absence of scratches on the surface of the barrier film sample on the barrier layer side was observed with an optical microscope 100 times.

○: No scratch was observed. X: One or more scratches were observed. Table 5 shows the results.

(Adhesion of OC layer)
In the evaluation of the scratch resistance, it was observed whether the OC layer was peeled off from the barrier layer. The results are shown in Table 5.

(Production of organic photoelectric conversion element)
A barrier film sample No. 1 previously subjected to a bending test (repeating bending 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm). 1-1 to 4-2 and the barrier film sample No. which was not bent. 1-1 to 4-2, indium tin oxide (ITO) transparent conductive film deposited with a thickness of 150 nm (sheet resistance 10 Ω / □) to a width of 2 mm using ordinary photolithography technology and wet etching Patterning was performed to form a first electrode. Since Sample 1-2 was low in flexibility and was damaged by the bending test, the subsequent evaluation was not performed.

  The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

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

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

First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and 3.0 wt% Then, a liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at room temperature and dried. Subsequently, 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 the vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then the substrate is fed at a deposition rate of 0.01 nm / second. Next, 0.6 nm of lithium fluoride is stacked, and then 100 nm of Al metal is stacked at a deposition rate of 0.2 nm / sec through a shadow mask having a width of 2 mm (vaporization is performed so that the light receiving portion is 2 × 2 mm). Thus, the second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing film and a photocurable 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), the barrier film samples No. 1 and No. 2 were repeatedly bent and overlapped with the surfaces of the two barrier films provided with the barrier layer inside. 1-1 to 4-2 and the barrier film sample No. which was not bent. 1-1 to 4-2 were prepared as sealing films.

  Organic photoelectric conversion element sample No. 1 using the bent barrier film as a substrate. 1-1 to 4-2 correspond to the barrier film sample No. Organic photoelectric conversion element sample Nos. 1-1 to 4-2 were used as sealing films, and the barrier film that was not subjected to the bending test was used as a substrate. 1-1 to 4-2 corresponding barrier film sample No. which was not bent. 1-1 to 4-2 as sealing films, each corresponding two sets of organic photoelectric conversion element sample Nos. Two sets of organic photoelectric conversion element sample Nos. 1-1 to 4-2 were produced. At the time of sealing, an epoxy-based photocurable adhesive is applied as a sealing material to the barrier layer of the sealing film, and the organic photoelectric conversion element is sandwiched between the barrier films to be in close contact with each other. Was cured by irradiation. Thus, the organic photoelectric conversion element sample No. 1-1 to 4-2 were obtained.

(Evaluation of energy conversion efficiency)
A barrier film sample that was repeatedly bent as described above and a barrier film sample No. 1 that was not bent. Each of the corresponding organic photoelectric conversion element sample Nos. On 1-1 to 4-2, a mask with an effective area of 4.0 mm ² is superimposed on the light receiving part, and light of 100 mW / cm ² of solar simulator (AM1.5G filter) is applied to each of the four light receiving parts. By irradiating and measuring IV characteristics, the short-circuit current density Jsc (mA / cm ² ) and the open circuit voltage Voc (V) were obtained. From the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%), the four-point average value of the energy conversion efficiency PCE (%) obtained according to the following formula 1 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 following evaluation was performed on the ratio of conversion efficiency / initial conversion efficiency after the acceleration test.

5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20% Barrier film sample No. Organic element sample No. 1 corresponding to each of 1-1 to 4-2. The evaluation results of 1-1 to 4-2 are shown in the column of the conversion efficiency remaining rate after the acceleration test in Table 6. Note that the barrier film sample No. Organic photoelectric conversion element sample No. 1 corresponding to each of 1-1 to 4-2. For 1-1 to 4-2, no difference was observed in the conversion efficiency remaining ratio before and after the acceleration test.

  In the evaluation of scratch resistance in Table 5, it was observed that Sample 1-12 had the OC layer peeled off from the barrier layer, indicating that the adhesive force between the barrier layer and the OC layer was low. For the other samples provided with the OC layer, no separation of the OC layer was observed.

  It can be seen from Tables 1 to 5 that the barrier film in which the barrier layer composed of the polysilazane of the present invention and the OC layer are laminated has a low water vapor transmission rate and high barrier performance before and after the bending test. Moreover, since the barrier film of the present invention has scratch resistance and anti-bending properties, it can be seen that it has roll-to-roll production suitability. Moreover, it turns out that the barrier film of this invention has high visible light transmittance | permeability, and has high transparency. Moreover, from Table 6, the organic photoelectric conversion element using the barrier film of the present invention as a substrate has little decrease in conversion efficiency when stored at high temperature and high humidity even when the barrier film subjected to the bending test is used. I understand.

  In the present invention, by providing a film to be converted into a barrier layer in advance by coating, the barrier layer has high surface smoothness and high uniformity of film thickness, and stress concentration is reduced, so winding resistance (scratch resistance) It is considered that a barrier film excellent in folding resistance and having good barrier properties after folding could be obtained. Therefore, it is possible to provide an extremely excellent barrier film that can be produced roll-to-roll according to the present invention, and an organic photoelectric conversion element manufactured using the barrier film of the present invention can be provided at an extremely low cost. It is.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode 13 Counter electrode 14 Photoelectric conversion part (bulk hetero junction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion unit 15 charge recombination layer 16 second photoelectric conversion unit 17 hole transport layer 18 electron transport layer 20 photosensor array 21 substrate 22 transparent electrode 23 counter electrode 24 photoelectric conversion part 24a buffer layer 24b photoelectric conversion layer

Claims (5)

  A barrier film having a barrier layer containing at least one silicon atom and oxygen atom on a substrate and an overcoat layer on the barrier layer, wherein the barrier layer is made of polysilazane. A barrier film, wherein the overcoat layer has inorganic nanoparticles having a number average particle diameter of 1 to 200 nm.   The barrier film according to claim 1, wherein the surface of the barrier layer has a ten-point average roughness Rzjis of 10 nm to 90 nm.   The barrier film according to claim 1, wherein the barrier layer has a ten-point average roughness Rzjis of 10 nm to 30 nm.   The organic photoelectric conversion element produced using the barrier film of any one of Claims 1-3.   In the manufacturing method of the barrier film of any one of Claims 1-3, after apply | coating the coating liquid containing polysilazane on a base material, polysilazane is plasma-processed by at least 2 frequency or more in discharge gas atmosphere. The manufacturing method of the barrier film characterized by forming a barrier layer by converting into a silicon oxide.

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