JP2015143033A - Gas barrier film, method of producing the same, and organic photoelectric conversion element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which has high barrier performance, bending resistance, and smoothness and is excellent in cutting processability, and an organic photoelectric conversion element using the same.SOLUTION: In the gas barrier film, a gas barrier layer is formed by applying a polysilazane-containing solution to at least one surface of a substrate. Two adjacent modified layers are formed on a surface of the gas barrier layer by applying a modification treatment. There are also provided a method of producing the gas barrier film, and the organic photoelectric conversion element using the gas barrier film.

Description

  The present invention relates to a gas barrier film and an organic photoelectric conversion element using the same. More specifically, gas barrier films mainly used in display materials such as packages for electronic devices, solar cells, organic EL elements, plastic substrates such as liquid crystals, and various device resin substrates and various device elements using gas barrier films. About.

  Conventionally, a gas 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 goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

As a method for forming such a gas barrier film, a technique for forming a gas barrier layer by a plasma CVD method (Chemical Vapor Deposition method) or a coating liquid containing polysilazane as a main component is applied. Techniques for surface treatment are known (see, for example, Patent Documents 1 to 3). However, any of these techniques has an insufficient function as a gas barrier layer such as an organic photoelectric conversion element, and the water vapor transmission rate is further lower than 1 × 10 ⁻² g / m ² · day. There was a need for improved gas barrier properties.

  Patent Document 1 discloses a technique characterized in that the film density of the outermost layer in the gas barrier layer is higher than the film density of the entire gas barrier layer.

  However, because the stress when bent is concentrated on the outermost layer with high density, it is easy to crack and inferior in bending resistance, and because it is a vapor deposition film formation method, particles in the gas phase are produced as by-products in the gas phase space. In some cases, uniform film formation may be hindered due to adhesion to the substrate, and the smoothness of the surface is poor. There was a problem that the remarkably decreased.

  Patent Document 2 discloses a technique for forming a gas barrier layer by converting a polysilazane film into silica by forming a polysilazane film by a wet method and performing plasma treatment.

  However, since the conversion reaction efficiency of the plasma treatment is low, it takes about 5 minutes for the silica conversion as in the example, and the film quality on the side opposite to the treatment side of the polysilazane film becomes uniform. As a result, it was found that the stress relaxation function does not work sufficiently and the bending resistance is poor. It was also found that the cut surface is prone to fraying during cutting, it is difficult to ensure an effective product width, and the production suitability is remarkably inferior.

  Patent Document 3 discloses a technique for forming a gas barrier layer by forming a polysilazane film by a wet method and irradiating with UV radiation in an atmosphere containing water vapor.

  However, the present inventors have confirmed that the dehydration reaction after silanol formation does not proceed sufficiently due to the atmosphere containing water vapor, the resulting film density is low, and it is not sufficient for gas barrier adaptation to organic photoelectric conversion elements. There was found.

JP 2004-66730 A JP 2007-237588 A Special table 2009-503157

  The present invention has been made in view of the above-described problems and situations, and the solution to the problem is to provide a gas barrier film excellent in cutting processing suitability together with high barrier performance, bending resistance, smoothness, and using the same. An organic photoelectric conversion element is provided.

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

1. A gas barrier film in which a polysilazane-containing liquid is applied to at least one surface of a base material to form a gas barrier layer, and the gas barrier layer has a density of two layers adjacent to the surface of the gas barrier layer by performing a modification treatment Different modified layers are formed,
When the film density on the surface side of the two modified layers is d ₁ , the film density on the inner side is d ₂ , and the film density in the unmodified region is d ₃ , d ₂ > d ₁ > d ₃ and a difference Δd (= d ₂ −d ₃ ) between the film density d ₂ and the film density d ₃ is 0.1 g / cm ³ or more.

2. 2. The gas barrier film as described in 1 above, wherein Δd is 0.15 g / cm ³ or more.

3. ^3. The gas barrier film as described in 2 above, wherein Δd is 0.2 g / cm ³ or more.

4). Wherein the modified layer of two layers, a film sum of density thickness regions having a _{d 1 L 1} and the film density thickness _{L 2} of the region having a _{d 2 (L 1 + L 2} ) is 30nm or more, and the ratio gas barrier film according to any one of the 1 to 3 _{L 2 / (L 1 + L} 2) is characterized in that at least 0.4.

5. 5. The gas barrier film according to 4, wherein the ratio L ₂ / (L ₁ + L ₂ ) is 0.6 or more.

6). 6. The gas barrier film according to 5, wherein the ratio L ₂ / (L ₁ + L ₂ ) is 0.8 or more.

  7). 7. The gas barrier film according to any one of 1 to 6, wherein the surface roughness (Ra) on the side subjected to the modification treatment of the gas barrier layer is 2 nm or less.

  8). 8. The gas barrier film according to any one of 1 to 7, wherein a smooth layer is provided between the substrate and the gas barrier layer.

  9. 9. The gas barrier film as described in 8 above, wherein the smooth layer is formed by curing a photosensitive resin composition containing an acrylate compound.

  10. 10. The gas barrier film according to 9, wherein the photosensitive resin composition contains reactive silica particles.

  11. The gas barrier film according to any one of 8 to 10, wherein a maximum cross-sectional height Rt (p) of the surface of the smooth layer is 10 nm or more and 30 nm or less.

12 In the method for producing a gas barrier film according to any one of 1 to 11,
A step of applying a polysilazane-containing liquid to at least one side of the substrate to form a coating film; and
A step of modifying the coating film,
The method for producing a gas barrier film, wherein the modification treatment is a step of irradiating a vacuum ultraviolet ray having a wavelength component of 180 nm or less.

  13. 13. The method for producing a gas barrier film as described in 12 above, wherein in the step of irradiating the vacuum ultraviolet ray, at least one condition of oxygen concentration, processing temperature, humidity, irradiation distance, and irradiation time is changed during irradiation.

  14 14. The method for producing a gas barrier film according to 12 or 13, wherein the dew point of the atmosphere in the step of irradiating the vacuum ultraviolet ray is 10 ° C. to −50 ° C.

  15. The method for producing a gas barrier film according to any one of 12 to 14, wherein a temperature condition in the step of irradiating the vacuum ultraviolet ray is 25C to 200C.

16. The irradiation intensity of the VUV in the step of irradiating vacuum ultraviolet rays are 10~200mJ / cm ^2, the manufacturing method of the gas barrier film described in any one of 12 to 15.

  17. The method for producing a gas barrier film according to any one of 12 to 16, wherein the irradiation time of the vacuum ultraviolet ray in the step of irradiating the vacuum ultraviolet ray is 0.1 to 15 seconds.

  18. The organic photoelectric conversion element characterized by using the gas barrier film according to any one of 1 to 11 above.

  19. 12. An organic EL device using the gas barrier film according to any one of 1 to 11 above.

  By the above means of the present invention, it is possible to provide a gas barrier film excellent in smoothness and cutting processability as well as high barrier performance and bending resistance. Moreover, the organic photoelectric conversion element using the same can be provided.

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

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

  The gas barrier film of the present invention is a gas barrier film having a gas barrier layer formed on a coating film of a polysilazane-containing liquid on at least one surface of a substrate, and adjacent to at least one of the gas barrier layers. The two modified layers are formed.

As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the film density d ₁ on the surface side and the inner film of two adjacent modified layers formed by the modification treatment of the gas barrier layer are used. When the density d ₂ and the film density d ₃ of the other region are set, the relationship d ₂ > d ₁ > d ₃ is satisfied, and the difference Δd (= d ₁ −− between the film density d ₁ and the film density d ₃ is satisfied. d ₃ ) is preferably 0.1 g / cm ³ or more.

Further, the gas barrier layer reforming two layers adjacent are formed by treatment of the modified layer, the film density d ₁ film thickness L ₁ of the region having a a film density d ₂ and the thickness L ₂ of the region having a it is preferable sum _(L 1 + _{L 2)} is at 30nm or more and the ratio _L 2 _{/ (L} 1 + _{L 2)} is 0.4 or more. In the present invention, the surface roughness (Ra) on the side subjected to the modification treatment is preferably 2 nm or less. Moreover, it is preferable that the said modification process is a process which irradiates the vacuum ultraviolet-ray which has a wavelength component of 180 nm or less.

  The method for producing a gas barrier film of the present invention includes a gas barrier layer formed by subjecting a coating film of a polysilazane-containing liquid to a modification treatment, and two modified layers adjacent to at least one of the gas barrier layers are provided. Preferably it is formed.

  The gas barrier film of the present invention can be suitably used for an organic photoelectric conversion element.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.

(Gas barrier film)
The gas barrier film of the present invention is a gas barrier film having a gas barrier layer formed on at least one surface of a base material by subjecting a coating film of a polysilazane-containing liquid to a modification treatment, wherein the gas barrier layer is silicon oxide or It is formed of a silicon oxynitride compound film, and two modified layers are formed in a region on one modified treatment side of the gas barrier layer.

  The gas barrier film of the present invention has a gas barrier layer formed by modifying one or more polysilazane films on at least one surface of a resin film substrate (support), for example, polyethylene terephthalate. As the layer, a single layer or a plurality of similar films may be laminated, and the gas barrier property can be further improved by the plurality of layers.

  In the present application, the “gas barrier layer” means a silicon oxide such as silicon dioxide or a silicon oxynitride compound formed by modifying one or more polysilazane films formed by applying a polysilazane-containing liquid. Even when a plurality of gas barrier layers are provided, two modified layers are formed in a region on the modification treatment side of each layer.

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

  As a method of forming a gas barrier layer, a method of forming a gas barrier layer containing a silicon oxide or a silicon oxynitride compound by applying a coating solution containing at least one polysilazane compound on a substrate and then modifying the coating solution. Is mentioned.

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

  The gas barrier layer according to the present invention includes two modified layers, and the modified layer has the following characteristics.

  1) In the gas barrier layer according to the present invention, in the dislocation line observation by the ultra high resolution transmission electron microscope (TEM) of the cross section, a clear interface in a region having different properties is not observed.

  On the other hand, when regions having different properties are stacked by vapor deposition, an interface always exists due to the properties. Dislocation lines such as screw dislocations and edge dislocations are generated at the time of deposition of gas phase molecules in the stacking direction due to minute nonuniformity occurring at the interface, and are observed by an ultrahigh resolution TEM.

  Since the gas barrier layer according to the present invention is a modification treatment of the coating film, it is presumed that regions having different properties can be formed without an interface without generating dislocation lines that are likely to occur during deposition of gas phase molecules.

  2) Of the gas barrier layer according to the present invention, a high density region is formed in the modified layer, and further, the distance between Si-O atoms in the high density region is measured from FT-IR analysis in the depth direction. Then, a microcrystalline region is confirmed, and a crystallized region is confirmed in a region having the highest density.

While SiO ₂ is normally crystallized by heat treatment at 1000 ° C. or higher, the surface region SiO ₂ of the gas barrier layer according to the present invention is crystallized even at a low temperature treatment of 200 ° C. or less on the resin substrate. Can be achieved. Although the reason is not clear, the present inventors have assumed that the cyclic structure of 3 to 5 contained in polysilazane has an interatomic distance advantageous for forming a crystal structure. The process of dissolution, rearrangement, and crystallization described above is unnecessary, and it is assumed that the modification process is involved in the existing short-range order, and the ordering can be performed with less energy. In particular, the treatment of irradiating with vacuum ultraviolet rays is preferable because the combination of the breakage of chemical bonds such as Si—OH by the irradiation of vacuum ultraviolet rays and the oxidation treatment with ozone generated in the irradiation space enables efficient treatment.

<Coating film of polysilazane-containing liquid>
The coating film of the polysilazane-containing liquid according to the present invention is formed by applying a coating liquid containing at least one polysilazane compound on a substrate.

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

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

  In order to apply the film base material without damaging the film base material, it is preferable that the film base material is converted to silica at a relatively low temperature as described in JP-A-8-112879.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Modification process)
For the modification treatment in the present invention, a known method based on the conversion reaction of the polysilazane film can be selected. Production of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a silazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate such as plastic. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet rays, which can be converted at a lower temperature, is preferred for adaptation to a plastic substrate.

<Plasma treatment>
In the present invention, a known method can be used for the plasma treatment as the modification treatment, but atmospheric pressure plasma treatment is preferable. In the case of atmospheric pressure plasma treatment, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

<< Atmospheric pressure plasma with two or more electric fields of different frequencies >>
Next, a preferable embodiment of the atmospheric pressure plasma will be described. Specifically, as described in International Publication No. 2007-026545, the atmospheric pressure plasma is formed by forming two or more electric fields having different frequencies in the discharge space, and the first high-frequency electric field and the second high-frequency electric field. It is preferable to form an electric field superimposed with the electric field.

Said first of said second high-frequency electric field than the frequency omega ₁ of the high-frequency electric field frequency omega ₂ is high, and, the intensity V ₁ of the first high frequency electric field, the intensity of the second high frequency electric field V ₂ And the intensity IV of the discharge starting electric field is
V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By adopting such discharge conditions, 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 perform high-performance thin film formation. Can do.

When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is , V ₁ ≧ 3.7 kV / mm can be applied to excite the nitrogen gas and bring it into a plasma state.

  Here, the frequency of the first power supply 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 formation of a high-frequency electric field from such two power sources is necessary for initiating the discharge of a discharge gas having a high discharge starting 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 form a dense and high-quality thin film by increasing the plasma density due to the high power density.

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

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

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

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

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

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

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

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

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

<Vacuum UV irradiation treatment; Excimer irradiation treatment>
In the present invention, a more preferable method for the modification treatment is treatment by vacuum ultraviolet irradiation. The treatment with vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the silazane compound, and bonds of atoms are only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of.

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

1. Excimer light emission is called an inert gas because atoms of rare gases such as Xe, Kr, Ar, and Ne do not form a molecule by chemically bonding. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Modified layer)
In the present invention, the modified layer formed by the modification treatment can be confirmed by a cross-sectional TEM observation method of the film after the modification treatment.

Cross-sectional TEM observation A cross-sectional TEM observation is performed on a film sample after creating a flake with the following FIB processing apparatus. At this time, if the sample is continuously irradiated with the electron beam, a contrast difference appears between a portion that is damaged by the electron beam and a portion that is not. The modified layer of the present invention is not easily damaged by electron beam because it is densified by the modification process, but the other part is damaged by the electron beam, and alteration is confirmed. The film thickness can be calculated by the cross-sectional TEM observation confirmed in this way.

(FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 5 to 60 seconds (2 layers of modified layer)
In the present invention, the modified layer is confirmed by the above-mentioned cross-sectional TEM observation method, and two adjacent layers having a further contrast difference are confirmed in the region. From this contrast difference, the film thicknesses of the region on the processing surface side and the region inside the region can be calculated.

(Film density)
In the present invention, the gas barrier layer is formed from a film of silicon oxide or silicon oxynitride compound, a film density d ₁ of the modified area of the treated surface side of the gas barrier layer, an inner film density of the modified region d ₂ and the film density d ₃ in the unmodified region can be obtained as follows.

X-ray reflectivity measurement of film density distribution (X-ray reflectivity measurement device) Rigaku Denki's thin film structure evaluation device ATX-G
(X-ray source target) Copper (1.2kW)
(Measurement) Measure the X-ray reflectivity curve using a 4-crystal monochromator, create a density distribution profile model, perform fitting, and calculate the density distribution in the film thickness direction.

The order of the numerical values of the film densities d ₁ , d _2, and d _{3 in} the present invention satisfies the relationship d ₂ > d ₁ > d ₃ and the difference Δd (= d ₁ between the film density d ₁ and the film density d ₃ -D ₃ ) is preferably 0.10 g / cm ³ or more. The Δd of the film density difference is preferably 0.1 g / cm ³ , more preferably 0.15 g / cm ³ , still more preferably 0.2 g / cm ³ or more.

The upper limit of the Δd value is obtained from the silicon oxide (quartz glass) density of 2.2 g / cm ³ and the polysilazane liquid coating density of 1.3 g / cm ³ , and the upper limit is 0.9 g / cm ³ . can do.

  As a method of adjusting Δd within the above range, it can be performed by adjusting conditions such as the (average) film thickness of the polysilazane film, the treatment intensity during the modification treatment, the oxygen concentration in the irradiation atmosphere, and the treatment time. For example, in the modification process using vacuum ultraviolet light, Δd can be changed to a higher value by controlling the conditions such that the (average) film thickness of the polysilazane film is thin, the vacuum ultraviolet light intensity is high, and the processing time is shortened. it can.

  In particular, in the modification treatment of the polysilazane film in the present invention, the modification treatment by vacuum ultraviolet irradiation is most preferable in forming two adjacent modification layers. Although the mechanism by which the two modified treatment layers can be formed is not clear, the present inventors have directly cut the silazane compound by light energy and surface oxidation reaction by active oxygen or ozone generated in the gas phase. It is presumed that the process proceeds simultaneously, resulting in a difference in reforming speed between the surface side and the inside of the reforming process, and as a result, two adjacent reformed layers are formed. Further, as a means for positively controlling the difference in the reforming rate, it is possible to control the surface oxidation reaction by active oxygen or ozone generated in the gas phase. That is, the desired film thickness and density of two adjacent modified layers can be obtained by changing the conditions that contribute to the surface oxidation reaction such as oxygen concentration, processing temperature, humidity, irradiation distance, and irradiation time during irradiation. Can do. In particular, a mode in which the oxygen concentration is changed during irradiation is preferable. By increasing the oxygen concentration in accordance with the change of the condition, the density on the processing side of two adjacent layers can be reduced and the film thickness can be increased.

  As the above modification treatment conditions, for example, when the polysilazane film thickness is 50 nm to 1000 nm, the vacuum ultraviolet illuminance is 10 to 200 mJ / cm 2, the irradiation distance is 0.1 to 10 mm, the oxygen concentration is 0 to 5%, and the dew point temperature is 10 ° C. to − It can be selected from 50 ° C., temperature 25 ° C. to 200 ° C., and processing time 0.1 to 150 sec.

(Thickness of the modified layer)
Of the modified layer in the present invention, the thickness _{L 1} of the region having a film density _{d 1,} the sum of the thickness _{L 2} of the region having a film density _{d 2 (L} 1 + _{L 2)} in the 30nm or more and its It is preferable that the ratio L ₂ / (L ₁ + L ₂ ) is 0.4 or more. The film thickness L ₁ and the film thickness L ₂ can be calculated from the cross-sectional TEM observation, and the sum (L ₁ + L ₂ ) is preferably 30 nm or more. More preferably, (L ₁ + L ₂ ) is preferably 60 nm or more. Further, L ₂ / (L ₁ + L ₂ ) is preferably 0.4 or more, more preferably 0.6 or more, and further preferably 0.8 or more.

  The gas barrier layer obtained by modifying the polysilazane film as in the present invention has two modified layers and different film densities, and the difference Δd and (average) film thickness are in the above ranges. As a result, it was found that cracks due to stress concentration can be prevented, and both high barrier properties and stress relaxation functions can be achieved. In particular, it is preferable to subject the gas barrier layer to vacuum ultraviolet treatment because the surface treatment can be efficiently performed in a short time with vacuum ultraviolet light, so that the effects of the present invention are remarkably exhibited.

<Surface roughness: smoothness>
The surface roughness (Ra) of the gas barrier layer on the modification treatment side according to the present invention is preferably 2 nm or less, more preferably 1 nm or less. When the surface roughness is within the above range according to the present invention, when used as a resin substrate for an organic photoelectric conversion element, the smooth film surface with few irregularities improves the light transmission efficiency and reduces the leakage current between the electrodes. Reduction is preferable because energy conversion efficiency is improved. The surface roughness (Ra) of the gas barrier layer according to the present invention can be measured by the following method.

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

<Cutability>
The gas barrier film of the present invention is excellent in cutting processability. That is, there is no fraying on the cut surface even after cutting, and an effective area can be earned.

  The conventional gas barrier film has a phenomenon that the edge of the cutting breaks with the film vigorously like glass due to the stress applied when cutting, and the effective area as a product decreases from the crack of the cutting surface, There was a problem of poor productivity. The present inventors have eagerly pursued the cause of the conventional gas barrier film that breaks vigorously like glass when cutting, but the mechanism could not be clarified. However, by using a gas barrier layer having a different film density in the modification treatment of the polysilazane film, it is found that the stress applied to the edge during the cutting process can be dispersed and the phenomenon of vigorous cracking like glass can be improved. The present invention has been reached.

(Configuration of gas barrier film)
(Substrate: Support)
The substrate (also referred to as “support”) of the gas barrier film of the present invention is particularly limited as long as it is formed of an organic material capable of holding a gas barrier layer having a barrier property described later. is not.

  For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films, and silsesquioxane having an organic-inorganic hybrid structure Examples thereof include a heat-resistant transparent film having a skeleton (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin film formed by laminating two or more layers of the resin. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the gas barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

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

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

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

  Moreover, in the support body which concerns on this invention, you may corona-treat before forming a vapor deposition film.

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

(Smooth layer)
The gas barrier film of the present invention may have a smooth layer. The smooth layer is used to flatten the rough surface of the transparent resin film support having protrusions or the like, or to fill the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the transparent resin film support to flatten the surface. Provided. Such a smooth layer is basically formed by curing a photosensitive resin.

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with acrylate, 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 pigment such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

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

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used in order to improve the film formability and prevent 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 Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropyle Glycol ethers such as ethylene glycol 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 di Ruki ether, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If the value is smaller than this range, the coatability is impaired when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or wireless bar at the stage of coating a silicon compound described later. There is a case. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

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

<Additives to smooth layer>
One preferred embodiment includes reactive silica particles (hereinafter, also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the above-described photosensitive resin. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. 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 antiglare 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. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent or cracks may occur when heat treatment is performed, or the optical properties such as transparency and refractive index of the gas barrier film may be affected.

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

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

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

  The thickness of the smooth layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer has a high transparency. When the film is provided only on one surface of the molecular film, curling of the smooth film can be easily suppressed.

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

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

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

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 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 (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and 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-eth Ciethoxy) 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 100 parts by mass of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

  The smooth 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. You can use what you want. 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.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

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

(Organic photoelectric conversion element)
The gas barrier film of the present invention can be used as various sealing materials and films. For example, it can be used in organic photoelectric conversion elements.

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

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

  The transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin. The (average) film thickness of the transparent conductive film is preferably a transparent conductive film in the range of 0.1 to 1000 nm.

  Next, an organic photoelectric conversion element using these gas barrier films and a resin support for an organic photoelectric conversion element on which a transparent conductive film is formed will be described.

[Sealing film and manufacturing method thereof]
The sealing film according to the present invention is characterized in that the gas barrier film is used as a substrate.

  In the gas barrier film, a transparent conductive film is further formed on the gas 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, and another layer is further formed thereon. One gas barrier film is used as a sealing film, and sealing is performed by overlapping adhesion.

  In particular, a resin-laminated (polymer film) metal foil cannot be used as a gas barrier film on the light extraction side, but is a low-cost and further moisture-permeable sealing material and does not intend to extract light (transparent) When it is not required), it is preferable as a sealing film.

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

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

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

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

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

[Encapsulation of organic photoelectric conversion elements]
In this invention, the transparent conductive film was formed on the resin film (gas barrier film) which has the said gas barrier layer based on this invention, and each layer of the organic photoelectric conversion element was formed on the produced resin support for organic photoelectric conversion elements. Thereafter, the organic photoelectric conversion element can be sealed using the sealing film so as to cover the cathode surface with the sealing film in an environment purged with an inert gas.

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

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

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

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm. However, when the coating amount of the adhesive is too large, tunneling, leaching, shrinkage, etc. may occur. Preferably, the amount of the adhesive is 3 to 5 μm in terms of dry (average) film thickness. It is preferable to adjust to.

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

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

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

<Ceramic layer>
In the present invention, as described above, in sealing the organic photoelectric conversion element, a ceramic layer formed of a compound of an inorganic oxide, nitride, carbide, or the like is provided in order to further enhance gas barrier properties. Can do.

Specifically, it is formed of SiO _x , Al ₂ O ₃ , In ₂ O ₃ , TiO _x , ITO (tin / indium oxide), AlN, Si ₃ N ₄ , SiO _x N, TiO _x N, SiC, or the like. be able to.

  The ceramic layer may be laminated by a known method such as a sol-gel method, a vapor deposition method, CVD, PVD, or a sputtering method.

  For example, polysilazane can be used and formed by the same method as the polysilazane film. In this case, it can be formed by applying a composition containing polysilazane to form a polysilazane film and then converting it to ceramic.

  In the atmospheric pressure plasma method, the ceramic layer according to the present invention can be obtained by selecting conditions such as a raw material (also referred to as a raw material), such as an organometallic compound, a decomposition gas, a decomposition temperature, and input power, so that silicon oxide or oxidation The composition of metal oxides mainly composed of silicon, and mixtures with metal carbides, metal nitrides, metal sulfides, metal halides, etc. (metal oxynitrides, metal oxide halides, etc.) can be made separately. .

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if silazane or the like is used as a raw material compound, silicon oxynitride 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 a raw material for forming such a ceramic layer, as long as it is a silicon compound, 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.

  Examples of such silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethyl Aminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1 , 3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propa Gil trimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclo Examples thereof include tetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  The decomposition gas for decomposing the raw material gas containing silicon to obtain the ceramic layer includes hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, and nitrous oxide gas. , Nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas and the like.

  By appropriately selecting a source gas containing silicon and a decomposition gas, a ceramic layer containing silicon oxide, nitride, carbide, or the like can be obtained.

  In the atmospheric pressure plasma method, a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to a 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.

  The discharge gas and the reactive gas are mixed and supplied to an atmospheric pressure plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. 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 laminated ceramic layer constituting the gas barrier resin substrate according to the present invention, for example, oxygen gas or nitrogen gas is further combined with the organic silicon compound at a predetermined ratio, and at least one of O atoms and N atoms is combined. A ceramic layer mainly containing silicon oxide according to the present invention containing Si atoms can be obtained.

  The thickness of the ceramic layer according to the present invention is preferably in the range of 10 to 2000 nm in consideration of gas barrier properties and light transmission properties, but is also well balanced in consideration of flexibility. In order to exhibit excellent performance, the thickness is preferably 10 to 200 nm.

  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 electric power generation layer (The layer which mixed the p-type semiconductor and the n-type semiconductor, the bulk heterojunction layer, and i layer) sandwiched between the anode and the cathode at least 1 is provided. Any element that has more than one layer and generates current when irradiated with light may be used.

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

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

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

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

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

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

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

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

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

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

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

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

  Below, the material which comprises these layers is described.

(Organic photoelectric conversion element material)
<P-type semiconductor material>
Examples of the p-type semiconductor material used for the power generation layer (bulk heterojunction layer) 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, zesulene, Compounds such as heptazesulene, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis (ethylenedithio) tetrathiafur Examples include valene (BEDT-TTF) -perchloric acid complex, and derivatives and precursors thereof.

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

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

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

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

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

  Examples of such 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. Or by applying energy such as heat as described in U.S. Patent Application Publication No. 2003/136964 and Japanese Patent Application Laid-Open No. 2008-16834, etc., the soluble substituent reacts to insolubilize (to form a pigment). ) Materials can be mentioned.

<N-type semiconductor material>
The n-type semiconductor material used for the bulk heterojunction layer according to the present invention is not particularly limited. For example, a perfluoro compound (perfluoropentacene) in which hydrogen atoms of a p-type semiconductor such as fullerene and octaazaporphyrin are substituted with fluorine atoms. And perfluorophthalocyanine), naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized polymers thereof as a skeleton A compound etc. can be mentioned.

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

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

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

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

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

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro material (perfluoropentacene, perfluorophthalocyanine, etc.) can be 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)>
In the transparent electrode according to the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element 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 may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The (average) film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

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

  The counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a nanowire, or a nanostructure. If the dispersion is, a transparent and highly conductive counter electrode can be formed by a coating method.

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

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

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

<Metal nanowires>
As the conductive fiber according to the present invention, an organic fiber or inorganic fiber coated with a metal, a conductive metal oxide fiber, a metal nanowire, a carbon fiber, a carbon nanotube, or the like can be used, and a metal nanowire is preferable.

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

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

  There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

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

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

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

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

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

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

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

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

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

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

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

<Patterning>
The method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.

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

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

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

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

(Preparation of a film having a smooth layer and a bleed-out prevention layer)
The gas barrier film is produced by transporting the above support at a speed of 30 m / min. After forming a bleed-out prevention layer on one side and a smooth layer on the opposite side, the adhesive protective film is pasted by the following forming method. A roll-like gas barrier film was obtained.

(Formation of bleed-out prevention layer)
A UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation is applied to one side of the above support, and after applying with a wire bar so that the (average) film thickness after drying is 4 μm, curing conditions; Under high pressure mercury lamp using 1.0 J / cm ² air, drying conditions; curing at 80 ° C. for 3 minutes to form a bleed-out prevention layer.

(Formation of smooth layer)
Subsequently, on the opposite surface of the support, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied, and after coating with a wire bar so that the (average) film thickness after drying was 4 μm, Drying 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 maximum cross-sectional height Rt (p) at this time was 16 nm.

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

(Production of gas barrier film)
[Preparation of Sample 1]
(Formation of gas barrier layer)
Next, a sample provided with the smooth layer and the bleed-out prevention layer was formed with a gas barrier layer on the conditions shown below.

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

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

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

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

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

(Reforming treatment conditions)
Excimer light intensity 130mW / cm ² (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds [Preparation of sample 2]
Sample 1 was prepared in the same manner except that the excimer irradiation time of the modification conditions in sample 1 was 3%, the first 1 second was treated with 1% oxygen concentration, and the remaining 2 seconds were treated with 3% oxygen concentration. .

[Preparation of Sample 3]
(Formation of gas barrier layer)
Similar to Sample 1, a gas barrier layer was formed on the sample provided with the smoothing layer and bleed-out prevention layer under the following conditions.

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

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

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

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

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

(Reforming treatment conditions)
Excimer light intensity 180 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 0.1%
Excimer irradiation time 1 second [Preparation of sample 4]
(Formation of gas barrier layer)
Similar to Sample 1, a gas barrier layer was formed on the sample provided with the smoothing layer and bleed-out prevention layer under the following conditions.

Gas barrier layer coating solution Perhydropolysilazane (PHPS) 20% by weight dibutyl ether solution AZ Electronic Materials Co., Ltd. Aquamica NN320
With a wireless bar, coating was performed so that the (average) film thickness after drying was 0.60 μm, and a coated sample was obtained.

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

(Second step; dehumidification treatment)
The dried sample was further dehumidified by being held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 1% RH (dew point temperature of −35 ° C.).

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

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

(Reforming treatment conditions)
Excimer light intensity 80mW / cm ² (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 5%
Excimer irradiation time 30 seconds [Preparation of sample 5]
(Formation of gas barrier layer)
Similar to Sample 1, a gas barrier layer was formed on the sample provided with the smoothing layer and bleed-out prevention layer under the following conditions.

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

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

(Second step; dehumidification treatment)
None (reformation treatment D)
The sample subjected to the drying treatment was subjected to a modification treatment under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

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

(Reforming treatment conditions)
Excimer light intensity 80mW / cm ² (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 5%
Excimer irradiation time 30 seconds [Preparation of sample 6]
(Formation of gas barrier layer)
Next, a sample provided with the smooth layer and the bleed-out prevention layer was formed with a gas barrier layer on the conditions shown below.

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

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

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

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

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

(Reforming treatment conditions)
Excimer light intensity 130mW / cm ² (172nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
10% oxygen concentration in the irradiation device
Excimer irradiation time 3 seconds [Preparation of sample 7]
Sample 7 was obtained in the same manner except that the modification treatment A in sample 1 was changed to the following modification treatment F.

(Modification F)
The sample subjected to the dehumidification treatment was subjected to plasma treatment under the following conditions to form a gas barrier layer.

  The support holding temperature during film formation was 120 ° C.

  The treatment was performed using a roll electrode type discharge treatment apparatus. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film transport direction, and gas and electric power are supplied to each electrode part, and processing is appropriately performed so that the coated surface is irradiated with plasma for 20 seconds as follows. went.

  In addition, the dielectric material which coat | covers each said electrode of a plasma discharge processing apparatus used what coat | covered the 1-mm-thick alumina by single-sided by the ceramic spraying process for both opposing electrodes.

  The electrode gap after coating was set to 0.5 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz, 6 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ²
[Preparation of Sample 8]
Sample 8 was obtained in the same manner except that the modification treatment A in sample 1 was changed to the following modification treatment G.

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

(Modification equipment)
Ushio Corporation: UV irradiation device Model UVH-0252C
The sample fixed on the operation stage was modified under the following conditions.

(Reforming treatment conditions)
UV light intensity 2000 mW / cm ²
Distance between sample and light source 30mm
Stage heating temperature 40 ℃
Oxygen concentration in irradiation device 5%
UV irradiation time 180 seconds [Preparation of sample 9] (Comparative example: Sputtering film formation)
Sample 9 was obtained in the same manner except that the method for forming the gas barrier layer in Sample 1 was changed as follows.

(Formation of gas barrier layer)
It formed by the method according to the barrier formation method of Example 1 in the column of [Example] of JP-A-2004-66730.

[Production of Sample 10] (Comparative Example; Sputter Film Formation)
Sample 10 was obtained in the same manner except that the method for forming the gas barrier layer in Sample 1 was changed as follows.

(Formation of gas barrier layer)
It formed by the method according to the barrier formation method of Example 2 in the column of [Example] of JP-A-2004-66730.

[Preparation of Sample 11] (Comparative Example: Normal Pressure Plasma Treatment of Polysilazane Film)
Sample 11 was obtained in the same manner except that the method for forming the gas barrier layer in Sample 1 was changed as follows.

(Formation of gas barrier layer)
The polysilazane film in Example 11 in the column “Example” of JP-A-2007-237588 was formed by a method according to a barrier formation method by atmospheric pressure plasma treatment.

[Preparation of Sample 12] (Comparative Example: Excimer Treatment of Polysilazane Film)
Sample 12 was obtained in the same manner except that the method for forming the gas barrier layer in Sample 1 was changed as follows.

(Formation of gas barrier layer)
It was formed by the method according to the barrier formation method by excimer irradiation treatment of the polysilazane film in Example 2 in the column of [Example] of JP-T-2009-503157.

  The film density and (average) film thickness of the obtained samples 1 to 12 were measured by the following methods.

<Film density measurement>
(X-ray reflectivity measuring device) Rigaku Electric's thin film structure evaluation device ATX-G
(X-ray source target) Copper (1.2kW)
(Measurement) Measure the X-ray reflectivity curve using a 4-crystal monochromator, create a density distribution profile model, perform fitting, and calculate the density distribution in the film thickness direction.

<(Average) film thickness>
(TEM image of cross section in film thickness direction)
Cross-sectional TEM observation The observation sample was subjected to TEM observation after a thin piece was prepared by the following FIB processing apparatus. At this time, if the sample is continuously irradiated with an electron beam, a contrast difference appears between the portion that is damaged by the electron beam and the portion that is not, so the modified film thickness was calculated by measuring that region.

(FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 200 nm
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 30 seconds Water vapor barrier evaluation of the obtained samples 1 to 11 was performed by the following method.

<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
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Preparation of water vapor barrier property evaluation cell Use a vacuum deposition device (JEOL-made vacuum deposition device JEE-400) on the gas barrier layer surface of 1 to 12, except for the portion (12 mm × 12 mm 9 locations) to be deposited on the barrier film sample before applying the transparent conductive film. Masked and vapor deposited metallic calcium. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the gas barrier property before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the barrier film which was not subjected to the bending treatment.

  The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

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

  The obtained water content was classified into the following five stages.

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

<Surface roughness: surface smoothness>
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments.

Raw material Surface roughness Ra is calculated from the cross-sectional curve of unevenness measured continuously with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope), and the measurement direction is determined by the stylus with a minimum tip radius. The measurement was made many times in the section of 30 μm, and the average roughness related to the amplitude of fine irregularities was obtained.

<Bending test>
The water vapor transmission rates of Samples 1 to 12 that were bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm were evaluated, and the degree of deterioration from the sample that was not bent was evaluated.

Water vapor transmission rate after bending test / Water vapor transmission rate without bending (%)
○: 85% or more Δ: Less than 60% ×: Less than 30% <Appropriate cutting process>
When the obtained gas barrier film samples 1 to 12 were cut into a B5 size using a disk cutter DC-230 (CADL), cracks generated at the cut ends were evaluated.

○: No crack occurrence Δ: No more than 5 crack occurrences ×: 5 or more crack occurrences Tables 1 and 2 show the contents and evaluation results of the above samples 1-12.

  As is clear from the results shown in Table 2, it was found that Samples 1 to 8 of the present invention were excellent in smoothness and water vapor barrier properties and excellent in bending and cutting processing suitability.

Example 2
Preparation of organic photoelectric conversion element Each of the above samples 1 to 12 was deposited with an indium tin oxide (ITO) transparent conductive film having a thickness of 150 nm (sheet resistance 10 Ω / □), using ordinary photolithography technology and wet etching. The first electrode was formed by patterning to a width of 2 mm. The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

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

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

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

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin, 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), two gas barrier film samples 1 to 12 were used, and an epoxy photocurable adhesive was applied as a sealing material to the surface provided with the gas barrier layer. After sandwiching the organic photoelectric conversion elements corresponding to the samples 1 to 12 obtained by the method described above between the adhesive application surfaces of the two gas barrier film samples 1 to 12 coated with the adhesive, The organic photoelectric conversion elements 1 to 12 were cured by irradiating UV light from one substrate side.

(Evaluation)
<Evaluation of durability of organic photoelectric conversion element>
<Evaluation of energy conversion efficiency>
About the produced photoelectric conversion element, the light of the intensity | strength of 100 mW / cm < ² > of a solar simulator (AM1.5G filter) is irradiated, the mask which made the effective area 4.0mm < ² > is piled up on a light-receiving part, and IV characteristic is evaluated. Thus, the short-circuit current density Jsc (mA / cm ² ), the open-circuit voltage Voc (V), and the fill factor FF (%) are respectively measured at the four light receiving portions formed on the same element, and obtained according to the following formula 1. The four-point average value of the energy conversion efficiency PCE (%) was estimated.
(Formula 1) PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial battery characteristics was measured, and the degree of deterioration 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.
Ratio of conversion efficiency / initial conversion efficiency after acceleration test 5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20% respectively Table 3 shows the evaluation results.

  As is apparent from the results shown in Table 3, the gas barrier film of the present invention has a low water vapor transmission rate. Furthermore, the organic photoelectric conversion element produced using the gas barrier film of the present invention has performance even under harsh environments. It can be seen that deterioration hardly occurs.

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)
14 p p layer 14 i i layer 14 n n layer 14 ′ first photoelectric conversion unit 15 charge recombination layer 16 second photoelectric conversion unit 17 hole transport layer 18 electron transport layer

Claims (19)

A gas barrier film in which a polysilazane-containing liquid is applied to at least one surface of a base material to form a gas barrier layer, and the gas barrier layer has a density of two layers adjacent to the surface of the gas barrier layer by performing a modification treatment Different modified layers are formed,
When the film density on the surface side of the two modified layers is d ₁ , the film density on the inner side is d ₂ , and the film density in the unmodified region is d ₃ , d ₂ > d ₁ > d ₃ and a difference Δd (= d ₂ −d ₃ ) between the film density d ₂ and the film density d ₃ is 0.1 g / cm ³ or more. The gas barrier film according to claim 1, wherein Δd is 0.15 g / cm ³ or more. The gas barrier film according to claim 2, wherein Δd is 0.2 g / cm ³ or more. Wherein the modified layer of two layers, a film sum of density thickness regions having a _{d 1 L 1} and the film density thickness _{L 2} of the region having a _{d 2 (L 1 + L 2} ) is 30nm or more, and the ratio gas barrier film according to any one of claims 1 to 3, _{L 2 / (L 1 + L} 2) is characterized in that at least 0.4. The gas barrier film according to claim 4, wherein the ratio L ₂ / (L ₁ + L ₂ ) is 0.6 or more. The gas barrier film according to claim 5, wherein the ratio L ₂ / (L ₁ + L ₂ ) is 0.8 or more.   The gas barrier film according to any one of claims 1 to 6, wherein the surface roughness (Ra) on the side subjected to the modification treatment of the gas barrier layer is 2 nm or less.   The gas barrier film according to claim 1, wherein a smooth layer is provided between the substrate and the gas barrier layer.   The gas barrier film according to claim 8, wherein the smooth layer is formed by curing a photosensitive resin composition containing an acrylate compound.   The gas barrier film according to claim 9, wherein the photosensitive resin composition contains reactive silica particles.   The gas barrier film according to any one of claims 8 to 10, wherein a maximum cross-sectional height Rt (p) of the surface of the smooth layer is 10 nm or more and 30 nm or less. In the manufacturing method of the gas-barrier film of any one of Claims 1-11,
A step of applying a polysilazane-containing liquid to at least one side of the substrate to form a coating film; and
A step of modifying the coating film,
The method for producing a gas barrier film, wherein the modification treatment is a step of irradiating a vacuum ultraviolet ray having a wavelength component of 180 nm or less.   The method for producing a gas barrier film according to claim 12, wherein in the step of irradiating the vacuum ultraviolet ray, at least one condition of oxygen concentration, processing temperature, humidity, irradiation distance, and irradiation time is changed during irradiation.   The manufacturing method of the gas-barrier film of Claim 12 or 13 whose dew point temperature of the atmosphere in the process of irradiating the said vacuum ultraviolet rays is 10 to -50 degreeC.   The manufacturing method of the gas-barrier film of any one of Claims 12-14 whose temperature conditions in the process of irradiating the said vacuum ultraviolet rays are 25 degreeC-200 degreeC. The irradiation intensity of the VUV in the step of irradiating vacuum ultraviolet rays are 10~200mJ / cm ^2, the manufacturing method of the gas-barrier film of any one of claims 12 to 15.   The method for producing a gas barrier film according to any one of claims 12 to 16, wherein the irradiation time of the vacuum ultraviolet ray in the step of irradiating the vacuum ultraviolet ray is 0.1 to 15 seconds.   The organic photoelectric conversion element using the gas barrier film of any one of Claims 1-11.   An organic EL device comprising the gas barrier film according to claim 1.