JP2011143551A - Gas barrier film, method of manufacturing the same and organic photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film excellent in high barrier performance, bending resistance, smoothness, and production suitability, a method of manufacturing the same, and an organic photoelectric conversion element using the same. <P>SOLUTION: In the gas barrier film having a gas barrier layer containing silicon and oxygen at least at one side of a substrate, when the hardness of a substrate surface side (B surface) of the gas barrier layer measured by a nano-indentation method is represented by H1, and the hardness of the opposite surface side (surface A) is represented by H2, the gas barrier film has the hardness ratio (H2/H1) of 1.5 or more to 10.0 or lower and the hardness H2 of the surface A of 2.0 GPa or higher. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a gas barrier film, a method for producing the same, and an organic photoelectric conversion element using the same. More specifically, the present invention relates to a gas barrier film used for display materials such as packages for electronic devices, solar cells, organic EL elements, plastic substrates such as liquid crystals, a manufacturing method thereof, and an organic photoelectric conversion element using the gas barrier film. It is.

  Conventionally, a gas barrier film in which a thin film composed of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is an article that requires blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the deterioration of packaging, food, industrial products and pharmaceuticals. In addition to packaging applications, for example, they are 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 (for example, see Patent Documents 1 to 3).

However, any of the above-disclosed techniques is insufficient as a function of a gas barrier layer such as an organic photoelectric conversion element, and the water vapor transmission rate is significantly lower than 1 × 10 ⁻² g / m ² · day. Thus, further improvement in gas barrier properties has been demanded.

  For example, 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, since the gas barrier layer is formed by vapor deposition, particles are generated in the gas phase as a by-product in the gas phase space, and uniform film formation is hindered by adhesion to the substrate. Therefore, since the smoothness of the surface is inferior, the adaptation to the organic photoelectric conversion element has a problem that the influence of the leakage current is increased and the conversion efficiency is remarkably lowered.

  Further, in the method described in Patent Document 2, a technique is disclosed in which a polysilazane coating film is formed by a wet method and plasma treatment is performed to convert the polysilazane coating film to silica to form a gas barrier layer.

  However, since the conversion reaction efficiency of the plasma treatment is low, as described in the examples, the time required for the silica conversion is as long as 5 minutes, and the film quality on the side opposite to the treatment side of the polysilazane coating film is almost the same. Since it became uniform, it was found that the stress relaxation function when bent was not sufficient and the bending resistance was poor.

  In addition, the method described in Patent Document 3 discloses a technique in which a polysilazane coating film is formed by a wet method, and a gas barrier layer is formed by irradiating 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 problems, and its object is to provide a gas barrier film excellent in high barrier performance, bending resistance, smoothness and production suitability, and a method for producing the same, and an organic material using the same. The object is to provide a photoelectric conversion element.

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

  1. In a gas barrier film having a gas barrier layer containing silicon and oxygen on at least one surface of the substrate, the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer is H1, and the opposite surface side ( When the hardness of surface A) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, and the hardness H2 of the surface A is 2.0 GPa or more. Gas barrier film.

  2. 2. The gas barrier film as described in 1 above, wherein the surface roughness (Ra) of the A surface of the gas barrier layer is 2.0 nm or less.

  3. After applying a polysilazane-containing liquid to at least one surface of the base material to form a polysilazane coating film, irradiation with vacuum ultraviolet rays is performed, and the base surface side (B surface) of the polysilazane coating film is subjected to nanoindentation. The hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less when the measured hardness is H1 and the hardness on the opposite surface side (A surface) is H2, and the hardness of the A surface A method for producing a gas barrier film for forming a gas barrier layer having H2 of 2.0 GPa or more, comprising a dehydration step of dehydrating the polysilazane coating film before or during the irradiation with vacuum ultraviolet rays. A method for producing a gas barrier film.

  4). 4. The method for producing a gas barrier film as described in 3 above, wherein the irradiation light source used in the irradiation treatment with vacuum ultraviolet rays has a wavelength component of 180 nm or less.

  5. 3. An organic photoelectric conversion element using the gas barrier film described in 1 or 2 above.

  According to the present invention, a gas barrier film excellent in smoothness and production suitability as well as high barrier performance and bending resistance, a production method thereof, and an organic photoelectric conversion element using the same can be provided.

An example of the load-displacement curve obtained according to the nanoindentation method is shown. It is a figure which shows an example of the contact state of the diamond indenter and a sample in the hardness measurement by a nano indentation method. 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.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The gas barrier film of the present invention is a gas barrier film having a gas barrier layer containing silicon and oxygen on at least one surface of the substrate, and the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer Is H1, and the hardness on the opposite surface side (A surface) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, and the hardness H2 of the A surface is 2 0.0 GPa or more. This feature is a technical feature common to the inventions according to claims 1 to 5.

  As a more preferred embodiment of the present invention, the surface roughness (Ra) on the A-side subjected to the modification treatment of the gas barrier layer having the above-mentioned characteristics defined in the present invention from the viewpoint of manifesting the effects of the present invention. , 2.0 nm or less is preferable. In the present invention, the modification treatment is preferably a vacuum ultraviolet treatment, and more preferably a treatment of irradiating vacuum ultraviolet rays having a wavelength component of 180 nm or less.

  As a method for producing a gas barrier film of the present invention, a polysilazane-containing liquid is formed on at least one surface of the base material to form a polysilazane coating film, and then an irradiation treatment with vacuum ultraviolet rays is performed to form the polysilazane coating film. When the hardness measured by the nanoindentation method on the substrate surface side (B surface) is H1, and the hardness on the opposite surface side (A surface) is H2, the hardness ratio (H2 / H1) is 1.5 or more. A method for producing a gas barrier film that forms a gas barrier layer having a hardness H2 of 2.0 GPa or more, wherein the A-side hardness H2 is 2.0 GPa or less, and before or during the irradiation process of the vacuum ultraviolet ray And a dehydration step of dehydrating the polysilazane coating film.

  Therefore, according to the present invention, since the hardness of the gas barrier layer is different between the A side which is the surface side and the B surface located on the substrate side, it has a stress relaxation function at the time of bending, and further, the surface of the gas barrier layer. By suppressing the roughness (Ra) to 2 nm or less, the stress concentration point can be suppressed, and the stress relaxation function at the time of bending is increased.

  In addition, by adopting a production method that converts the polysilazane-containing coating into a barrier layer, the surface roughness can be easily suppressed, and a barrier layer with a uniform thickness can be obtained. Increase.

  The use of an irradiation light source that is a vacuum ultraviolet ray having a wavelength component of 180 nm or less, specifically, an excimer improves processing efficiency, shortens processing time, improves productivity, and improves the apparatus and illumination light source. The lifetime of

  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 containing silicon and oxygen on at least one surface of the substrate, and the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer Is H1, and the hardness on the opposite surface side (A surface) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, and the hardness H2 of the A surface is 2. It is 0 GPa or more.

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

  In the present invention, the “gas barrier layer” is a layer made of silicon oxide such as silicon dioxide formed by modifying one or more polysilazane coating films formed by applying a polysilazane-containing liquid. The ratio of the hardness H2 on the surface side (A surface) opposite to the hardness H1 of the surface located on the base material surface side (B surface) of each gas barrier layer (H2 / H1) Is in the range of 1.5 to 10.0.

In the present invention, “gas barrier property” means that the water vapor permeability (60 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method in accordance with JIS K 7129-1992 is 1 ^{× 10 -3 g / (m 2} · 24h) or less, the oxygen permeability was measured by the method based on JIS K 7126-1987 is not more than ^{1 × 10 -3 ml / m 2} · 24h · atm That means.

  As a method for forming a gas barrier layer according to the present invention, a coating liquid containing a single polysilazane compound is applied on at least one surface side on a base material, and then a modification treatment is performed, thereby containing a silicon oxide. And a method of forming a gas barrier layer.

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

  The gas barrier layer according to the present invention preferably has regions with different hardness in the film thickness direction, and preferably 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 coating film modification process, 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 region having high hardness is formed on the reforming treatment side. Further, from the FT-IR analysis in the depth direction, Si having an (average) film thickness of 30 nm in the vicinity of the surface. When the distance between —O atoms is measured, a microcrystalline region is confirmed, and a crystallized region is confirmed in the 3 nm region near the surface.

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, in the treatment of irradiating with vacuum ultraviolet rays, 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, the loss of light energy = suppression of thermal energy can be suppressed. This is preferable because it allows efficient processing.

[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 wet coating method can be adopted as the 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.

  As the polysilazane used for coating so as not to damage the film substrate, a compound having a structural unit that is converted to silica by being ceramicized at a relatively low temperature described in JP-A-8-112879 shown below is preferable. .

However, each of R ₁ , R ₂ and R _{3 in} the formula independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, the obtained gas barrier film is particularly preferably perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms from the viewpoint of compactness.

  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 the polysilazane which is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane described in JP-A-8-112879 exemplified above (Japanese Patent Laid-Open No. 5-238827). Glycidol-added polysilazane obtained by reacting glycidol (JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (JP-A-6-240208), and metal carboxylate Metal silicic acid salt-added polysilazane (Japanese Patent Laid-Open No. 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), metal Add fine particles Metal particles added polysilazane (JP-A 7-196986 JP), and the like to be.

  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 generally in the range of 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 the methyl group with the lowest molecular weight, the adhesion to the base material as the base is improved, and the hard and brittle silica film can be toughened, and the film thickness is increased. However, it is preferable in terms of suppressing the occurrence of cracks.

  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.

[Process for forming polysilazane coating film]
The polysilazane coating film formed from the polysilazane-containing liquid according to the present invention preferably has moisture removed before or during the modification treatment. Therefore, it is preferable that a first step which is a drying step for removing the solvent in the polysilazane coating film and a second step which is a subsequent dehydration step for removing moisture in the polysilazane coating film are preferably added.

(First step: drying step)
In the first step, 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 a high temperature from the viewpoint of rapid treatment, but the temperature and treatment time can be appropriately determined in consideration of thermal damage to the resin substrate. For example, when a polyethylene terephthalate 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 thermal damage to the substrate is reduced, and is preferably set within 30 minutes if the heat treatment temperature is 200 ° C. or lower.

(Second process: Dehydration process)
The second step (dehydration step) is a step for removing moisture in the formed polysilazane coating film. As a method for removing moisture, the first method is preferably maintained in a low humidity environment. Since the humidity in the low humidity environment changes depending on the temperature, the relationship between the temperature and the humidity shows a preferable form by the definition of the dew point temperature. A preferable dew point temperature is 4 degrees or less (temperature 25 degrees / humidity 25%), a more preferable dew point temperature is -8 degrees (temperature 25 degrees / humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 degrees / humidity 1%). ) -31 degrees or less. Next, as a second method, a form maintained in a reduced pressure environment can be mentioned. Specifically, the pressure environment is lower than normal pressure (1 atm), specifically, at least 0.4 atm or less, preferably 0.1 atm or less, more preferably 0.01 atm or less to obtain the effect. .

  Next, as a third method, a form maintained in a high temperature environment can be mentioned. In this case, the combined use with the second method is effectively used. The temperature in the third method is selected in the range of 50 to 200 ° C.

  The time maintained by the first method to the third method is appropriately adjusted according to the thickness of the polysilazane coating film.

  The polysilazane coating 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 coating film]
The water content of the polysilazane coating film according to the present invention can be detected by the following analysis method.

<Headspace-gas chromatograph / mass spectrometry>
Equipment: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min) → 10 ° C./min→150° C.
Column: DB-624 (0.25 mmid × 30 m)
Inlet: 230 ° C
Detector: SIM (m / z) = 18
HS condition: 190 ° C, 30min
In the present invention, the water content in the polysilazane coating film is defined as a value obtained by dividing the water content obtained by the above analysis method by the volume of the polysilazane coating film, and preferably in a state where moisture is removed by the second step. It is 0.1% or less, and a more preferable water content is 0.01% or less (below the detection limit).

  This is a preferred embodiment because moisture is removed before or during the modification treatment as in the present invention to accelerate the dehydration reaction of the polysilazane coating film converted to silanol.

[Modification treatment of polysilazane coating film]
For the modification treatment of the polysilazane coating film in the present invention, a known method based on the conversion reaction of the polysilazane coating film can be selected.

  Formation of a silicon oxide film by a substitution reaction of a silazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt in a system using a flexible substrate such as plastic. In the present invention, a plasma treatment capable of a conversion reaction at a lower temperature and a conversion reaction using ozone or ultraviolet rays are preferable for adaptation to a plastic substrate. In particular, in the method for producing a gas barrier film of the present invention, polysilazane is preferable. It is characterized by a method of modifying the coating film by subjecting it to irradiation with vacuum ultraviolet rays.

  Hereinafter, in the gas barrier film of the present invention, plasma treatment and ultraviolet irradiation treatment applicable to the modification of the polysilazane coating film, and in particular, vacuum ultraviolet irradiation treatment applied to the gas barrier film manufacturing method of the present invention will be described.

(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 or an 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is 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 atmospheric pressure plasma will be described. Specifically, as described in the specification of 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. It is preferable to form an electric field that overlaps the high-frequency 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 start electric field satisfy 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 a discharge condition, for example, even a discharge gas having a high discharge starting electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. be able to.

  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 , By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited 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 light (synonymous with ultraviolet light) have high oxidation ability, and a silicon oxide film having high density and insulation can be produced at low temperature.

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” specifically means ultraviolet rays (UV light) having a wavelength of 400 nm or less, radiation rays including X-rays and electron beams. In a preferred embodiment of the method according to the present invention, ultraviolet rays of 100 to 400 nm, more preferably 150 to 180 nm are used.

  In the irradiation of ultraviolet rays, the irradiation intensity or 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, for example, 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. ^The distance between the substrate and the lamp is set so as to be ^2, and irradiation for 0.1 second to 10 minutes can be performed.

  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 and 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 should be reflected by 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 (for example, a silicon wafer) having a polysilazane coating film on its surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known, and for example, it is possible to use those manufactured by I-Graphics Co., Ltd. Further, when the substrate having the polysilazane coating film on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in the 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.

(Irradiation treatment using vacuum ultraviolet rays)
In the method for producing a gas barrier film of the present invention, irradiation treatment with vacuum ultraviolet rays is used as the modification treatment of the polysilazane coating film.

  The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the silazane compound, and oxidizes with active oxygen or ozone while directly cleaving the bonds of atoms by the action of only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by advancing the reaction.

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

Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules. However, noble gas atoms (excited atoms) that have gained energy by discharge can combine with other atoms to form molecules. 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. Moreover, since excess light is not emitted and there is little light energy loss (= thermal energy conversion), the temperature of a target object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In addition to the rare gas alone, a rare gas halide can also be used as a gas species for obtaining excimer emission.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a 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), the electric discharge accumulates on the surface of the dielectric 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. Therefore, in order to cause discharge in the entire discharge space, the outer electrode covers the entire outer surface and transmits light to extract light to the outside. Must be a thing. 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 closing 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.

  In particular, the Xe excimer lamp is excellent in luminous efficiency because it emits short 172 nm ultraviolet light having a wavelength of 180 nm or less at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane coating 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 turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated with a single wavelength in the ultraviolet region, so that an increase in the surface temperature of the object to be fired is suppressed. For this reason, it is suitable for flexible film materials, such as a polyethylene terephthalate film said to be easily influenced by heat.

[Gas barrier layer hardness]
The gas barrier film of the present invention has a gas barrier layer containing silicon and oxygen on at least one surface of the substrate, and the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer is H1, When the hardness on the opposite surface side (A surface) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, and the hardness H2 of the A surface is 2.0 GPa or more. It is characterized by being.

  The hardness distribution of the barrier layer in the present invention can be calculated by a nanoindentation method.

  The nano-indentation method is to continuously load and unload an indenter with a very small load on a sample, and measure the hardness and reduced modulus from the obtained load-displacement curve. It is a method to do.

(Measurement principle of nanoindentation method)
The nanoindentation method can be used to measure indentation hardness at the nano level by adding an indentation hardness measurement module (configured with a transducer and an indentation tip) to an atomic force microscope (AFM). This is the latest measurement method. While applying a load of μN or less, a diamond indenter is pushed into the sample, and the indentation depth is measured with nanometer accuracy. From this measurement, a load-displacement curve diagram can be obtained, and the characteristics relating to the elasto-plastic deformation of the material can be quantitatively evaluated. In the case of a thin film, in order to perform measurement without being affected by the substrate, it is necessary to push in to a depth of 1/10 to 1/3 of the film thickness.

  FIG. 1 shows an example of a load-displacement curve obtained according to the nanoindentation method.

  FIG. 2 is a diagram illustrating an example of a contact state between a diamond indenter and a sample in hardness measurement by the nanoindentation method. In FIG. 2, 1 is the initial surface of the sample when the indenter is not in contact, 2 is the profile of the sample surface when a load is applied through the indenter, and 3 is the sample after removing the indenter. It is a surface profile.

  The hardness H is obtained from the equation H = W / A (W is a load, A is a contact area). However, in the nanoindentation method, since the load is very small, A cannot be obtained directly from an indentation or the like.

Therefore, as shown in FIG. 2, hc has an equation of hc = ht−ε · W / S (where ε is a constant unique to the indenter and S is the slope described in FIG. 1), and A = 24.5hc2. If ht, W, and S are known, H can be obtained. The composite elastic modulus Er can be calculated from Er = S · π ^1/2 / 2 / A ^1/2 . It is presumed that if Er is large, plastic deformation is easy, and if Er is small, elastic deformation is easy.

  In the present invention, measurement is performed using a Tribscope manufactured by Hysitoron, attached to a scanning probe microscope (SPI3800N manufactured by Seiko Instruments Inc.). The working indenter is a cube corner tip (90 °).

  The sample size is 20 mmφ × 10 mm at maximum, but is fixed to the sample table with an adhesive or the like. Since the load range of this apparatus is as low as 10 mN, it is suitable for measuring the hardness and elastic modulus of a thin film having a film thickness of about 10 nm to 1 μm. Although the above method can measure materials from DLC films to polymers, it is suitable for measurement of hard materials such as the inorganic gas barrier layer according to the present invention.

  In the present invention, when the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer is H1, and the hardness on the opposite surface side (A surface) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, more preferably 3.0 or more and 8.5 or less, and further preferably 4.5 or more and 7.0. It is as follows.

  Moreover, although the hardness H2 of A surface is 2.0 GPa or more, Preferably, it is 2.0 GPa or more and 3.0 GPa or less.

  In the present invention, after the polysilazane coating layer is formed on the substrate and the gas barrier layer is formed by the modification treatment, the hardness H1 on the substrate surface side (B surface) and the hardness H2 on the opposite surface side (A surface) The specific measurement method is as follows.

  First, the hardness H2 of the gas barrier layer surface (A surface) of the produced gas barrier film is measured by the nanoindentation method according to the above method. Next, according to the film thickness information of the hardness H1 region and the film thickness information of the hardness H2 region described in the measurement of the thickness of the modified layer described later, the film thickness region of the hardness H1 by sputtering or the like from the gas barrier layer surface (A surface). And the hardness H1 region is exposed, and the hardness H1 is measured by the nanoindentation method in the same manner.

  As a method of adjusting the hardness ratio (H2 / H1) according to the present invention within the range specified by the present invention, selection of the modifying means, (average) film thickness, moisture content, and modification treatment of the polysilazane coating film are performed. This can be done by adjusting conditions such as the treatment intensity, the oxygen concentration in the irradiation atmosphere, and the treatment time. For example, in the modification process using vacuum ultraviolet light, the hardness ratio is adjusted to be higher by controlling the conditions such that the (average) film thickness of the polysilazane coating film is thin, the vacuum ultraviolet light intensity is high, and the processing time is shortened. be able to.

For example, when the polysilazane coating film thickness is 50 nm to 1000 nm, it can be selected from vacuum ultraviolet illuminance of 10 to 100 mJ / cm ² , oxygen concentration of 0 to 5%, and processing time of 0.1 to 150 sec.

(Measurement of modified layer thickness)
In the gas barrier film of the present invention, the (average) film thickness of the surface side (A surface) region having the hardness H2 on the surface to be subjected to the modification treatment, and the hardness H1 of the substrate surface side (B surface) which is the opposite side. The calculation of the (average) film thickness of the region having the can be determined as follows.

(TEM image of cross section in film thickness direction)
A thin piece is prepared from the observation sample by the following FIB processing apparatus, and then TEM observation is performed. At this time, if the sample is continuously irradiated with the electron beam, a contrast difference appears between the portion that is damaged by the electron beam and the portion that is not so, and can be calculated by measuring the region. The region with high hardness on the modification treatment side is not easily damaged by electron beam, but the other part is damaged by electron beam and the alteration is confirmed.

<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 The gas barrier layer obtained by modifying the polysilazane coating film as in the present invention is the surface A on the modification treatment side and the opposite side (base material side). It has been found that the hardness is different from the B surface, and that the ratio and the (average) film thickness are within the above ranges, thereby preventing cracking due to stress concentration and achieving both a high barrier property and a stress relaxation function. In particular, the vacuum barrier treatment of the gas barrier layer is preferable 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]
In the gas barrier film of the present invention, the surface roughness (Ra) of the surface A which is the surface on the modification treatment side of the gas barrier layer according to the present invention is preferably 2.0 nm or less, more preferably 1. 0 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 A surface 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 cross-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.

<Configuration of gas barrier film>
(Base material)
The substrate (hereinafter also referred to as a support) that can be applied to the gas barrier film of the present invention is particularly limited as long as it is formed of an organic material that can hold a gas barrier layer having a barrier property described later. It is not something.

  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. As for the thickness of a base material, about 5-500 micrometers is preferable, More preferably, it is 25-250 micrometers.

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

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

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

  Moreover, in the base material which concerns on this invention, you may perform a corona treatment before forming a vapor deposition film.

Furthermore, you may form an anchor coating agent layer in the base-material surface concerning this invention for the purpose of the adhesive improvement with a 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 a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(Smooth layer)
The 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 substrate with protrusions or the like, or to fill the unevenness and pinholes generated in the transparent inorganic compound layer with the protrusions existing on the transparent resin film substrate. Is provided. Such a smooth layer is basically formed by curing a photosensitive resin.

  As the photosensitive resin constituting 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 Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as acrylate, 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 the reactive monomer having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n -Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, Dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate Glycidyl 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, tri Lopylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2 , 4-trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyl tri Examples include methoxysilane and 1-vinyl-2-pyrrolidone. 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. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 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, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) 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) oxy , Michler's 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 And a combination of a photoreductive dye such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  The method for forming the smooth layer is not particularly limited, but the smooth layer can be formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition 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.

  Examples of the solvent 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. Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, di Glycol ethers such as propylene 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 Lumpur dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value represented 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 coating property may be impaired when the coating means comes into contact with the surface of the smooth layer in the coating method such as a wire bar or wireless bar at the stage of coating the silicon compound. is there. 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>
Preferred additives for the smooth layer include 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. It is a waste. 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 that can be applied to the gas barrier film of the present invention, when a film having a smooth layer is heated, unreacted oligomers migrate from the film substrate to the surface and contaminate the contact surface. It is provided on the opposite surface of the base material having a smooth layer for the purpose of suppressing the phenomenon that occurs.

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

  Moreover, as a unit price unsaturated organic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-e Xoxyethoxy) 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, for example, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like should be used in combination. Can do.

  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.

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

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

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon 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 prepared as a coating solution by mixing a hard coat agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can form by apply | coating to a material 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.

  In the present invention, the thickness of the bleed-out prevention layer 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, and among them, it is characterized by being used for an organic photoelectric conversion element.

  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 substrate to receive sunlight from this side. That is, on the gas barrier film of the present invention, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the substrate is used as an anode, a porous semiconductor layer is provided thereon, a cathode made of a metal film is 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 substrate to the surroundings and encapsulating the element, thereby allowing moisture such as outside air or oxygen The influence on the element can be sealed.

  The resin base material for organic photoelectric conversion elements is obtained by forming a transparent conductive film on the gas barrier layer of the gas barrier film formed in this way.

  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 the gas barrier film of the present invention and a resin base material for an organic photoelectric conversion element on which a transparent conductive film is formed will be described.

[Sealing film and manufacturing method thereof]
In the present invention, the gas barrier film of the present invention is used as a substrate as the sealing film according to the present invention.

  In the gas barrier film of the present invention, a transparent conductive film is further formed on the gas barrier layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated thereon, using this as an anode, Further, another gas barrier film as a sealing film can be sealed by overlapping.

  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) In this case, 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 An alloy foil, a stainless steel foil, a tin (Sn) foil, a high nickel alloy foil, etc. are mentioned. 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. When the thickness exceeds 50 μm, the cost increases 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.

  In the metal foil laminated with a resin film (polymer film), as the resin film, various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. 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, chloride Examples thereof include vinylidene resins. 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, after forming a transparent conductive film on the resin film (gas barrier film) which has the gas barrier layer of this invention, and forming each layer of an organic photoelectric conversion element on the produced resin substrate for organic photoelectric conversion elements, Using the sealing film, the organic photoelectric conversion element can be sealed by covering the cathode surface with the sealing film in an environment purged with an inert gas.

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

  In sealing an organic photoelectric conversion element using a 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 of 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 with an impulse sealer and sealed.

  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, if the amount of adhesive applied is too large, tunneling, seepage, shrinkage, etc. may occur, so the amount of adhesive should be 3-5 μm in dry (average) film thickness. It is preferable to adjust.

  Hot melt lamination is a method in which a hot melt adhesive is melted and an adhesive layer is applied to a substrate, but the thickness of the adhesive layer is generally set within a wide range of 1 to 50 μm. . Commonly used base resins for hot melt adhesives include EVA, ethylene-ethyl acrylate copolymer resin (EEA), polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. Are added as a tackifier and wax as a plasticizer.

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

  Generally, low density polyethylene (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 coating 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 present invention, the ceramic layer is formed by selecting conditions such as an organometallic compound, a decomposition gas, a decomposition temperature, and input power as a raw material (also referred to as a raw material) in an atmospheric pressure plasma method. It is possible to make different compositions such as metal oxides mainly composed of silicon oxide, and mixtures with metal carbides, metal nitrides, metal sulfides, metal halides, etc. (metal oxynitrides, metal oxide halides, etc.) it can.

  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, dimethyldiethoxy. Silane, 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 Diethylaminotrimethylsilane, 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 Propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclo Examples thereof include tetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51 (manufactured by Tama Chemical Co., Ltd.), and the like.

  Examples of the decomposition gas for obtaining the ceramic layer by decomposing the source gas containing silicon include, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide Examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  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 or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon or the like is 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.

  In the present invention, the thickness of the ceramic layer 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 of 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 pinched | interposed into both an anode and a cathode (it is also called the layer where a p-type semiconductor and an n-type semiconductor were mixed, a bulk heterojunction layer, and i layer). May be any element that has at least one layer and generates a current when irradiated with light.

  The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.

(1) Anode / power generation layer / cathode (2) Anode / hole transport layer / power generation layer / cathode (3) Anode / hole transport layer / power generation layer / electron transport layer / cathode (4) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (5) Anode / hole transport layer / first light-emitting layer / electron transport layer / intermediate electrode / hole transport layer / second light-emitting layer Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, which are substantially two layers and heterojunction. Alternatively, a bulk heterojunction in a mixed state in one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  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 ((2), ( 3)) is preferred. Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself also sandwiches the power generation layer with a layer made of a p-type semiconductor material and a single n-type semiconductor material as shown in (4). 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 (5)) 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. 3 for the purpose of improving sunlight utilization (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. 3 is a cross-sectional view showing an example of a solar cell made of a bulk heterojunction organic photoelectric conversion element. In FIG. 3, the bulk heterojunction type organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a power generation layer 14 as 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. 3, 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. 3, 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 shown in FIG. 4 has a so-called p-i-n three-layer configuration. 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. However, a p-layer composed of a single p-type semiconductor material and an n-layer composed of a single n-type semiconductor material. By sandwiching, 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. 5 is a cross-sectional view showing a solar cell made of an organic photoelectric conversion element having a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second power generation layer 16, and then the counter electrode 13 are stacked. By stacking, a tandem structure can be obtained. The second power generation layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first power generation layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. Further, both the first power generation layer 14 ′ and the second power generation layer 16 may have the above-described three-layer structure of pin.

  Below, the material which comprises these layers is described.

[Organic photoelectric conversion element material]
(P-type semiconductor material)
In the present invention, examples of the p-type semiconductor material used for the power generation layer (bulk heterojunction layer) include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low molecular weight compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, thacumanthracene, bisanthene, zeslene. , Heptazethrene, pyranthrene, violanthene, isoviolanthene, circobiphenyl, anthradithiophene, etc., porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis (ethylenedithio) tetra Examples include thiafulvalene (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. Pentacene derivatives having substituents described in JP-A-107216 and the like, pentacene precursors described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  Examples of the conjugated polymer include a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer, a polythiophene-diketopyrrolopyrrole copolymer described in International Publication No. 2008/000664, and a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160 , Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, 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, as an oligomer material instead of a polymer material, for example, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis which is a thiophene hexamer is used. Oligomers such as (3-butoxypropyl) -α-sexithiophene can be preferably used.

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

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

  Examples of such materials include materials that can be insolubilized by polymerizing the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a soluble substituent reacts and insolubilizes by applying energy such as heat as described in U.S. Patent Application Publication No. 2003/136964 and JP-A-2008-16834 (pigment). Material).

(N-type semiconductor material)
In the present invention, the n-type semiconductor material used for the bulk heterojunction layer is not particularly limited. For example, perfluoro compounds (perfluorocarbons such as fullerene, octaazaporphyrin, etc.) in which hydrogen atoms of a p-type semiconductor are substituted with fluorine atoms Fluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized compounds thereof Examples thereof include polymer compounds.

  However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (˜50 fs) and efficiently are preferable. Examples of fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotube, multi-wall nanotube, single-wall nanotube, nanohorn (conical type), and the like. Some of these are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups. The fullerene derivative substituted by these etc. can be mentioned.

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

(Hole transport layer / electron block layer)
In the organic photoelectric conversion element 10 according to the present invention, the hole transport layer 17 is provided between the bulk heterojunction layer and the anode, so that charges generated in the bulk heterojunction layer can be taken out more efficiently. This is preferable.

  As a material constituting these hole transport layers 17, for example, PEDOT such as trade name BaytronP, polyaniline and its doped material, cyan compounds described in WO2006019270, etc. are used. Can do. Note that electrons generated in the bulk heterojunction layer do not flow to the anode side in 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. An electronic block function having a rectifying effect is provided. 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. Moreover, the layer which consists of a p-type semiconductor material single-piece | unit used for the bulk hetero junction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

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

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro compound (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, a p-type semiconductor used for a bulk heterojunction layer. The electron transport layer having a HOMO level deeper than the HOMO level of the material is provided with a hole blocking function that has a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side. The 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)
It is good also as a structure which has various intermediate | middle layers in an organic photoelectric conversion element for the purpose of the improvement of energy conversion efficiency and the improvement of element lifetime. 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 selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers 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 made of a conductive material, but in addition to a conductive material, a resin for holding these may be used in combination. As the conductive material for the counter electrode, a material having a low work function (4 eV or less) metal, alloy, electrically conductive compound, or a mixture thereof as an electrode material is used. Specific examples of such electrode materials include, for example, 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 (Al2O3) 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.

  By using a metal material 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. It is preferable because the conversion efficiency is improved.

  Further, 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. A dispersion is preferable because 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)
Further, the intermediate electrode material required in the case of the tandem structure as described in the item (5) or FIG. 5 is preferably a layer using a compound having both transparency and conductivity. Materials used for electrodes (transparent metal oxides such as ITO, AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, 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 fibers applicable to the present invention, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used. Metal nanowires are preferable.

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

  In the present invention, the metal nanowires preferably have an average length of 3.0 μm or more in order to form a long conductive path with one metal nanowire and to exhibit appropriate light scattering properties. Furthermore, 3.0 to 500 μm is preferable, and 3.0 to 300 μm is particularly preferable. 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.

  In the present invention, the metal composition of the metal nanowire is not particularly limited, and may be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire 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 preferably applied as a method for producing metal nanowires in the present invention. can do.

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

(Optical function layer)
The organic photoelectric conversion element of the present invention may have various optical function 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 thick, which is not preferable.

  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>
In the production of the organic photoelectric conversion device of the present invention, a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a method for forming a transport layer / electrode include a vapor deposition method, a coating method (cast method, spin coat method). And the like. 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>
In the present invention, the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like 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 application such as die coating or dip coating, or directly at the time of application using a method such as an ink jet method or screen printing. Patterning may be performed.

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

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

Example 1
<< Preparation of substrate 1 >>
As a thermoplastic resin base material, a substrate of a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films Ltd.) that has been easily bonded on both sides is annealed at 170 ° C. for 30 minutes. Used as 1.

<< Production of Substrate 2 Having Smooth Layer and Bleed-Out Prevention Layer >>
While forming the base material 1 at a speed of 30 m / min, after forming a bleed-out preventing layer on one side and a smooth layer on the opposite side by the following forming method, an adhesive protective film is used to prevent the smooth layer from being damaged. Were bonded to obtain a roll-shaped substrate 2.

[Formation of bleed-out prevention layer]
On one side of the substrate 1, a UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7535) manufactured by JSR Corporation was applied and applied with a wire bar so that the average film thickness after drying was 4.0 μm. Thereafter, curing was performed at 80 ° C. for 3 minutes as a drying condition using a high-pressure mercury lamp under 1.0 J / cm ² air as a curing condition to form a bleed-out prevention layer.

[Formation of smooth layer]
Next, an average after applying and drying a UV curable organic / inorganic hybrid hard coat material (OPSTAR Z7501) manufactured by JSR Corporation on the surface of the substrate 1 opposite to the surface on which the bleed-out prevention layer is formed. After coating with a wire bar so that the film thickness becomes 4 μm, after drying at 80 ° C. for 3 minutes as a drying condition, using a high-pressure mercury lamp in an air atmosphere, a curing condition of 1.0 J / Curing was performed at cm ² to form a smooth layer, and a substrate 2 was produced.

  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 by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is determined by the stylus having a minimum tip radius. This is the average roughness of the amplitude of fine irregularities measured in a 30 μm section many times.

<< Production of gas barrier film >>
Samples 1 to 17 which are gas barrier films were produced according to the following method.

[Preparation of Sample 1: Present Invention]
A gas barrier layer was formed according to the following method on the smooth layer of the base material 2 provided with the smooth layer and the bleed-out prevention layer prepared above, and Sample 1 was prepared.

(Preparation and application of gas barrier layer coating solution)
Perhydropolysilazane (PHPS) 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN120-20) is used as the gas barrier layer coating solution 1, and the (average) film thickness after drying with a wireless bar However, it apply | coated on the smooth layer so that it might become 0.30 micrometer, and the coating sample 1 which formed the polysilazane coating film was produced.

(First step; drying treatment)
The obtained coated sample 1 was treated for 1 minute in an atmosphere of a temperature of 80 ° C. and a humidity of 3% RH (dew point temperature of 12 ° C.) to obtain a dried coated sample 1.

(Second step; dehydration step)
The dried coated sample 1 was further held for 10 minutes in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.), and dehydrated to obtain a dehydrated coated sample 1.

(Modification A)
The coated sample 1 subjected to the dehydration treatment was subjected to the modification treatment A under the following conditions to form a gas barrier layer, whereby a sample 1 was obtained. The dew point temperature during the reforming treatment was -8 ° C.

<Modification processing equipment>
Irradiation device: manufactured by M.D. Com., Excimer irradiation device MODEL: MECL-M-1-200, wavelength: 172 nm, lamp-filled gas: Xe
The modified sample A was applied to the coated sample 1 fixed on the operation stage under the following conditions.

<Reforming treatment conditions>
Excimer light intensity: 60 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer irradiation time: 5 seconds [Preparation of sample 2: the present invention]
Sample 2 was prepared in the same manner as in the preparation of Sample 1, except that the modification process B shown below was used instead of the modification process A as a method for forming the gas barrier layer.

(Modification B)
Using the coated sample 1 that had been subjected to the same dehydration treatment as the preparation of the sample 1, the modification treatment B was performed under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

<Modification processing equipment>
Irradiation device: excimer irradiation device manufactured by M.D. Com., MODEL: MECL-M-1-200, wavelength: 172 nm, lamp gas: Xe
The modified sample B was applied to the coated sample 1 fixed on the operation stage under the following conditions.

<Reforming treatment conditions>
Excimer light intensity: 60 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 0.1%
Excimer irradiation time: 1 second [Preparation of sample 3: the present invention]
Sample 3 was prepared in the same manner as in the preparation of Sample 2, except that the dehydration step as the second step was omitted.

[Preparation of Sample 4: Present Invention]
In the preparation of Sample 3, when applying and drying with a wireless bar when forming the gas barrier layer, the air is blown to the surface of the polysilazane coating film to accelerate drying, and blown to the surface to cause unevenness (= roughening the surface) Sample 4 was prepared in the same manner except that () was formed.

[Preparation of Sample 5: Present Invention]
Sample 5 was prepared in the same manner as in the preparation of Sample 4 except that the modification process B was changed to the following modification process C.

<Modification C>
In the same manner as Modification B, except that the wavelength was changed to 222 nm, the lamp-filled gas was changed to KrCl, and the modification treatment time was changed to 10 seconds.

[Preparation of Sample 6: Present Invention]
Sample 6 was prepared in the same manner as in the preparation of Sample 1 except that, instead of the modification treatment A, a modification treatment D, which is the following atmospheric pressure plasma treatment method, was performed as a modification treatment for the formed polysilazane coating film. Was made.

(Modification D)
The dehydrated coated sample 1 used for preparing Sample 1 was subjected to atmospheric pressure plasma treatment (modification treatment D) under the following conditions to form a gas barrier layer, and Sample 6 was obtained. At this time, the substrate holding temperature during the reforming treatment was 120 ° C.

  The reforming treatment D was performed using a roll electrode type discharge treatment apparatus. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel with the transport direction of the coated sample 1, and gas and power are supplied to each electrode part under the following conditions, and the polysilazane coating film surface is irradiated with plasma for 15 seconds. Went.

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

<Gas conditions>
Discharge gas: N ₂ gas Reaction gas: 7.0% by volume of oxygen gas with respect to the total gas
<Power requirements>
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 7: Present Invention]
Sample 7 was prepared in the same manner as Sample 6 except that the modification process D was changed to the following modification process E.

<Modification E>
In the modification process D, the modification process E was performed in the same manner except that the plasma irradiation time was changed to 60 seconds.

[Production of Samples 8 to 11: Present Invention]
In the preparation of the sample 2, the dehydration conditions in the second step (dehydration step) were changed as follows, and the modification time in the modification process B was changed to 3 seconds (this is referred to as the modification process F). Samples 8 to 11 were obtained in the same manner except for).

(Second process: Dehydration process conditions)
Sample 8: Hold for 20 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) Sample 9: Hold for 5 minutes in a vacuum dryer at 50 ° C. and 0.01 atm. , Held for 20 minutes in an atmosphere of humidity 1.0% RH (dew point temperature −31 ° C.) Sample 11: held for 5 minutes in a vacuum dryer at a temperature of 100 ° C. and 0.001 atm.
Sample 12 was prepared in the same manner as in the preparation of Sample 1, except that the method for forming the gas barrier layer was changed to the following method.

(Formation of gas barrier layer)
A gas barrier layer was formed according to the gas barrier film forming method (CVD film forming method) described in Example 1 of JP-A-2004-66730.

[Production of Sample 13: Comparative Example]
Sample 13 was prepared in the same manner as in the preparation of Sample 1, except that the method for forming the gas barrier layer was changed to the following method.

(Formation of gas barrier layer)
A gas barrier layer was formed according to the gas barrier film forming method (CVD film forming method) described in Example 2 of [Example] of JP-A-2004-66730.

[Production of Sample 14: Comparative Example]
In the preparation of Sample 1, the second step (dehydration process) was omitted, the modification process A was changed to the modification process D, and the modification time was changed to 20 seconds. Obtained.

[Production of Sample 15: Comparative Example]
In the preparation of Sample 1, Sample 15 was prepared in the same manner except that the second step (dehydration treatment) was omitted and the gas barrier layer modification treatment A was replaced with the following modification treatment G. The film hardness of the gas barrier layer formed by the modification process G is uniform film hardness (2.11 GPa) in the entire film thickness region (hardness H1 = hardness H2).

(Modification G)
The atmospheric pressure plasma treatment of the polysilazane coating film described in Example 1 of JP-A-2007-237588 is referred to as a modification treatment G.

[Production of Sample 16: Comparative Example]
Sample 16 was prepared in the same manner as Sample 1 except that the second step (dehydration process) was omitted and the gas barrier layer was modified in the following modified process H instead of modified process A.

(Modification H)
The excimer irradiation treatment of the polysilazane coating film described in Example 2 of [Example] of JP-T-2009-503157 was designated as modification treatment H.

[Preparation of Sample 17: Comparative Example]
A sample 17 was obtained in the same manner as in the preparation of the sample 14 except that the gas barrier layer modification time in the modification process D was changed to 5 seconds (this modification process I).

<Measurement of characteristic values of gas barrier film>
[Measurement of average film thickness in hardness H1 region and H2 region]
The average film thickness of the hardness H1 area | region and H2 area | region in the barrier layer of the obtained samples 1-17 was measured with the following method.

(Measurement of average film thickness)
Each of the prepared samples was subjected to TEM observation after an ultrathin section was prepared using the following FIB processing apparatus. At this time, by continuing to irradiate the sample with the electron beam, a contrast difference appears between the portion that is damaged by the electron beam and the portion that is not, and by measuring the region, the average of the modified hardness H2 region on the A plane side The film thickness and the average film thickness in the hardness H1 region on the B surface side that was not modified were calculated. In addition, the average film thickness was calculated | required as the arithmetic average value which measured the film thickness of 50 places.

<FIB processing equipment, conditions>
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 200 nm
<TEM observation conditions>
Electron microscope device: JEM2000FX (acceleration voltage: 200 kV) manufactured by JEOL
Electron beam irradiation time: 30 seconds (measurement of hardness H1 and H2 of gas barrier layer)
1) Measurement of A surface side hardness H2 The gas barrier layer surface (A surface) of each of the samples prepared above was measured according to the nanoindentation method described above. Specifically, hardness H2 was measured using a scanning probe microscope (SPI3800N manufactured by Seiko Instruments Inc.) and Triscope from Hysitoron. Note that a cube corner tip (90 °) was used as the working indenter.

2) Measurement of Hardness H1 on the B Side Next, the surface of the gas barrier layer (A surface) of each sample was sputtered until the hardness H1 region was removed based on the measurement information of the average film thickness until the hardness H1 was exposed. After trimming by the above, the hardness in the hardness H1 region was measured by the same method as described above to obtain the hardness H1.

  Table 1 shows the results obtained above and the basic structure of the gas barrier film.

<< Evaluation of gas barrier film >>
The gas barrier film was evaluated according to the following method.

(Evaluation of surface smoothness: measurement of surface roughness)
The surface roughness Ra of each sample was calculated from an uneven sectional curve continuously measured with a detector having a stylus with a minimum tip radius using an atomic force microscope (AFM, DI3100AFM manufactured by Digital Instruments). With a stylus having a tip radius of, the measurement direction was measured many times within a section of 30 μm, and the average roughness (nm) related to the amplitude of fine irregularities was determined.

(Evaluation of water vapor barrier properties)
The water vapor permeability was measured according to the following method, and the water vapor barrier property was determined according to the following evaluation rank.

<Vacuum evaporation system>
Vapor deposition apparatus: Vacuum vapor deposition apparatus 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)
<Production of water vapor barrier property evaluation cell>
On the gas barrier layer forming surface of each sample, the above-mentioned vacuum vapor deposition apparatus (JEOL vacuum vapor deposition apparatus JEE-400) is used to deposit a portion (12 mm × 12 mm) of a gas-barrier film sample before attaching a transparent conductive film. The portion other than the portion was masked, and metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited on the entire surface of one side of the sheet from another metal deposition source. After sealing with aluminum, the vacuum state is released, and in a dry nitrogen gas atmosphere, the silica sealing side (through Nagase Chemtex Co., Ltd.) is sealed on quartz glass with a thickness of 0.2 mm via a sealing UV curable resin (manufactured by Nagase ChemteX). An evaluation cell was produced by facing and 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 under high temperature and high humidity of 60 ° C. and 90% RH, 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 gas 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 was used. Similarly, it was stored under high temperature and high humidity at 60 ° C. and 90% RH, and it was confirmed that no metallic calcium corrosion occurred even after 1000 hours.

  Based on the water content obtained as described above, the water barrier property was evaluated by classifying into the following five stages.

5: Water vapor transmission amount is less than 1 × 10 ⁻⁴ g / m ² / day 4: Water vapor transmission amount is 1 × 10 ⁻⁴ g / m ² / day or more, 1 × 10 ⁻³ g / m ² / day Less than 3: The water vapor transmission rate is 1 × 10 ⁻³ g / m ² / day or more and less than 1 × 10 ⁻² g / m ² / day 2: The water vapor transmission amount is 1 × 10 ⁻² g / m ² / day or more and less than 1 × 10 ⁻¹ g / m ² / day 1: Water vapor transmission amount is 1 × 10 ⁻¹ g / m ² / day or more (evaluation of bending resistance)
For each sample, after bending 100 times with a radius of 10 mm and an angle of 180 degrees so that the gas barrier layer forming surface is on the outside, the water vapor transmission rate was measured by the same method as above, and the bending was performed. From the water vapor transmission rate (water vapor transmission rate obtained by the evaluation of the water vapor barrier property) of the sample that was not measured, the water vapor barrier property deterioration rate was measured according to the following formula, and the bending resistance was evaluated according to the following criteria.

Water vapor barrier deterioration rate = {1-[(water vapor barrier degree after bending test (= reciprocal of water vapor permeability)) / water vapor barrier degree of non-bent sample (= reciprocal of water vapor permeability)]} × 100 (%)
5: Water vapor barrier deterioration rate is less than 10% 4: Water vapor barrier deterioration rate is 10% or more and less than 20% 3: Water vapor barrier deterioration rate is 20% or more and less than 50% 2: Water vapor barrier deterioration rate is 50 % Or more, less than 70% 1: Table 2 shows each evaluation result obtained when the steam barrier property deterioration rate is 70% or more.

  As is clear from the results shown in Table 2, it can be seen that Samples 1 to 11 of the present invention are superior in surface smoothness, water vapor barrier property and bending resistance to the comparative example.

Example 2
<< Production of organic photoelectric conversion element >>
Samples 1 to 17 prepared in Example 1 were prepared by depositing 150 nm of indium tin oxide (ITO) transparent conductive films (sheet resistance 10 Ω / □), and then normal photolithography technology and wet etching were performed. The first electrode was formed by patterning to a width of 2 mm using Next, the patterned first electrode is cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, then dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning. It was.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was applied and dried so that the average film thickness was 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 the following operation was performed in a nitrogen atmosphere.

First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and 3.0 wt% Then, a liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm and the film was filtered (filtered), and allowed to dry at room temperature. Subsequently, the heat processing for 15 minutes were performed at 150 degreeC, and the photoelectric converting layer was formed into a film.

Next, the substrate on which the series of functional layers is formed is moved into the vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then the substrate is fed at a deposition rate of 0.01 nm / second. Next, 0.6 nm of lithium fluoride is stacked, and then 100 nm of Al metal is stacked at a deposition rate of 0.2 nm / sec through a shadow mask having a width of 2 mm (vaporization is performed so that the light receiving portion is 2 × 2 mm). Thus, the second electrode was formed.

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

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), two samples, samples 1 to 17, which are gas barrier films produced in Example 1, were used, and epoxy-based light was used as a sealing material on the surface provided with the gas barrier layer. A curable adhesive was applied. After sandwiching the organic photoelectric conversion elements corresponding to the samples 1 to 17 obtained by the method described above between the adhesive application surfaces of the two gas barrier film samples 1 to 9 coated with the adhesive, The organic photoelectric conversion elements 1 to 17 were cured by irradiating UV light from one substrate side.

<< Evaluation of organic photoelectric conversion element >>
About each produced said organic photoelectric conversion element, durability was evaluated in accordance with the following method.

[Evaluation of durability]
Each organic photoelectric conversion device prepared above, was irradiated with light having an intensity of 100 mW / cm ² solar simulator (AM1.5G filter), a superposed mask in which the effective area 4.0 mm ² on the light receiving portion, the IV characteristics By evaluating the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V) and the fill factor FF (%), the four light receiving portions formed on the organic photoelectric conversion element were measured, A four-point average value of energy conversion efficiency PCE (%) obtained according to the following formula 1 was estimated.

Formula 1
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
Measure the conversion efficiency PCE1 as the initial battery characteristics, then measure the conversion efficiency PCE2 after the accelerated test stored at a temperature of 55 ° C. and a humidity of 85% RH for 1000 hours. The durability was evaluated according to the following evaluation rank.

Conversion efficiency remaining rate (%) = (conversion efficiency after acceleration test PCE2 / initial conversion efficiency PCE1) × 100
5: The conversion efficiency remaining rate is 90% or more 4: The conversion efficiency remaining rate is 80% or more and less than 90% 3: The conversion efficiency remaining rate is 50% or more and less than 80% 2: Conversion The efficiency remaining rate is 30% or more and less than 50% 1: The conversion efficiency remaining rate is less than 30% Table 3 shows the results obtained.

  As is clear from the results shown in Table 3, the organic photoelectric conversion device produced using the gas barrier film of the present invention has less performance deterioration even in a harsh environment and superior durability compared to the comparative example. I understand.

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

Claims (5)

  In a gas barrier film having a gas barrier layer containing silicon and oxygen on at least one surface of the substrate, the hardness measured by the nanoindentation method on the substrate surface side (B surface) of the gas barrier layer is H1, and the opposite surface side ( When the hardness of surface A) is H2, the hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less, and the hardness H2 of the surface A is 2.0 GPa or more. Gas barrier film.   2. The gas barrier film according to claim 1, wherein the surface roughness (Ra) of the A surface of the gas barrier layer is 2.0 nm or less.   After applying a polysilazane-containing liquid to at least one surface of the base material to form a polysilazane coating film, irradiation with vacuum ultraviolet rays is performed, and the base surface side (B surface) of the polysilazane coating film is subjected to nanoindentation. The hardness ratio (H2 / H1) is 1.5 or more and 10.0 or less when the measured hardness is H1 and the hardness on the opposite surface side (A surface) is H2, and the hardness of the A surface A method for producing a gas barrier film for forming a gas barrier layer having H2 of 2.0 GPa or more, comprising a dehydration step of dehydrating the polysilazane coating film before or during the irradiation with vacuum ultraviolet rays. A method for producing a gas barrier film.   The method for producing a gas barrier film according to claim 3, wherein the irradiation light source used in the irradiation treatment with vacuum ultraviolet rays has a wavelength component of 180 nm or less.   An organic photoelectric conversion element using the gas barrier film according to claim 1.

Images