JP2013039786A - Gas barrier film, method for producing gas barrier film, and organic electronic device having gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film capable of achieving a high productivity, a high gas barrier performance and a high gas barrier stability (hygrothermal resistance, bending durability), to provide a method for producing the gas barrier film, and to provide an electronic device using the gas barrier film.SOLUTION: The gas barrier film against three gases having a resin substrate 4, at least one barrier layer 2, and an adjacent layer 1 which is located adjacent to the barrier layer at least at the substrate side, is characterized in satisfying the following conditions (1) and (2). (1) The adjacent layer 1 has a region including at least M atom (M denotes Si, Ti, Zr, Al and Zn), O atom and C atom at the same time, and an atomic composition ratio of C/M is 0.2-2.2 and an atomic composition ratio of O/M is 1.0-2.0, (2) the barrier layer has a region including at least Si atom and N atom at the same time, and an atomic composition ratio of N/Si is 0.3-0.8 and an atomic composition ratio of C/Si is <0.1.

Description

  The present invention mainly relates to a gas barrier film used for a display material such as a package of an electronic device or the like, or a plastic substrate such as an organic electroluminescence element, a solar cell, or a liquid crystal, and a manufacturing method thereof, and an organic electronic using the gas barrier film It is about the device.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals.

  In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

  As a method for producing such a gas barrier film, a chemical deposition method (plasma CVD) in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to form a film on a substrate while being oxidized by oxygen plasma under reduced pressure. And a sputtering method in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen.

These methods have been preferably used for the production of metal oxide thin films including SiO ₂ because a thin film having an accurate composition can be produced on the substrate. There were problems such as requiring time to open to the atmosphere, difficulty in continuous production, and significant increase in equipment size.

  In order to solve such problems, a method of producing a silicon oxide thin film by applying a silicon-containing compound and modifying the coating film for the purpose of improving productivity, and a chemical vapor deposition method (CVD method) Attempts have been made to generate plasma at atmospheric pressure to form a film at atmospheric pressure, and gas barrier films have been studied.

  As a silicon oxide film that can be generally produced by a solution process, a technique of producing an alkoxide compound as a raw material by a method called a sol-gel method is known.

  This sol-gel method generally requires heating to a high temperature, and further, there is a problem that a large volume shrinkage occurs in the course of the dehydration condensation reaction, and many defects are likely to occur in the film.

  In order to prevent this, methods have been found to mix organic substances that are not directly involved in the production of oxides into the raw material solution. However, these organic substances remain in the film, and there is concern that the barrier properties of the entire film may be reduced. Has been.

  For these reasons, it has been difficult to directly use an oxide film produced by a sol-gel method as a protective film of a flexible electronic device.

  As another method, it has been proposed to produce silicon oxide using a silazane compound having a basic structure of silazane structure (Si-N) as a raw material. In this case, the reaction is not from dehydration condensation polymerization but from nitrogen to oxygen. Since this is a direct substitution reaction, it is known that a dense film having a mass yield before and after the reaction of 80% to 100% or more and few defects in the film due to volume shrinkage can be obtained.

  However, the production of a silicon oxide thin film by a substitution reaction of a silazane compound requires a high temperature of 450 ° C. or higher and cannot be applied to a flexible substrate such as plastic.

  In recent years, using optical energy of 100 nm to 200 nm called vacuum ultraviolet light (VUV light) larger than the interatomic bonding force in the silazane compound, the bonds of atoms are directly cut by the action of only photons called photon processes. There has been proposed a method for producing a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed.

  For example, Patent Document 1 discloses a technique in which a polysilazane film is formed by a wet method and a part of the polysilazane film is converted to silica to form a gas barrier layer by vacuum ultraviolet treatment. However, the disclosed production method irradiates the vacuum ultraviolet ray for 1 to 5 minutes for a long time. For example, when considering continuous production like roll-to-roll, a very long irradiation line is required. Productivity is not high.

  Patent Document 2 discloses a technique for forming a gas barrier layer by forming a polysilazane film by a wet method and irradiating UV light in an atmosphere containing water vapor.

  However, the dehydration reaction after silanol formation does not proceed sufficiently due to the atmosphere containing water vapor, and the resulting film density is low, and the gas barrier performance is not sufficient. In order to dehydrate-condense the residual silanol, it is necessary to apply heat of about 300 ° C. to 400 ° C. or similar energy, and it has been difficult to develop a high gas barrier property particularly with a flexible resin substrate.

  Therefore, as a result of intensive studies by the present inventors, it is necessary to have an appropriate oxygen source and an appropriate light energy for activating the polysilazane bond in order to efficiently improve the polysilazane. It has been found. Especially when reforming using excimer light, the amount of excimer light reaching the film surface varies greatly depending on the oxygen concentration in the atmosphere, so control is performed so that the oxygen concentration does not become too high for efficient processing. It is necessary. In addition, the presence of excessive moisture as an oxygen source promotes the formation of silanol as described above, and causes a significant deterioration in barrier properties.

  Therefore, the barrier layer obtained by converting the polysilazane coating film by VUV irradiation under a low oxygen concentration atmosphere of 0.1% or less and under low humidity has a dense and high barrier property, and is more than a film formed by CVD or the like. Since it can be flattened with few defects, an excellent barrier film can be formed.

  However, in the accelerated deterioration performance evaluation under heating / humidification environment, the barrier property evaluation by the Ca method is that the barrier property deteriorates suddenly at a certain point after the permeation of water vapor, and the barrier property is lost. It has been confirmed by organic device element evaluation, and has become a major issue in obtaining a stable gas barrier film.

  Regarding providing a layer between the resin base material and the barrier layer, it is possible to provide a primer layer between the base material and the barrier layer mainly for improving adhesion between the resin base material and the barrier layer. It is disclosed in Document 4.

JP 2009-255040 A Special table 2009-503157 JP 2009-101620 A JP 2011-718

  The present invention has been made in view of the above-mentioned problems, and the object thereof is a gas barrier film capable of achieving high gas barrier performance and high gas barrier performance stability (wet heat resistance, bending resistance), and a gas barrier film. And an electronic device using the gas barrier film.

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

1. A gas barrier film comprising a resin substrate, at least one barrier layer, and an adjacent layer 1 adjacent to the barrier layer at least on the substrate side, wherein the following (1) and (2) are satisfied: Sex film.
(1) The adjacent layer 1 has a region containing at least M atoms (M represents Si, Ti, Zr, Al, Zn), O atoms, and C atoms at the same time. Is 0.2 to 2.2, and O / M is 1.0 to 2.0.
(2) The barrier layer has at least a region containing Si atoms and N atoms at the same time, and N / Si is 0.3 to 0.8 and C / Si <0.1 in terms of atomic composition ratio.

  2. 2. The gas barrier film according to 1 above, wherein the barrier layer further contains O atoms, and O / Si is 0.2 to 1.3 in terms of atomic composition ratio.

  3. 3. The gas barrier film according to 1 or 2, further comprising an adjacent layer 2 adjacent to the barrier layer on the side opposite to the substrate, in addition to the adjacent layer 1 adjacent to the barrier layer on the substrate side. Characteristic gas barrier film.

  4). 4. The gas barrier film according to any one of 1 to 3, wherein the M atom is Si.

  5). It is a manufacturing method of the gas barrier film of any one of said 1-4, Comprising: After apply | coating the coating liquid of the composition containing perhydropolysilazane on the said adjacent layer 1, it performs a conversion process. The manufacturing method of the gas-barrier film characterized by forming the barrier layer containing an inorganic substance.

  6). 6. The method for producing a gas barrier film according to 5, wherein the conversion treatment is an ultraviolet irradiation treatment.

  7). An organic electronic device sealed with the gas barrier film described in any one of 1 to 4 above.

  According to the present invention, a gas barrier film capable of achieving high gas barrier performance and high gas barrier performance stability, a method for producing the gas barrier film, and an electronic device using the gas barrier film can be provided.

It is sectional drawing which shows an example of the solar cell of this invention which has a bulk heterojunction type organic photoelectric conversion element. It is sectional drawing which shows an example of the solar cell which has an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer. It is sectional drawing which shows an example of the solar cell which has an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer. It is sectional drawing which shows the structure of the produced gas barrier film.

  Hereinafter, the present invention will be described in detail.

  As described above, the performance deterioration of the gas barrier film in a heated / humidified environment, that is, the phenomenon in which the barrier property suddenly deteriorates at a certain point after starting to permeate water vapor, The cause was not grasped at all, and could not be linked to improvement means.

  As the inventors proceeded with the study, the inventors have inferred that the reason why the barrier property deteriorates rapidly and a stable barrier film cannot be obtained is mainly due to the following three points.

1) Adhesion between the resin substrate and the barrier layer suddenly deteriorates due to wet heat, and the barrier film breaks 2) Breakage of the barrier layer due to internal stress accumulated during the conversion of the coating type barrier layer 3) Water from the substrate side In order to obtain a stable barrier film that does not deteriorate its barrier properties rapidly due to deterioration of the quality of the polysilazane-modified film due to, a stable polysilazane conversion barrier layer modified with a good film quality on a flexible resin substrate It was thought that it was most important to develop a barrier layer underneath that would hold.

  As described above, Patent Document 3 or Patent Document 4 discloses a barrier film in which a primer layer is provided between a base material and a barrier layer mainly for improving adhesion between the resin base material and the barrier layer.

  However, the film quality of the polysilazane modified film varies greatly depending on the composition of the barrier layer lower layer, and if an appropriate barrier layer lower layer is selected, the modification efficiency and performance stability can be greatly improved. The current situation has never been known.

  Thus, in order to eliminate the rapid deterioration of the barrier property of the polysilazane modified film that is the barrier layer, there is no adhesion deterioration with the substrate even under wet heat, and to relieve the internal stress accumulated in the barrier layer, In order to suppress the supply of moisture as an oxygen source from the base material side during the formation of the barrier layer, the adjacent layer 1 having an atomic composition ratio within the scope of the present invention may be formed as the barrier layer lower layer (adjacent layer 1).

  Further, in order to further improve the stability including process resistance and the like, it is preferable to further provide a similar layer (adjacent layer 2) on the barrier layer.

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

<< Gas barrier film and method for producing gas barrier film >>
The gas barrier film of the present invention and the method for producing the gas barrier film will be described.

The gas barrier film of the present invention comprises a resin base material, at least one barrier layer, and at least one adjacent layer 1 adjacent to the barrier layer at least on the base material side, and further, the adjacent The layer 1 and the barrier layer satisfy the following (1) and (2).
(1) The adjacent layer 1 has a region containing at least M atoms (M represents Si, Ti, Zr, Al, Zn), O atoms, and C atoms, and C / M is 0.2 to 2. .2 and O / M is 1.0 to 2.0.
(2) The barrier layer has at least a region containing Si atoms and N atoms at the same time, and N / Si is 0.3 to 0.8 and C / Si <0.1.

  Further, the barrier layer more preferably has a region containing O atoms simultaneously in addition to Si atoms and N atoms, and O / Si satisfies 0.2 to 1.3. C / Si is preferably less than 0.1, and most preferably below the detection limit. If it is 0.1 or more, the gas barrier properties deteriorate.

  In addition to the adjacent layer 1 adjacent to the barrier layer on the substrate side, it is more preferable that the adjacent layer 2 adjacent to the barrier layer is further provided on the side opposite to the substrate.

  Further, the M atoms contained in the adjacent layer 1 represent Si, Ti, Zr, Al, and Zn, and are most preferably Si atoms.

  As a method for producing a gas barrier film of the present invention, in the formation of a gas barrier layer, after applying a coating solution of a composition containing perhydropolysilazane on the adjacent layer 1, a conversion treatment (also referred to as a modification treatment) is performed. A barrier layer containing an inorganic material is formed by applying.

  Further, the conversion process is an ultraviolet irradiation process.

  The step of modifying the coating after the step of forming a coating by applying a solution containing perhydropolysilazane will be described in detail later.

[Gas barrier properties]
The gas barrier property referred to in the present invention is a 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 · 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1.01325 × 10 ⁵ Pa).

[Configuration of gas barrier film]
Note that the gas barrier layer (also simply referred to as a barrier layer or a barrier film) may be a single layer (a layer that can be formed by one application) or a plurality of similar layers. By providing a plurality of layers, the gas barrier property can be further improved. Moreover, although a gas barrier layer may be provided only on one side of the base material, a similar gas barrier layer may be provided on both sides of the base material.

  Moreover, it becomes possible to suppress base-material deformation | transformation by providing the layer similar to the adjacent layer 1 also in the back surface side of the base material on the opposite side to the side which provided the adjacent layer 1 and barrier layer on a base material. In addition to maintaining the curl balance, it is more preferable in that the device fabrication process resistance and handling suitability are also improved. Such curl balance can be adjusted by optimizing the film thickness, curing conditions, and the like of a layer (also referred to as a back coat layer) provided on the back side.

  When providing a plurality of barrier layers, a barrier layer may be further laminated on the barrier layer as described above, but a barrier layer is further provided on the adjacent layer 2 provided on the barrier layer. Are also preferably used. Thus, by providing the adjacent layer 2 having the same atomic composition ratio as that of the adjacent layer 1 between the barrier layers, the second barrier layer can be expected to have the same effect as the first barrier layer. Therefore, it is considered that two barrier layers in a more desirable modified state can be formed.

[Formation of gas barrier layer]
The gas barrier layer of the present invention is formed by applying a coating solution of a composition containing polysilazane, preferably perhydropolysilazane, onto the adjacent layer 1 and then subjecting it to a modification treatment by irradiation with vacuum ultraviolet rays (VUV light). A barrier layer is formed.

  The barrier layer containing an inorganic substance in the present invention has at least a region containing Si atoms and N atoms at the same time, and more preferably has a region containing Si atoms, N atoms and O atoms at the same time.

  Specific examples of inorganic substances include silicon oxide, silicon nitride, and silicon oxynitride.

  Further, the atomic composition ratio of the barrier layer in the present invention is characterized in that N / Si is 0.3 to 0.8, and O / Si more preferably satisfies 0.2 to 1.3. preferable. C / Si is less than 0.1 and is most preferably below the detection limit. If it is 0.1 or more, the gas barrier property is lost.

  Each atomic composition ratio of Si atom, N atom, O atom, and C atom is determined by XPS surface analysis.

  The XPS surface analyzer used for the surface analysis is not particularly limited, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  The barrier layer having the atomic composition ratio of the present invention is obtained by subjecting a coating film of perhydropolysilazane to vacuum ultraviolet irradiation in an appropriate oxidizing gas atmosphere and a low humidity environment as described later, and an adjacent layer 1 described later. It becomes possible to form efficiently by arranging two of the configurations provided in the lower layer.

[Formation of coating film containing polysilazane]
(Application method)
The coating film containing polysilazane according to the present invention is produced by wet coating a coating solution containing at least one polysilazane compound on a substrate.

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

  The coated film is preferably annealed to obtain a uniform dry film from which the solvent has been removed. The annealing temperature is preferably 60 to 200 ° C, more preferably 70 to 160 ° C. The annealing time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 2 hours.

  As described above, by performing annealing in the above-described range before the conversion process following the next step, a uniform coating film can be stably obtained.

  The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease).

  In addition, once the coating liquid and coating film containing polysilazane are exposed to a high humidity state, it is difficult to dehydrate from the coating liquid and coating film, and furthermore, the hydrolysis reaction starts to proceed. To an atmosphere having a dew point of 10 ° C. (25 ° C., 39% RH) or less, more preferably an atmosphere having a dew point of 8 ° C. (25 ° C., 10% RH) or less, from the preparation stage of the coating solution to the end of the modification treatment. By handling, generation of Si—OH in the film can be suppressed. More preferably, the dew point is −31 degrees (25 ° C., 1% RH) or less. In addition, when a thin film is formed, the surface area per volume of the coating film increases and the influence of water vapor increases, so it is particularly important to control the atmospheric humidity between the application of the polysilazane-containing solution and the modification treatment by VUV light irradiation. It is.

  The dew point temperature is an index representing the amount of moisture in the atmosphere, and the dew point temperature is a temperature at which condensation starts when air containing water vapor is cooled.

  It can be obtained by measuring directly with a dew point thermometer, or by obtaining the water vapor pressure from the temperature and relative humidity and obtaining the temperature at which the water vapor pressure is the saturated water vapor pressure. When the relative humidity is 100%, the current temperature is directly at the dew point temperature.

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

  In order not to damage the film base material, it is converted to silica by being ceramicized at a relatively low temperature as represented by the following general formula (1) described in JP-A-8-112879. Compounds are preferred.

General formula (1)
—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, each of R ₁ , R ₂ and R ₃ 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, perhydropolysilazane (also referred to as PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a gas barrier layer (also simply referred to as a barrier layer) to be obtained. preferable.

  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 toughened, and there is an advantage that generation of cracks can be suppressed even when the film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

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

  As another example of polysilazane which is ceramicized at low temperature, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane represented by the general formula (1) with a silicon alkoxide (for example, JP-A-5-23827), glycidol A glycidol-added polysilazane obtained by reacting an alcohol (for example, JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (for example, JP-A-6-240208), and a metal carboxylate Metal carboxylate-added polysilazane (for example, JP-A-6-299118) obtained, and acetylacetonate complex-added polysilazane (for example, JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex. ), Added metal fine particles And metal fine particles added polysilazane obtained (e.g., JP-A-7-196986 JP), and the like.

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

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

(Composition containing perhydropolysilazane)
The composition containing perhydropolysilazane in the present invention is not particularly limited as long as it contains perhydropolysilazane, and the material other than perhydropolysilazane in the composition can be applied with perhydropolysilazane and its solvent. Any material may be used as long as it has a certain level of compatibility.

  Further, the composition may contain a catalyst such as amine or metal added to promote the oxidation reaction at about 0.1 to 10% by mass relative to perhydropolysilazane. 5-5 mass% containing is preferable at the point of application | coating property and shortening of reaction.

  The content of perhydropolysilazane excluding the solvent and additives in the composition is preferably 80% by mass or more from the viewpoint of barrier properties, and 100% by mass, that is, consisting of only perhydropolysilazane, It is most preferable in that a dense film having a high barrier property can be formed.

  Examples of materials that can be obtained as perhydropolysilazane in the present invention include Aquamica NN120, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, and NP140 manufactured by AZ Electronic Materials.

[Conversion treatment of perhydropolysilazane]
(Conversion treatment by UV irradiation)
The conversion treatment (modification treatment) in the present invention applied to the composition containing perhydropolysilazane is performed by irradiating with ultraviolet rays in an appropriate oxidizing gas atmosphere and a low humidity environment.

  Irradiation with ultraviolet light generates active oxygen and ozone, and an oxidation reaction proceeds, whereby an inorganic film having a desired composition can be obtained.

  Since this active oxygen and ozone are very reactive, the polysilazane in the coating film formed from the composition containing perhydropolysilazane is oxidized directly without passing through silanol, resulting in higher density and defects. A silicon oxide or silicon oxynitride film with a low content is formed.

  The conversion treatment in the present invention is more preferably performed in combination with a heat treatment.

  Further, ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion for the shortage of reactive ozone and introduced into the ultraviolet irradiation portion.

  Although the wavelength of the ultraviolet light irradiated at this time is not particularly limited, the wavelength of the ultraviolet light is preferably 100 to 450 nm, and more preferably vacuum ultraviolet light (VUV light) of about 100 to 300 nm is irradiated.

As the light source, a low-pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. The output of the lamp ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, preferably 10~5000mJ / cm ² as irradiation energy, 100 to 2000 mJ / cm ² is more preferable. Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² .

  Among these, as the wavelength, vacuum ultraviolet rays (VUV light) of 100 to 200 nm are most preferable, and the oxidation reaction can be advanced at a lower temperature and in a shorter time. As a light source, a rare gas excimer lamp such as a xenon excimer lamp is most preferably used.

  Although polysilazane in a coating film formed from a composition containing perhydropolysilazane is irradiated with ultraviolet rays in an oxidizing gas atmosphere, polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. The film thickness and density of the silica film can be controlled by the intensity of ultraviolet light, irradiation time, and wavelength (light energy density), and should be appropriately selected, such as using different types of lamps to obtain a desired film structure. Is possible. In addition to continuous irradiation, multiple irradiations may be performed, and so-called pulse irradiation in which the multiple irradiations are performed in a short time may be used.

  In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to promote the reaction (also referred to as oxidation reaction, conversion treatment, or modification treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. You may select suitably the method which can maintain the smoothness of a coating film.

  As temperature to heat, the range of 50-200 degreeC is preferable, More preferably, it is the range of 80-150 degreeC, As the heating time, the range of 1 second-10 hours is preferable, More preferably, it is 10 seconds-1 hour Heating in a range.

(Conversion treatment by vacuum ultraviolet (VUV) irradiation)
Among the light irradiation treatments, vacuum ultraviolet (VUV light) treatment is more preferable.

  This vacuum ultraviolet ray (VUV light) irradiation breaks the molecular bond of polysilazane, and even a small amount of oxygen in the film or atmosphere can be efficiently converted into ozone or active oxygen. Is converted to ceramics (silica modification), and the resulting ceramic film becomes denser. VUV light irradiation is effective at any time point after the coating film is formed.

  Specifically, vacuum ultraviolet rays (VUV light) of 100 to 200 nm are used as the vacuum ultraviolet rays in the present invention. The irradiation intensity and / or irradiation time of vacuum ultraviolet rays can be set as appropriate. As the vacuum ultraviolet irradiation apparatus, a commercially available lamp (for example, manufactured by USHIO INC.) Can be used.

  VUV light 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 provided with a coating film formed from a composition containing perhydropolysilazane can be processed in a vacuum ultraviolet ray baking furnace equipped with a vacuum ultraviolet ray generation source. The vacuum ultraviolet baking furnace itself is generally known, and for example, Ushio Electric Co., Ltd. can be used. Moreover, when the base material provided with the coating film formed from the composition containing perhydropolysilazane is in the form of a long film, in the drying zone equipped with the vacuum ultraviolet ray generation source as described above while transporting it. By continuously irradiating with vacuum ultraviolet rays, the surface can be ceramicized.

  Since the vacuum ultraviolet light is larger than the interatomic bonding force of most substances, it can be preferably used because the bonding of atoms can be cut directly by the action of only photons called photon processes. By using this action, the reforming process can be efficiently performed at a low temperature without requiring hydrolysis.

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

Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon, e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric) in a similar very thin discharge called micro discharge, the electric charge accumulates on the dielectric surface, and the micro discharge disappears. The dielectric barrier discharge is a discharge in which this micro discharge spreads over the entire tube wall and 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, the electrodes, and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

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

  In order to prevent this, it is necessary to create 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 illumination. 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 illumination 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 outer surface of the lamp. 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.

  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. If the curved surface is mirrored with aluminum, it becomes a light reflector.

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

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light with a long wavelength that causes a temperature increase due to light is not emitted and energy is irradiated with a short wavelength in the ultraviolet region, the surface temperature of the irradiation object can be suppressed from increasing.

  Moreover, if the irradiation intensity of vacuum ultraviolet rays is high, the probability that a photon and a chemical bond in polysilazane will collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification). However, if the irradiation time is too long, the flatness may be deteriorated and other materials of the gas barrier film may be damaged. In general, the progress of the reaction is considered based on the integrated light quantity expressed by the product of the irradiation intensity and the irradiation time. The value may be important.

Therefore, in the present invention, in the VUV light irradiation step, it is preferable to perform a modification treatment that gives a maximum irradiation intensity of 100 to 200 mW / cm ² at least once. If it is below this intensity, the reforming efficiency will deteriorate rapidly, and it will take time for the treatment. If the irradiation intensity is higher than this, damage to the lamp and other parts of the lamp unit will increase, and the lamp itself will deteriorate. Will be accelerated.

  The irradiation time of VUV light can be arbitrarily set, but the irradiation time in the high illuminance process is preferably 0.1 second to 3 minutes. More preferably, it is 0.5 second to 1 minute.

  The oxygen concentration at the time of VUV light irradiation is preferably 500 to 10,000 ppm (1%). More preferably, it is 1000-5000 ppm. If the oxygen concentration is higher than the above concentration range, the reforming efficiency is lowered. If the oxygen concentration is lower than the above range, the replacement time with the atmosphere becomes longer, and at the same time, continuous production like roll-to-roll is possible. When performing, the amount of air (including oxygen) entrained in the VUV light irradiation chamber is increased by web transport, and the oxygen concentration cannot be adjusted unless a large flow rate of gas is allowed to flow.

  In the polysilazane-containing coating film, oxygen and a small amount of water are mixed at the time of application, and there are adsorbed oxygen and adsorbed water on the substrate and the adjacent resin layer other than the polysilazane-containing coating film. It was found that there are enough oxygen sources to supply oxygen required for the reforming reaction without introducing oxygen. Further, as described above, VUV light of 172 nm is absorbed by oxygen, and the amount of light of 172 nm reaching the film surface is reduced, so that the processing efficiency by light is lowered. That is, at the time of VUV light irradiation, it is preferable to perform the modification treatment in a state where the VUV light efficiently reaches the coating film in a state where the oxygen concentration is as low as possible.

  As the gas other than oxygen at the time of VUV light irradiation, a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

[Adjacent layer 1]
The gas barrier film of the present invention comprises a resin base material, at least one barrier layer, and at least one adjacent layer 1 adjacent to the barrier layer on at least the base material side.

  The adjacent layer 1 in the present invention has a region containing at least M atoms (M represents Si, Ti, Zr, Al, Zn), O atoms, and C atoms at the same time, and C / M is 0.2-2. .2 and O / M satisfies 1.0 to 2.0, and has carbon atoms derived from an organic group at a predetermined ratio.

  Each atomic composition ratio of M atom (M represents Si, Ti, Zr, Al, Zn), O atom, and C atom is determined by XPS surface analysis.

  The XPS surface analyzer used for the surface analysis is not particularly limited, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

(Method for forming adjacent layer 1)
The adjacent layer 1 in the present invention is preferably formed by coating.

  The coating film thickness can be appropriately set depending on the material and the substrate, but the thickness after drying is preferably about 10 nm to 100 μm, more preferably about 100 nm to 10 μm, and for flattening the surface of the substrate. About 1 μm to 6 μm is most preferable because it can also serve as a planarizing layer and a stress relaxation layer.

(Material for forming the adjacent layer 1)
As a material for forming the adjacent layer 1 in the present invention, the finally obtained film has M atoms (M represents a metal such as Si, Ti, Zr, Al, Zn), O atoms, and C atoms simultaneously. If the relationship of C / M is 0.2 to 2.2 and O / M is 1.0 to 2.0 is established in the atomic composition ratio in the region Is not to be done.

  The region where the atomic composition ratio is satisfied does not have to be the entire region of the formed film, but it is preferably at least 1 nm, more preferably at least 10 nm continuously in the film thickness direction.

  The material for forming the adjacent layer 1 includes a metal acid polymer having an organic group which is an organic / inorganic hybrid material, a condensate of metal acid oligomers, and a mixture thereof (metals are Si, Ti, Zr, Al, Zn) And the like, and may be a copolymer composed of two or more different metal acid units or a mixture thereof.

  In the present invention, the C atom contained in the adjacent layer 1 may be derived from an additive, but is more preferably derived from an organic group that substitutes a metal of a metal acid polymer or metal acid oligomer. preferable.

  Furthermore, the metal atom represented by M is more preferably an Si atom from the viewpoint of affinity with the Si atom contained in the barrier layer.

  Specific examples of the material include polysiloxane having an organic group (also referred to as organic polysiloxane) and polytitanic acid having an organic group, and organic polysiloxane is preferable.

  Organopolysiloxane is a general term for siloxanes having a constitutional unit having 1 to 2 organic groups per silicon atom in a silicon-containing polymer in which the main chain is composed of siloxane bonds. Among the basic structural units, it is more preferable to include an organic polysiloxane, that is, silsesquioxane having one organic group bonded to a silicon atom and the remaining three bonded to oxygen.

  As the organic group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group , 3-ethylbutyl group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and other alkyl groups, vinyl group, allyl group and other alkenyl groups, ethynyl group and other alkynyl groups, phenyl group and tolyl An aryl group such as a group, an aralkyl group such as a benzyl group and a phenethyl group, and other unsubstituted monovalent hydrocarbon groups may be mentioned, and may have a substituent such as fluorine. Also included are alkoxy groups such as methoxy and ethoxy groups.

  Specific compounds that can be used as a raw material for forming the adjacent layer 1 include, for example, methyl hydropolysiloxane, methylsilsesquioxane, hydrosilsesquioxane (manufactured by Konishi Chemical Co., Ltd.), tetrasilanophenyl. Examples include cage-like organic silsesquioxane such as POSS, polydiethoxysiloxane, diethoxysiloxane-ethyl titanate copolymer, polydibutyl titanate, and organic polysilazane.

  It is also possible to apply a commercially available material as the organic polysiloxane that forms the adjacent layer 1.

  In addition to the methyl silsesquioxane and hydrosilsesquioxane (Konishi Chemical Co., Ltd.), Nittobo inorganic / organic nanocomposite material SSG coat (SSG coat HB21BN, SSG coat HB31BN), ceramic manufactured by JSR Corporation Examples thereof include a coating material Glasca (Glaska HPC7003), diethoxysilane-ethyl titanate copolymer PSITI-019 manufactured by Gelest, and the like.

  In addition, in the present invention, in order to form an organic polysiloxane film, T unit (the number of organic groups bonded to silicon atoms in the basic structural unit of polysiloxane is one, and the remaining three are bonded to oxygen. A solution containing silsesquioxane having a D) unit (polysiloxane) in that it can form a film having high solubility in a coating solvent and good coating properties and smoothness. The organic polysiloxane film is formed using a solution containing an organic polysiloxane having two organic groups bonded to silicon atoms and the remaining two bonded to oxygen. It may be formed. At this time, it is preferable that at least a part of the D unit organopolysiloxane is crosslinked by heat treatment or the like to form a T unit silsesquioxane. Thereby, the highly stable adjacent layer 1 having appropriate hardness can be formed.

  For the purpose of accelerating the curing (condensation reaction) of the organic polysiloxane film, an amine catalyst, an organometallic catalyst having palladium, tin or the like, or an alkoxysilane such as tetraethoxysilane may be added to the material liquid. In addition, for the purpose of improving the adhesion to the substrate or the barrier layer, it is also preferable to add a silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltriethoxysilane. Moreover, you may add a small amount of binders, such as resin, in order to improve applicability | paintability. Moreover, you may use the hardening reaction by an ultraviolet-ray.

  As the organic / inorganic hybrid material forming the adjacent layer 1, a commercially available thermosetting hard coat agent or the like can also be applied.

  For example, TutProm series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, nano hybrid silicone manufactured by Adeka, various silicone resins manufactured by Shin-Etsu Chemical, etc.

(Function of adjacent layer 1)
In the prior art, in the barrier layer, the main purpose was how to proceed the hydrolysis and dehydration condensation reaction of polysilazane, whereas in the present invention, before the modification treatment by vacuum ultraviolet ray (VUV light) irradiation, during the treatment, It is considered most important for efficient reforming how the hydrolysis reaction of polysilazane is not caused after the treatment.

  Once the hydrolysis reaction proceeds before the reforming process and a large amount of Si-OH is formed in the film, the barrier layer can be used for the reforming process by irradiating VUV light thereafter. It becomes difficult to form a layer exhibiting barrier properties having a region containing Si atoms, N atoms, and O atoms at the same time.

  Therefore, in the present invention, as described above, the atomic composition ratio of the present invention is achieved by irradiating VUV light in an optimum low oxygen concentration atmosphere and in a low humidity environment, and allowing only direct oxidation by active oxygen to proceed. It is important to form a barrier layer made of Si, N, and O having the following.

  Further, as described above, it has been found that simply optimizing the environment at the time of reforming is not sufficient to obtain a stable barrier performance. It is presumed that the quality of the polysilazane modified film may be deteriorated by moisture entering from an undercoat layer such as a coat layer, a planarization layer, or an adhesion layer.

  Therefore, it has been found that if the adjacent layer 1 having the atomic composition of the present invention is previously provided in the lower layer for forming the polysilazane modified film, silanol groups and the like are not generated, and the modification of the polysilazane can be made efficient. The present invention has been reached.

  Actually, the atomic composition of the modified polysilazane film varies depending on the state of the lower layer, and it can be confirmed by XPS surface analysis described above and barrier performance evaluation by the Ca method described later that this affects the barrier performance.

[Adjacent layer 2]
In the present invention, in addition to the adjacent layer 1 adjacent to the barrier layer on the base material side, it is more preferable to further include an adjacent layer 2 adjacent to the barrier layer on the side opposite to the base material.

  The adjacent layer 2 in the present invention is not only a role as a protective layer that improves device manufacturing process resistance, conveyance, suitability for winding process, etc., but also the barrier property is not rapidly deteriorated by being provided on the upper layer of the barrier layer. It has been found by the present inventors that the present invention is very effective for obtaining such a stable barrier film. It is speculated that this may be because the barrier layer is thought to be able to suppress the degradation of the barrier property, which is thought to be caused by abrupt destruction during accelerated degradation due to wet heat, at the nano level. However, details are unknown.

  The material that can be preferably used for the adjacent layer 2 is not particularly limited as long as the adhesion to the adjacent barrier layer is maintained, but the polysiloxane as mentioned above for forming the adjacent layer 1 is used. A material containing polysilsesquioxane or the like as a main component is preferably used from the viewpoints of adhesion, stress relaxation, heat resistance, and the like.

  As for the method for forming the adjacent layer 2, a wet process such as coating is preferably used as in the method for the adjacent layer 1.

  The film thickness of the adjacent layer 2 is not particularly limited, but the thickness after drying is preferably about 10 nm to 100 μm, and more preferably about 100 nm to 10 μm.

[Base material (also called support)]
The substrate (support) in the present invention is not particularly limited as long as it can hold the adjacent layer 1 and the gas barrier layer of the present invention, but is applicable to mass production such as roll-to-roll. A plastic film is preferable because it is easy to handle and can be reduced in cost.

  Examples of the plastic film include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE ), Polypropylene (PP), Polystyrene (PS), Nylon (Ny), Aromatic polyamide, Polyetheretherketone, Polysulfone, Polyethersulfone, Polyimide, Polyetherimide, and other resin films, Sil with organic-inorganic hybrid structure A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having sesquioxane as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin can be used.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and from the viewpoint of optical transparency, heat resistance, and the like. A heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can also be preferably used.

  The thickness of the support according to the present invention is preferably in the range of 5 μm to 500 μm, more preferably in the range of 25 μm to 250 μm.

  The support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it becomes possible to make a transparent gas barrier film, so it can also be used as a transparent substrate such as a photoelectric conversion element (solar cell). Because it becomes.

  Here, that the support is transparent means that the light transmittance of visible light (400 nm to 700 nm) is 80% or more.

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

  The plastic film support used in the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

  Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  Moreover, in the plastic film which concerns on this invention, before forming the adjacent layer 1, you may give a corona treatment.

  Moreover, you may form an anchor coat layer on the support body in this invention in order to improve the adhesiveness with respect to the support body surface of the adjacent layer 1. FIG.

  The anchor coat layer is not particularly limited as long as it improves the adhesion between the plastic film and the adjacent layer 1. For example, when the adjacent layer 1 is a highly inorganic polysiloxane, an organic-inorganic hybrid material is used. A material having both organic and inorganic properties is preferably used.

  In addition, it is also possible to expect higher adhesion by forming a thin film of monomolecular level to nano level like a silane coupling agent and providing an anchor coat layer with a material capable of forming a molecular bond at the layer interface. It can be preferably used.

  Incidentally, a method of increasing the adhesion by adding such a silane coupling agent to the adjacent layer 1 can also be preferably used.

  In the present invention, a stress relaxation layer for relaxing the stress applied to the gas barrier layer, a smooth layer for smoothing the surface of the resin support, a bleed out prevention layer for preventing bleed out from the resin support, etc. It may be provided separately.

<< Use of gas barrier film >>
Applications of the gas barrier film of the present invention include applications as resin substrates for various electronic devices such as packages for electronic devices, or display materials such as organic EL elements, solar cells, and liquid crystals.

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

  Among these, the gas barrier film of the present invention is preferably used for an electronic device.

  Hereinafter, as an example of an electronic device having the gas barrier film of the present invention, an organic photoelectric conversion element and a solar cell having the element will be described.

[Organic photoelectric conversion element]
The organic photoelectric conversion element according to the present invention has the gas barrier film of the present invention as a component, but when used for the organic photoelectric conversion element, the gas barrier film of the present invention is preferably transparent, specifically, It is preferable to use a transparent gas barrier film as a constituent member of the support of the organic photoelectric conversion element and to receive sunlight from the gas barrier film side.

  Here, “transparent” means that the light transmittance of visible light (400 nm to 700 nm) is 80% or more.

  That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the support is used as an anode, a porous semiconductor layer is provided thereon, and a cathode made of a metal film is prepared to produce an organic photoelectric conversion element. The organic photoelectric conversion element can be sealed by stacking a stop material (although it may be the same), adhering the gas barrier film support and the periphery, and encapsulating the element. The influence on the element due to can be sealed.

  The resin support for organic photoelectric conversion elements is obtained by producing a transparent conductive film on the gas barrier layer (also simply referred to as a barrier layer) of the gas barrier film produced in this manner. The transparent conductive film can be produced by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.

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

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

[Sealing film and manufacturing method thereof]
In the present invention, a gas barrier film having the gas barrier layer (also simply referred to as a barrier layer) is preferably used as the substrate.

  In the gas barrier film having the barrier layer, a transparent conductive film is further formed on the barrier layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated on the transparent conductive film. Further, another gas barrier film is sealed as a sealing film by overlapping.

  As another sealing material (sealing film) used, the gas barrier film of the present invention can be used. Also, for example, known gas barrier films used for packaging materials, such as plastic films deposited with silicon oxide or aluminum oxide, dense ceramic layers, and flexible impact relaxation polymer layers alternately A gas barrier film or the like laminated on the substrate can be used as the sealing film.

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

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

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

  The thickness of the metal foil is preferably 6 to 50 μm. If the thickness is less than 6 μm, depending on the material used for the metal foil, pinholes may be vacant during use, and required barrier properties (moisture permeability, oxygen permeability) may not be obtained. 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 a metal foil laminated with a resin film (polymer film), various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used as the resin film. 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, when sealing the gas barrier films, if the film thickness exceeds 300 μm, the film handling property deteriorates during sealing work and it becomes difficult to heat-seal with an impulse sealer or the like, so the film thickness is 300 μm or less. Is desirable.

[Preferred embodiment of sealing of organic photoelectric conversion element]
The preferable aspect of sealing used for the organic photoelectric conversion element which is one of the organic electronic devices of this invention is demonstrated.

  As an example of production of the organic photoelectric conversion device according to the present invention, a transparent conductive film is formed on the gas barrier film of the present invention having a barrier layer, and each layer of the organic photoelectric conversion device is formed on the resin support for the organic photoelectric conversion device. After the formation, the organic photoelectric conversion element can be sealed using the sealing film so as to cover the cathode surface with the sealing film in an environment purged with an inert gas.

As the inert gas, a rare gas such as He and Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90% by volume to 99%. It is preferably 9% by volume. Preservability is improved by sealing in an environment purged with an inert gas.

  Moreover, in sealing the organic photoelectric conversion element using the metal foil laminated with the resin film (polymer film), a ceramic layer is produced 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 μm to 2.5 μm. However, if the amount of adhesive applied is too large, tunneling, leaching, crimping, etc. may occur, so the amount of adhesive is preferably adjusted to 3 μm to 5 μm in dry film thickness. It is preferable to do.

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

  The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 μm to 50 μm. As a resin used for the extrusion laminate, LDPE, EVA, PP, etc. are generally used.

  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 an organic photoelectric conversion element and a solar cell is demonstrated as an example of the electronic device which concerns on this invention, this invention is not limited to these.

  In addition, although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated in detail hereafter, the solar cell which concerns on this invention has the organic photoelectric conversion element which concerns on this invention as the structure, and is preferable of a solar cell. The configuration can be similarly described.

  The organic photoelectric conversion element is not particularly limited, and has at least one anode and cathode, and a power generation layer (also referred to as a p-type semiconductor and n-type semiconductor mixed layer, a bulk heterojunction layer, or an i layer) sandwiched therebetween. Any element that has more than one layer and generates current when irradiated with light may be used.

  The preferable specific example of the layer structure of an organic photoelectric conversion element (The preferable layer structure of a solar cell is also the same) is shown below.

(I) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

  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, and even if these layers form a heterojunction with substantially two layers. Alternatively, a bulk heterojunction in a mixed state in one layer may be manufactured, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

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

  For the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 1 described below, a hole transport layer 14 on each of the pair of comb-like electrodes, A back-contact type organic photoelectric conversion element in which the electron transport layer 16 is produced and the photoelectric conversion unit 15 is disposed thereon can also be configured.

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

  FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element.

  In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a bulk heterojunction power generation layer 14, an electron transport layer 18, and a cathode 13 in this order on one surface of a substrate 11. Are stacked.

  The substrate 11 is a member that holds the anode 12, the hole transport layer 17, the power generation layer 14, the electron transport layer 18, 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 relatively functions as an electron donor (donor), and the n-type semiconductor material relatively functions as an electron acceptor (acceptor).

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is produced. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes.

  For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

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

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

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

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

  Below, the material which comprises these layers is described.

[Organic photoelectric conversion element material]
The material used for formation of the electric power generation layer (it is also called a photoelectric converting layer) of the organic photoelectric conversion element concerning this invention is demonstrated.

(P-type semiconductor material)
Examples of the p-type semiconductor material preferably used as the power generation layer (bulk heterojunction layer) of the organic photoelectric conversion device according to the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, circobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

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

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO2008000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

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

  Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process is possible and that can produce a crystalline thin film and achieve high mobility after drying is preferable.

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

  Examples of such a material include materials that can be insolubilized by polymerizing and crosslinking the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or by applying energy such as heat, as described in US 2003/136964 and JP-A 2008-16834, etc., the soluble substituent reacts to insolubilize (pigmentation). Material) and the like.

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

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

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61- Butyric 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, US Pat. No. 7,329,709, etc. It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as fullerene having a cyclic ether group such as a calligraphy.

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

  As a material constituting these layers, for example, as the hole transport layer 17, PEDOT such as Product name BaytronP manufactured by Stark Vitec, polyaniline and its doped material, described in WO 06/19270, etc. Cyanide compounds can be used.

  Note that the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the anode side. The electronic block function 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.

  A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. It is preferable to produce a coating film in the lower layer before producing the bulk heterojunction layer because it has the effect of leveling the application surface and reduces the influence of leakage and the like.

(Electron transport layer / hole blocking layer)
Since the organic photoelectric conversion element 10 is capable of extracting charges generated in the bulk heterojunction layer more efficiently by forming the electron transport layer 18 between the bulk heterojunction layer and the cathode, these layers It is preferable to have.

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, or the like) can be used. Similarly, a p-type semiconductor material used for a bulk heterojunction layer is used. The electron transport layer having a HOMO level deeper than the HOMO level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side.

  Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.

  Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.

  A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable.

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

(Transparent electrode (first electrode))
In the transparent electrode according to the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element configuration, but preferably the transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 nm 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 of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used.

Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The counter electrode can be produced by producing a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.

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

  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 conductive fiber, a nanowire, or a nanostructure. A dispersion of nanowires is preferable because a transparent and highly conductive counter electrode can be produced by a coating method.

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

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

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately stacking them. Is preferable.

(Metal nanowires)
In 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 as the conductive fibers, but metal nanowires are preferred.

  In general, a 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.

  As a metal nanowire, in order to produce a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 μm to 500 μm. In particular, the thickness is preferably 3 μm to 300 μm. 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 the present invention, the average diameter of the metal nanowires is preferably 10 nm to 300 nm, and more preferably 30 nm to 200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  The metal composition of the metal nanowire is not particularly limited, and can 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. In the present invention, when the metal nanowire includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.

  For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in (1) can be easily produced in an aqueous system, and since the conductivity of silver is the highest among metals, it is preferable as the method for producing metal nanowires according to the present invention. Can be applied.

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

(Optical function layer)
The organic photoelectric conversion element according to the present invention may have various optical function layers for the purpose of more efficient light reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection layer 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 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  Examples of the light diffusion 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 formation method / surface treatment method)
Examples of a method for producing a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a vapor deposition method and a coating method (including a cast method and a spin coat method). Among these, examples of the method for producing 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. Also, the coating method is 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 cast 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 inkjet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, a flexographic printing method, or the like.

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

  The power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be manufactured 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 of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition, etching or lift-off. Alternatively, the pattern may be produced by transferring a pattern produced 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
As described below, the gas barrier films 1 to 7 of the present invention are formed by forming the adjacent layer 1 on the base material and further forming the barrier layer thereon (further forming the adjacent layer 2 thereon). Was made. FIG. 4 is a sectional view showing the configuration. In the figure, 4 indicates a support, 3 indicates an adjacent layer 1, 2 indicates a barrier layer, and 1 indicates an adjacent layer 2.

<< Production of Gas Barrier Film 1 >>
[Preparation of substrate]
(Support)
In the present invention, as a support, a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films Co., Ltd.) subjected to easy-adhesion processing on both sides is annealed at 170 ° C. for 30 minutes, and then on the back side, the following: A bleed-out prevention layer (not shown in FIG. 4) was used.

(Preparation of bleed-out prevention layer)
On the back side of the polyester film, UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation was applied, and after applying with a wire bar so that the film thickness after drying was 4 μm, curing conditions: 1.0 J / Cm ² , in air, using a high-pressure mercury lamp, drying conditions; curing at 80 ° C. for 3 minutes to produce a bleed-out prevention layer.

[Adjacent layer 1]
(Formation of adjacent layer 1)
The inorganic / organic nanocomposite material SSG Coat HB21BN (manufactured by Nittobo Co., Ltd.) is applied on the surface of the base material (the bleed-out prevention layer is not formed) on the condition that the film thickness after drying is 4.0 μm. Then, the adjacent layer 1 in the gas barrier film 1 was formed by drying at 80 ° C. for 10 minutes.

(Atomic composition ratio of adjacent layer 1)
Each atomic composition ratio of M atoms (M represents Si, Ti, Zr, Al, Zn), O atoms, and C atoms in the adjacent layer 1 was confirmed by a combination of sputtering and XPS surface analysis.

Etching from the surface to the depth direction using the sputtering method, using the XPS surface analyzer, the outermost surface is set to 0 nm, sputtering is performed at a rate of 5 nm / min in terms of SiO ₂ thermal oxide film, and each atomic composition ratio is set. It was measured. In the region of about 150 to 200 nm (SiO ₂ thermal oxide equivalent value) from the surface layer, the ratio of Si, O, and C atoms is almost constant, and C / Si = 2.0 and O / Si = 1.2. It was confirmed that there was.

  The XPS surface analyzer used for the surface analysis is not particularly limited, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

[Barrier layer]
(Formation of barrier layer)
Next, a barrier layer was formed on the adjacent layer 1 of the substrate by the following steps (a) and (b).

Step (a): Formation of perhydropolysilazane layer As a solution containing perhydropolysilazane (PHPS), a 20% by mass dibutyl ether solution (Aquamica NN120-20 (PHPS) manufactured by AZ Electronic Materials Co., Ltd.), an amine catalyst (N , N, N ′, N′-tetramethyl-1,6-diaminohexane) containing 5% by mass of NAX120-20), the content of amine catalyst relative to the perhydropolysilazane (PHPS) concentration Is adjusted to 1.0% by mass, and after coating by spin coating using a solution diluted to 10% by mass with a dibutyl ether solvent, the obtained coating film is dried at 80 ° C. for 1 minute. A perhydropolysilazane-containing layer having a thickness of 150 nm after drying was prepared. The film thickness was confirmed by the fact that a clear interface was seen from the cross-sectional photograph of TEM (Transmission Electron Microscope).

Step (b): Preparation of barrier layer by modification treatment (oxidation) of perhydropolysilazane layer For the film substrate having the perhydropolysilazane layer obtained in the above step (a), vacuum ultraviolet rays described below The gas barrier film 1 of the present invention was produced by performing (VUV) irradiation to form a barrier layer.

<Vacuum ultraviolet (VUV light) irradiation treatment conditions>
The irradiation conditions of vacuum ultraviolet rays (VUV light) were set and irradiated using the following apparatus so that the distance between the lamp and the sample (also referred to as Gap) was 3 mm. The irradiation time was changed by adjusting the movable speed of the movable stage.

  In addition, the oxygen concentration during irradiation with vacuum ultraviolet rays (VUV light) is adjusted by measuring the flow rate of nitrogen gas and oxygen gas introduced into the irradiation chamber with a flow meter, and nitrogen gas / oxygen gas of the gas introduced into the chamber. The flow rate ratio was adjusted.

Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm ²
Stage temperature: 100 ° C
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1%
Stage movable speed: transported 8 times at 10 mm / sec (atomic composition ratio of barrier layer)
In the same manner as the measurement method of the atomic composition ratio in the adjacent layer 1, each atomic composition ratio in the barrier layer was confirmed by combining the sputtering method and the XPS surface analysis.

Etching from the surface to the depth direction using the sputtering method, using the XPS surface analyzer, the outermost surface is set to 0 nm, sputtering is performed at a rate of 1 nm / min in terms of SiO ₂ thermal oxide film, and each atomic composition ratio is set. It was measured. A continuous region where the ratio of Si, N, and O atoms is almost constant is 2 nm or more in the depth direction in a region of about 5 to 100 nm (converted value of SiO ₂ thermal oxide film) from the surface layer excluding the outermost layer region. It was confirmed that N / Si = 0.6 and O / Si = 0.6. C / Si was less than 0.1.

<< Production of Gas Barrier Film 2 >>
In the production of the gas barrier film 1, the gas barrier film 2 of the present invention was produced in the same manner except that the material for forming the adjacent layer 1 was changed to diethoxysilane-ethyl titanate copolymer PSITI-019 (manufactured by Gelest). did.

(Atomic composition ratio of adjacent layer 1 and barrier layer)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer of the gas barrier film 2 was determined, the adjacent layer 1 was approximately C / Si = 2.1, O / Si = 1.9, and the barrier layer was It was confirmed that N / Si = 0.5 and O / Si = 0.9. Moreover, it was less than 0.1 about C / Si.

<< Production of Gas Barrier Film 3 >>
In the production of the gas barrier film 1, the gas barrier film 3 of the present invention was produced in the same manner except that the material for forming the adjacent layer 1 was changed to SSG coated HB31BN (manufactured by Nittobo Co., Ltd.).

(Atomic composition ratio of adjacent layer 1 and barrier layer)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer of the gas barrier film 3 was determined, the adjacent layer 1 was approximately C / Si = 2.2, O / Si = 1.0, and the barrier layer was It was confirmed that N / Si = 0.8 and O / Si = 0.2. C / Si was less than 0.1.

<< Production of Gas Barrier Film 4 >>
In the production of the gas barrier film 1, the present invention is similarly applied except that the material for forming the adjacent layer 1 is changed to a 9: 1 mixture of methylsilsesquioxane and hydrosilsesquioxane (manufactured by Konishi Chemical Co., Ltd.). The gas barrier film 4 was prepared.

(Atomic composition ratio of adjacent layer 1 and barrier layer)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer of the gas barrier film 4 was determined, the adjacent layer 1 was approximately C / Si = 0.2, O / Si = 2.0, and the barrier layer was It was confirmed that N / Si = 0.3 and O / Si = 1.3. C / Si was less than 0.1.

<< Production of Gas Barrier Film 5 >>
In the production of the gas barrier film 1, the material for forming the adjacent layer 1 is changed to a 10: 1 mixture of Glasca HPC7003 (main agent) and HPC404H (curing accelerator) (manufactured by JSR), and the adjacent layer 2 is changed to the following: A gas barrier film 5 of the present invention was produced in the same manner except that it was provided as described above.

(Formation of adjacent layer 2)
On the barrier layer of the base material, after applying a layer mainly composed of glass mosquito which is the same material as the adjacent layer 1 under the condition that the film thickness after drying is about 600 nm, the barrier layer is dried at 80 ° C. for 10 minutes. The adjacent layer 2 in the gas barrier film 5 was formed by performing the same VUV irradiation treatment (stage moving speed: transported 3 times at 10 mm / second) as in the formation.

(Atomic composition ratio of adjacent layer 1, barrier layer, adjacent layer 2)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer in the gas barrier film 5 was determined, the adjacent layer 1 and the adjacent layer 2 were approximately C / Si = 0.5 and O / Si = 1.6. It was confirmed that the barrier layer had N / Si = 0.6 and O / Si = 0.7. C / Si was less than 0.1.

<< Production of Gas Barrier Film 6 >>
In the production of the gas barrier film 5, the material forming the adjacent layer 1 and the adjacent layer 2 is changed to methylsilsesquioxane (manufactured by Konishi Chemical Co., Ltd.) (however, the same as that added to the polysilazane used for forming the barrier layer) A gas barrier film 6 of the present invention was produced in the same manner except that 1% of an amine catalyst was added.

(Atomic composition ratio of adjacent layer 1, barrier layer, adjacent layer 2)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer in the gas barrier film 6 was determined, the adjacent layer 1 and the adjacent layer 2 were approximately C / Si = 0.5 and O / Si = 1.7. It was confirmed that the barrier layer had N / Si = 0.6 and O / Si = 0.7. C / Si was less than 0.1.

<< Production of Gas Barrier Film 7 >>
In the production of the gas barrier film 5, the gas barrier property of the present invention was the same except that the material for forming the adjacent layer 1 was changed to SSG coated HB21BN (manufactured by Nittobo Co., Ltd.). Film 7 was produced.

(Atomic composition ratio of adjacent layer 1, barrier layer, adjacent layer 2)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer in the gas barrier film 7 was determined, the adjacent layer 1 was approximately C / Si = 2.0, O / Si = 1.2, and the barrier layer was N / Si = 0.6, O / Si = 0.6, and the adjacent layer 2 was confirmed to be approximately C / Si = 0.5 and O / Si = 1.6. C / Si was less than 0.1.

  Subsequently, comparative films 8 to 13 were produced.

<< Production of Comparative Film 8 >>
Similarly to the production of the gas barrier film 1 of the present invention, a layer corresponding to the adjacent layer 1 is formed using SSG-coated HB21BN (manufactured by Nittobo Co., Ltd.), a perhydropolysilazane-containing layer is formed in the same manner, and a polysilazane is further formed. The comparative film 8 was produced by performing the modification | reformation process of as follows.

(Formation of barrier layer)
The dried perhydropolysilazane-containing layer was heated at 80 ° C. for 5 minutes under a humidity of 90% RH to form a layer in which polysilazane was converted into an inorganic film.

(Atomic composition ratio of the layer corresponding to the adjacent layer 1 and the barrier layer)
As in the case of the gas barrier film 1 of the present invention, when the atomic composition ratio of each layer of the comparative film 8 was determined, the layer corresponding to the adjacent layer 1 was approximately C / Si = 2.0, O / Si = 1.2 It was confirmed that the barrier layer was about N / Si = 0.1 or less and O / Si = 2.3. C / Si was less than 0.1.

<< Production of Comparative Film 9 >>
In the production of the comparative film 8, the comparative film 9 was produced in the same manner except that the modification treatment of the perhydropolysilazane-containing layer was performed by oxygen plasma treatment (SAMCO, oxygen plasma apparatus, PC-300). did.

(Atomic composition ratio of the layer corresponding to the adjacent layer 1 and the barrier layer)
As in the case of the comparative film 8, the atomic composition ratio of each layer of the comparative film 9 was determined. The layers corresponding to the adjacent layer 1 were approximately C / Si = 2.0 and O / Si = 1.2. The barrier layer was confirmed to be approximately N / Si = 0.1 or less and O / Si = 2.1. C / Si was less than 0.1.

<< Production of Comparative Film 10 >>
In the production of the gas barrier film 1 of the present invention, a comparative film 10 was produced in the same manner except that the adjacent layer 1 was not formed.

(Atomic composition ratio of barrier layer)
As in the case of the comparative film 8, when the atomic composition ratio of the barrier layer of the comparative film 10 was determined, it was confirmed that N / Si = 0.1 or less and O / Si = 2.2. . C / Si was less than 0.1.

<< Production of Comparative Film 11 >>
In the production of the gas barrier film 1, a layer corresponding to the adjacent layer 1 is formed using an amine catalyst type of perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica NAX120-20) instead of the material forming the adjacent layer 1. The comparative film 11 was produced by forming. The perhydropolysilazane-containing layer corresponding to the adjacent layer 1 was heated at 80 ° C. under a humidity of 90% RH for 5 minutes to form a layer in which polysilazane was converted into an inorganic film.

(Atomic composition ratio of the layer corresponding to the adjacent layer 1 and the barrier layer)
As in the case of the gas barrier film 1, when the atomic composition ratio of each layer in the comparative film 11 was determined, the layer corresponding to the adjacent layer 1 was approximately C / Si = 0.1 or less, O / Si = 2. 3. It was confirmed that the barrier layer had N / Si = 0.1 or less and O / Si = 2.2. C / Si was less than 0.1.

<< Production of Comparative Film 12 >>
In the production of the comparative film 11, a comparative film 12 was produced in the same manner except that the layer corresponding to the adjacent layer 1 was changed to the following hard coat layer.

(Formation of a layer corresponding to the adjacent layer 1)
A UV curable organic / inorganic hybrid hard coat material, OPSTAR Z7501 (manufactured by JSR Corporation) is applied to the surface side of the polyester film substrate provided with a bleed-out prevention layer on the back surface so that the film thickness after drying is 4 μm. Then, after drying at 80 ° C. for 3 minutes, a layer corresponding to the adjacent layer 1 was formed by curing at 1.0 J / cm ² with a high-pressure mercury lamp in an air atmosphere.

(Atomic composition ratio of the layer corresponding to the adjacent layer 1 and the barrier layer)
As in the case of the comparative film 11, the atomic composition ratio of each layer of the comparative film 12 was determined. The layers corresponding to the adjacent layer 1 were approximately C / Si = 5.6, O / Si = 1.5. The barrier layer was confirmed to be approximately N / Si = 0.5 and O / Si = 1.0. C / Si was less than 0.1.

<< Production of Comparative Film 13 >>
In the production of the comparative film 11, a layer corresponding to the adjacent layer 1 is referred to JP 2009-101620 A with a hydroxyl group / methacrylic group-containing aromatic acrylic resin and a silane coupling agent KBM903 (Shin-Etsu Silicone) at 1%. The comparative film 13 was produced by changing to an acrylic resin layer formed by applying and adding a solution further added with an aliphatic isocyanate, and forming a barrier layer by vapor deposition.

(Atomic composition ratio of the layer corresponding to the adjacent layer 1 and the barrier layer)
As in the case of the comparative film 11, the atomic composition ratio of each layer of the comparative film 13 was determined. The layer corresponding to the adjacent layer 1 was approximately C / Si = 20, O / Si = 8, and the barrier layer was It was confirmed that N / Si = 0.1 or less and O / Si = 2.1. C / Si was less than 0.1.

<< Evaluation of water vapor transmission rate (WVTR) characteristics of gas barrier film >>
[Evaluation 1: Evaluation of bending resistance (60 ° C., 90% RH)]
For the gas barrier films 1 to 7 and the comparative films 8 to 13 of the present invention, in order to confirm the change in the gas barrier properties before and after bending, the film is bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm in advance. For the gas barrier film subjected to the process of repeating the above and the gas barrier film not subjected to the above bending process, the water vapor transmission rate (WVTR) is measured according to the method described below, and the four-level rank evaluation is performed as shown below. The gas barrier properties were evaluated.

(Measurement device of water vapor transmission rate)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of vapor barrier evaluation cell)
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), except for each film (gas barrier films 1 to 7, comparative films 8 to 13) other than the portion (12 mm × 12 mm 9 locations) to be vapor deposited Masked and vapor deposited metallic calcium.

  Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

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

  At this time, in the present invention, the WVTR obtained from the corrosion rate until the corrosion area of the cell reaches 1% is 1% WVTR, and the corrosion area is 100%, that is, the WVTR obtained from the corrosion rate until full corrosion occurs. It will be called 100% WVTR (also called average WVTR).

(Rank evaluation)
4: Less than 1 × 10 ⁻³ g / m ² / day 3: 1 × 10 ⁻³ g / m ² / day or more and less than 3 × 10 ⁻³ g / m ² / day 2: 3 × 10 ⁻³ g / day m ² / day or more, less than 1 × 10 ⁻¹ g / m ² / day 1: 1 × 10 ⁻¹ g / m ² / day or more [Evaluation 2: Evaluation of high temperature and high humidity resistance]
The obtained films 1 to 13 were not bent and stored in a high-temperature and high-humidity tank (constant temperature and humidity oven: Yamato Humidic Chamber IG47M) adjusted to 60 ° C. and 90% RH for 100 hours. In the same manner, the water vapor transmission rate was measured with 100% WVTR, and the same rank evaluation was performed.

[Evaluation 3: Evaluation of rapid corrosion degree]
The rapid corrosion degree in the present invention has a gas barrier property of a certain level or more, and whether the permeation rate (corrosion rate) has increased abruptly since water vapor began to permeate the gas barrier film (100% WVTR / The smaller the 30% WVTR is, the smaller the rapid deterioration, that is, it can be judged that it is stable), and it is used as an index of the stability of the gas barrier film itself.

  Similar to Evaluations 1 and 2, the following three ranks were evaluated.

  However, in the present invention, the WVTR obtained from the corrosion rate until the corrosion area of the cell reaches 30% is referred to as 30% WVTR.

(Rank evaluation)
3: 1% WVTR is less than 3 × 10 ⁻³ g / m ² / day, and 100% WVTR / 30% WVTR is less than 10. 2: 1% WVTR is less than 3 × 10 ⁻³ g / m ² / day. And 100% WVTR / 30% WVTR was 10 or more and 100 or less 1: 1% WVTR was 3 × 10 ⁻³ g / m ² / day or more, and 100% WVTR / 30% WVTR was obtained by 100 or more. The results are shown in Table 1.

  As is clear from the results shown in Table 1, the gas barrier films 1 to 7 of the present invention each have a high gas barrier property (low water vapor transmission rate) and a high temperature compared to the comparative gas barrier films 8 to 13. It is clear that even when the humidity is increased or stored in a wider temperature range, it exhibits excellent barrier properties and excellent flexibility (cracking resistance).

Example 2
<< Production of Organic Photoelectric Conversion Elements 1-13 >>
150 nm of indium tin oxide (ITO) transparent conductive film deposited on the gas barrier films 1 to 7 of the present invention produced in Example 1 and comparative films 8 to 13 (sheet resistance 10Ω / □) (conductive film) The first electrode was fabricated by patterning the film that had been heat-treated before formation) into a width of 2 mm using a normal photolithography technique and wet etching.

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

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

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

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

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

  Each obtained organic photoelectric conversion element is moved to a nitrogen chamber, and sealing is performed using a sealing cap and a UV curable resin, thereby producing organic photoelectric conversion elements 1 to 13 having a light receiving portion of 2 × 2 mm size. did.

  Subsequently, the gas barrier film sample for sealing and the organic photoelectric conversion element were sealed according to the following method.

  In an environment purged with nitrogen gas (inert gas), each of the gas barrier films 1 to 13 is used and an epoxy photocurable adhesive is applied as a sealing material to the surface provided with the gas barrier layer. These were prepared as the respective sealing films 1 to 13 for the corresponding organic photoelectric conversion elements 1 to 13.

  Next, the organic photoelectric conversion elements 1 to 13 are sandwiched and adhered between the adhesive application surfaces of the two gas barrier film samples coated with the adhesive, and then irradiated with UV light from one substrate side. Then, the organic photoelectric conversion elements 1 to 13 were sealed, and the organic photoelectric conversion elements 1 to 7 of the present invention and comparative organic photoelectric conversion elements 8 to 13 were obtained.

<< Production of solar cells and evaluation of energy conversion efficiency >>
Evaluation of the organic photoelectric conversion elements 1 to 7 obtained above and the comparative organic photoelectric conversion elements 8 to 13 was performed by using the respective elements to produce solar cells 1 to 7 and comparative solar cells 8 to 13, respectively. The energy conversion efficiency was obtained, and the durability as an element was evaluated for each.

In addition, each evaluation of the organic photoelectric conversion elements 1 to 7 and the comparative organic photoelectric conversion elements 8 to 13 is performed by irradiating light of 100 mW / cm ² of solar simulator (AM1.5G filter) with an effective area of 4 A mask with a thickness of 0.0 mm ² was placed on the light receiving portion, and the IV characteristics as solar cells 1 to 7 and comparative solar cells 8 to 13 were evaluated.

Specifically, the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%) were measured for each of the four light receiving portions formed on the element, and according to the following formula 1. A four-point average value of the obtained energy conversion efficiency PCE (%) was estimated.

Formula 1
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as an initial battery characteristic obtained was measured, and the degree of deterioration over time was measured as the conversion efficiency remaining rate after the forced deterioration test stored for 2000 hours in a temperature 60 ° C., humidity 90% RH environment. It calculated | required as ratio of the conversion efficiency after a test / initial conversion efficiency, and durability was evaluated according to the following reference | standard (OPV element performance).

3: The conversion efficiency remaining rate is 70% or more 2: The conversion efficiency remaining rate is 40% or more and less than 70% 1: The conversion efficiency remaining rate is less than 40%. is there.

  The obtained results are shown in Table 1.

  As is clear from the results shown in Table 1, for the comparative solar cells 8 to 13 provided with the organic photoelectric conversion elements 8 to 13 prepared using the comparative film, the organic photoelectric prepared using the gas barrier film of the present invention. It turned out that the solar cells 1-7 of this invention provided with the conversion elements 1-7 show very high durability also in the very severe environment (high temperature, high humidity conditions) of 60 degreeC and 90% RH.

1 Adjacent layer 2
2 Barrier layer 3 Adjacent layer 1
4 Support

Claims (7)

A gas barrier film comprising a resin substrate, at least one barrier layer, and an adjacent layer 1 adjacent to the barrier layer at least on the substrate side, wherein the following (1) and (2) are satisfied: Sex film.
(1) The adjacent layer 1 has a region containing at least M atoms (M represents Si, Ti, Zr, Al, Zn), O atoms, and C atoms at the same time. Is 0.2 to 2.2, and O / M is 1.0 to 2.0.
(2) The barrier layer has at least a region containing Si atoms and N atoms at the same time, and N / Si is 0.3 to 0.8 and C / Si <0.1 in terms of atomic composition ratio.   2. The gas barrier film according to claim 1, wherein the barrier layer further contains O atoms and has an atomic composition ratio of O / Si of 0.2 to 1.3. 3.   The gas barrier film according to claim 1 or 2, further comprising an adjacent layer 2 adjacent to the barrier layer on the side opposite to the base in addition to the adjacent layer 1 adjacent to the barrier layer on the base side. Gas barrier film characterized by   The gas barrier film according to any one of claims 1 to 3, wherein the M atom is Si.   It is a manufacturing method of the gas-barrier film of any one of Claims 1-4, Comprising: After apply | coating the coating liquid of the composition containing perhydropolysilazane on the said adjacent layer 1, it performs a conversion process. A method for producing a gas barrier film, comprising forming a barrier layer containing an inorganic substance.   6. The method for producing a gas barrier film according to claim 5, wherein the conversion treatment is an ultraviolet irradiation treatment.   An organic electronic device, wherein the organic electronic device is sealed with the gas barrier film according to claim 1.

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