JP2011036779A - Method of manufacturing gas barrier film and organic photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a gas barrier film capable of achieving remarkably high gas barrier performance and an organic photoelectric conversion element using the gas barrier film manufactured by the manufacturing method. <P>SOLUTION: The method of manufacturing the gas barrier film by applying a polysilazane film at least on one surface of a base material and carrying out plasma-treatment to form the barrier film includes: a first step of removing a solvent in the application of the polysilazane film before the plasma treatment; and a second step of successively removing water. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention mainly relates to a method for producing 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 EL element, a solar cell, or a liquid crystal, and the gas barrier property produced by the production method. The present invention relates to an organic photoelectric conversion element using a film.

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

As a method for forming such a gas barrier film, a technique is known in which a coating liquid containing polysilazane as a main component is applied and surface treatment is performed (for example, see Patent Documents 1 and 2). However, any of these techniques has an insufficient function as a gas barrier layer of an organic photoelectric conversion element or the like, and a further gas barrier that has a water vapor transmission rate significantly lower than 1 × 10 ⁻² g / m ² · day. There was a need for improved sex.

  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 by performing an atmospheric pressure plasma treatment to form a barrier layer. Furthermore, although there is a reference to the preferred form and drying of the type of solvent for dissolving or dispersing the polysilazane, the polysilazane film before the plasma treatment is performed, in order to make the progress of silica conversion sufficiently There is no mention of moisture content.

  In Patent Document 2, a polysilazane layer is formed and treated with a gas containing water vapor in the presence of amines or acids, followed by heat treatment (for example, 120 ° C., 2.5 minutes described in Examples). And a technique for promoting the hydrolysis reaction and converting the polysilazane component to silica by gas discharge treatment. However, although the hydrolysis reaction of the polysilazane component proceeds in the gas contact treatment and the heat treatment, it is found that if it proceeds too much, it becomes a silica film containing a large amount of Si-OH, and therefore, sufficient barrier performance cannot be obtained. all right.

  On the other hand, a film forming technique for forming a functional body containing silicon atoms and at least one of oxygen atoms and nitrogen atoms with atmospheric pressure plasma of nitrogen 2 frequency is disclosed (for example, see Patent Document 3). .

  As a result of confirmation by the present inventors, although a functional body formed by a high-density and stable nitrogen plasma can be obtained, since it is a CVD film formation method, particles in the gas phase are generated as by-products in the plasma space. It has been found that uniform film formation may be hindered by adhesion to the substrate, and it is difficult to withstand gas barrier applications for organic photoelectric conversion elements and the like.

JP 2007-237588 A JP 2000-246830 A JP 2004-84027 A

  Accordingly, an object of the present invention is to provide a method for producing a gas barrier film capable of achieving extremely high gas barrier performance, and an organic photoelectric conversion element using the gas barrier film produced by the production method.

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

  1. In the method for producing a gas barrier film in which a polysilazane film is applied to at least one surface of a substrate and a gas barrier layer is formed by performing a plasma treatment, a first step of removing the solvent during the application of the polysilazane film before the plasma treatment; The manufacturing method of the gas barrier film characterized by including the 2nd process of removing a water | moisture content following it.

  2. 2. The method for producing a gas barrier film as described in 1 above, wherein the water content of the polysilazane film after the second step is 0.1% or less.

  3. 3. The method for producing a gas barrier film as described in 1 or 2 above, wherein the plasma treatment is atmospheric pressure plasma treatment.

  4). 4. The method for producing a gas barrier film as described in 3 above, wherein the atmospheric pressure plasma treatment is nitrogen two-frequency discharge.

5). 5. The gas barrier film according to 3 or 4 above, which is a plasma treatment containing N ₄ ⁺ ions having a time average density of 8.0 × 10 ¹⁶ [m ⁻³ ] or more in the atmospheric pressure plasma treatment. Production method.

  6). It has a gas barrier film formed by the manufacturing method of the gas barrier film of any one of said 1-5, The organic photoelectric conversion element characterized by the above-mentioned.

  By the production method of the present invention, it is possible to obtain a gas barrier film that is excellent in production suitability and handleability and can achieve high gas barrier performance, and is useful as a resin base material for organic photoelectric conversion elements having high gas barrier properties. A film can be obtained.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. Is a graph displaying the N ₄ ⁺ ion density per 1/4 the cycle of the frequency of the voltage applied to the electrode of the plasma discharge treatment apparatus.

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

  The gas barrier film has a gas barrier layer formed by subjecting one or more polysilazane films to plasma treatment on at least one surface of a resin film support, for example, polyethylene terephthalate, and the gas barrier layer may be a single layer or a plurality of layers. Similar layers may be laminated, and a plurality of layers can further improve the gas barrier property.

  As a method for forming a gas barrier layer, a gas barrier layer containing silicon oxide is formed by applying a coating solution containing at least one polysilazane compound on a substrate and then performing plasma treatment in an oxidizing gas atmosphere. A method is mentioned.

  The supply of the silicon compound for forming the gas barrier layer of silicon oxide forms a gas barrier layer that is more uniform and smooth when applied to the surface of the gas barrier film substrate than when supplied as a gas as in CVD. be able to. In the case of a CVD method or the like, it is well known that unnecessary foreign substances called particles are generated in the gas phase simultaneously with the step of depositing the source material having increased reactivity in the gas phase on the substrate surface. By preventing the raw material from being present in the plasma reaction space, the generation of these particles can be suppressed.

(Polysilazane film)
The polysilazane film in the present invention is formed by applying a coating solution containing at least one polysilazane compound on a substrate.

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

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

  In order to apply the film base material without damaging the film base material, it is preferable that the following general formula (I) is converted to silica by being ceramicized at a relatively low temperature as described in JP-A-8-112879.

However, each of R ¹ , R ² and R ^{3 in} the formula is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, etc. Then, perhydropolysilazane in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred from the viewpoint of the denseness as a gas barrier film to be obtained.

  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 marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

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

  As an organic solvent for preparing a liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used.

  Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

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

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

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

(First step and second step)
The polysilazane film in the present invention is characterized in that moisture is sufficiently removed by the first step and the second step before the plasma treatment. Further, the method includes a first step for removing the solvent in the polysilazane film and a second step for removing the water in the polysilazane film. At this time, moisture may be removed in the first step, which is preferable because the load in the subsequent second step is reduced.

  In the first step, drying conditions for mainly removing the solvent can be appropriately determined by a method such as heat treatment, but the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably high from the viewpoint of rapid treatment, but the temperature and treatment time can be determined in consideration of thermal damage to the resin substrate.

  For example, when a PET substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and heat damage to the substrate is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

  When handling volatile solvents, especially when handling volatile solvents with a low flash point, it is not preferable to set the first process in a low-humidity environment in order to consider major accidents such as explosions and fires caused by static electricity. A medium humidity environment is preferred. The medium humidity environment refers to humidity at which static electricity or the like is not easily generated, and indicates a dew point of 14 to 20 ° C. Moreover, you may dry under reduced pressure in order to make it easy to remove a solvent. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  The second step is a step for removing moisture in the polysilazane film, and the method for removing moisture is preferably in a form maintained in a low humidity environment. Since the humidity in the low humidity environment varies depending on the temperature, a preferable form of the relationship between the temperature and the humidity is indicated by the definition of the dew point temperature.

  A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 ° C./humidity 1%). ) −31 ° C. or lower, and the maintained time varies depending on the thickness of the polysilazane film. Under the condition of a polysilazane film thickness of 1 μm or less, the preferable dew point temperature is maintained at −8 ° C. or lower for 5 minutes or longer. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

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

  The polysilazane film in the present invention is preferably plasma-treated while maintaining its state even after moisture is removed in the second step.

(Water content of polysilazane film)
The water content of the polysilazane film in the present invention can be detected by the following analysis method.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min) → 10 ° C./min→150° C.
Column: DB-624 (0.25 mmid * 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C., 30 min.

  The water content in the polysilazane film in the present invention is defined as a value obtained by dividing the water content obtained by the above analytical method by the volume of the polysilazane film, and preferably 0.1% in a state where moisture is removed by the second step. % Or less. A more preferable moisture content is 0.01% or less (below the detection limit).

  In the present invention, high gas barrier properties can be obtained by removing moisture from the polysilazane film before the plasma treatment. This is because in the process of forming a silicon oxide layer from a polysilazane film by plasma treatment, plasma energy is absorbed by adsorbing the surface that inhibits densification or removing the moisture in the polysilazane film. The present inventors presume that the water is efficiently consumed in the conversion reaction without being consumed in the water elimination reaction.

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

<Atmospheric pressure plasma treatment>
Next, a preferable embodiment for the atmospheric pressure plasma treatment will be described. Specifically, the atmospheric pressure plasma treatment in the present invention is one in which two or more electric fields having different frequencies are applied to the discharge space, as described in International Publication No. 07/26545 pamphlet. It is preferable to apply an electric field superimposed with the second high-frequency electric field.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge start electric field Of the second high-frequency electric field is 1 W / cm ² or more, and the relationship with the intensity IV satisfies V1 ≧ IV> V2 or V1> IV ≧ V2.

  By adopting such a discharge condition, for example, even a discharge gas having a high discharge starting electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. be able to.

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

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

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

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, due to the high power density, it is possible to increase the plasma density and form a dense and high-quality thin film.

In the atmospheric pressure plasma treatment in the present invention, the time average density is 8.0 × 10 ¹⁶ [m ⁻³ ] or more, more preferably 1.2 × 10 ¹⁷ [m ⁻³ ] or more, more preferably 2.0 × 10. It is preferable to contain ¹⁷ [m ⁻³ ] or more N ₄ ⁺ ions. In addition, as an upper limit of a time average density, it is 1 * 10 < ²⁰ > [m <^-3> ].

The time average density of N ₄ ⁺ ions is considered to be an index indicating the high plasma density of the plasma discharge treatment gas and the stability of the plasma state, and the plasma treatment discharge is empirically or trial and error as in the past. Instead of adjusting the control parameters of the apparatus, it is possible to perform a favorable plasma discharge process by controlling the control parameters of the plasma discharge processing apparatus so as to obtain a time average density as in the present invention.

Further in the control parameters, by varying the peak value of the current density with a good correlation with the time average density of N ₄ ⁺ ions in the plasma discharge processing gas, readily N ₄ plasma discharge processing gas It becomes possible to set the time average density of ⁺ ions.

In addition, since it is difficult to actually measure the density of N ₄ ⁺ ions in the plasma discharge processing gas, plasma simulation is used to define the density value. Further, since the density of N ₄ ⁺ ions changes with time depending on the electric field between the periodically changing electrodes, by calculating the time average of the density of N ₄ ⁺ ions calculated by the plasma simulation, The density of N ₄ ⁺ ions is defined.

Therefore, the N ₄ ⁺ ion density or time average density in the present invention is not an actual measurement value but a value obtained by a plasma simulation described below.

  In the present invention, Computational Fluid Dynamics (CFD) software “CFD-ACE +” (manufactured by CFD Research, USA) is used for the simulation.

In addition, the reaction data when obtaining the N ₄ ⁺ ion density, that is, the reaction constants, etc. A. Kossyi et al. , “Kinetic scheme of the non-equilibrium discharge in nitrogen-oxygen mixtures”, Plasma Sources Sci. Technol. 1 (1992) 207-220 (British Physical Society, literature 1), and P.I. Segur and F.M. Massines, “The role of numeric modeling to the behavior and to predict the extensibility of the bloodstream. 13th Int. Conf. on Gas Discharges and their Applications, Glasgow, 2000, 15. The value published in the published academic paper of (Document 2) is used.

Here, calculation of N ₄ ⁺ ion density by the computational fluid dynamics software will be described. In the discharge space between the electrodes of the plasma discharge treatment apparatus, elementary reactions as shown in the following formulas (1) to (9) are generated only by elementary reactions involving electrons.

Elastic collision: e + A → e + A (1)
Electronic excitation: e + A → e + A ^* (2)
Vibration excitation: e + A → e + A (vib) (3)
Rotational excitation: e + A → e + A (rot) (4)
Dissociation: e + AB → e + A + B (5)
Ionization: e + A → e + e + A ⁺ (6)
Electron attachment: e + A → A ⁻ (7)
Dissociative adhesion: e + AB → A + B ⁻ (8)
Superelastic collision: e + A ^* → e + A (9).

Here, A is a neutral gas molecule or atom such as a discharge gas or a source gas, or a radical derived therefrom, and A ^* indicates that the molecule is in an electronically excited state. In the discharge space, various elementary reactions such as elementary reactions between electrons and ions, elementary reactions between neutral molecules, atoms and radicals or between them and ions, and elementary reactions between ions occur.

In addition, under the pressure near atmospheric pressure, the contribution of the three-body reaction becomes more important than in the conventional case of low pressure. For example, assuming that the plasma discharge treatment gas is composed of only nitrogen gas, at low pressure,
_{^{N 2 (a '1 Σu -}} ) + N 2 (a' 1 Σu -) → N 4 + + e (10)
_{^{N 2 (A 3 Σu +)}} + N 2 (a '1 Σu -) → N 4 + + e (11)
The elementary reaction represented by is the main production reaction of N ₄ ⁺ ions.

However, the pressure of near atmospheric ^{_{pressure, N 2 (a '1 Σu}} -) and N _{2 (A} ³ Σu ⁺⁾ collision of nitrogen molecules and other nitrogen molecules in the excited state, such as is frequently the excitation Even if the nitrogen gas in the state is generated, energy is lost due to collision and it is deactivated very quickly, so that the contribution to the N ₄ ⁺ ion generation in the equations (10) and (11) is reduced.

On the other hand, under the pressure near atmospheric pressure, N ₂ ⁺ + 2N ₂ → N ₄ ⁺ + N ₂ (12) compared with the case of low pressure.
The probability of the occurrence of the three-body reaction indicated by is greatly increased, and it is considered that N ₄ ⁺ ions are mainly generated by this reaction.

N ₄ ⁺ ions are mainly nitrogen molecules and nitrogen atoms present in a large amount in the plasma discharge treatment gas, or, for example, oxygen molecules and oxygen atoms when oxygen molecules are mixed as a reactive gas. , steal electrons from the other collide with NO _X, split into two N ₂ lost from the gas. In addition, there is a path that is combined with electrons existing in the gas to become two N ₂ and lost from the gas.

In the simulation, based on these elementary reactions in the discharge space and secondary electron emission that occurs when positive ions collide with the negative electrode, the one-dimensional plasma solves the following governing equation: By performing the simulation, the density of N ₄ ⁺ ions and the like are calculated. The source gas in the plasma discharge processing gas is ignored in the simulation according to the present invention.

  Here, y is a position in a one-dimensional space direction, that is, a direction from one electrode to the other electrode, ne is an electron density, Je is an electron flux, Se is an electron generation / annihilation term, and μe is an electron mobility. , De means the electron diffusion coefficient, and the subscript (i) means the density or flux in the case of ions. In addition, nn is a neutral particle (radical or excited particle) density, Dn is a diffusion coefficient of neutral particles, εe is an average electron energy, Q is an electron energy flux, E is an electric field, kloss is an electron energy loss rate coefficient, Ngas Means gas density.

  The relationship of the above equation (20) is established between the average electron energy εe and the electron temperature Te. The electric field E is obtained from the negative gradient obtained by solving the equation (21), which is a Poisson equation, with respect to the potential φ. The constants e, k, and ε0 mean elementary charge, Boltzmann constant, and vacuum dielectric constant, respectively.

  In addition, the electron density is obtained from the equations (13) and (14), the ion density is obtained from the equations (13) and (15), and neutral particles (excited particles and radicals) are obtained from the equations (16) and (17). The density is calculated from the equation (18) and the equation (19), the average electron energy, from the relationship of the equation (20), the electron temperature, and from the equation (21), the potential (potential).

In the plasma simulation, the voltage applied to the electrodes, the frequency of the voltage, the electrode spacing, the relative permittivity of the dielectric covering the electrodes, and the thickness of the dielectric are varied in the plasma discharge processing apparatus. To determine the density of N ₄ ⁺ ions.

  Further, the electron mobility μe and the diffusion coefficient De required for solving the governing equation, that is, the so-called electron swarm parameter are all the reaction cross sections for the electrons in the documents 1 and 2 described above. It is obtained by inputting it into the Boltzmann equation analysis program of “ACE +”.

When the governing equation is solved in this way, the time-varying density of N ₄ ⁺ ions in the plasma discharge processing gas is calculated as illustrated in FIGS. 4 (A) to (D). In the present invention, as described above, the time average of the calculated density of N ₄ ⁺ ions is obtained, and the density of N ₄ ⁺ ions is defined by the time average. 4A to 4D show the N ₄ ⁺ ion density for each ¼ period of the voltage frequency having a higher frequency among the voltages applied to the two electrodes of the plasma discharge processing apparatus. To (D) in order, and the solid line indicates the density of N ₄ ⁺ ions. The dotted line in the figure is the electron density.

The plasma discharge treatment gas in the present invention may contain oxygen plasma. Oxygen plasma is generated by adding an oxidizing gas such as oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, etc. to the plasma discharge treatment gas, but does not fall below the time average density of the N ₄ ⁺ ions. Oxygen plasma may be included in the range.

<Support>
The support of the gas barrier film in the present invention is not particularly limited as long as it is formed of an organic material capable of holding a gas barrier layer having a barrier property described later.

  For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films, and silsesquioxane having an organic-inorganic hybrid structure Examples thereof include a heat-resistant transparent film having a skeleton (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin film formed by laminating two or more layers of the resin.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), etc. are preferably used, and optical transparency, heat resistance, inorganic layer, gas barrier, etc. In terms of adhesion to the layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  The support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, various uses are possible as a transparent gas barrier film.

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

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

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

  Moreover, in the support body which concerns on this invention, you may corona-treat before forming a vapor deposition film. Further, an anchor coating agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion with the vapor deposition film.

<Anchor coat agent layer>
Examples of the anchor coating agent used in this anchor coating agent layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

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

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.

  It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

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

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

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

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used in order to improve the film formability and prevent the generation of pinholes in the film.

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

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

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

  One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the above-described photosensitive resin.

  Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin also contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be a thing.

  Further, as the photosensitive resin, a resin whose solid content is prepared by appropriately mixing a general-purpose diluting solvent with such reactive silica particles or an unsaturated organic compound having a polymerizable unsaturated group can be used. .

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties.

  From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent, cracks may occur when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier film may be affected.

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

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

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

  The thickness of the smooth layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficiently, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the smooth film, and the smooth layer is made of a transparent polymer film. It becomes possible to easily suppress curling of the smooth film when it is provided only on one of the surfaces.

<Bleed-out prevention layer>
The bleed-out prevention layer is a smooth layer for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the film support to the surface and contaminate the contact surface. On the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer includes a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or Mention may be made of monounsaturated organic compounds having one polymerizable unsaturated group.

  Here, examples of the polyunsaturated organic compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Moreover, as a unit price unsaturated organic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-e Xoxyethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

  The smooth layer in the present invention may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator and the like as other components of the hard coat agent and the matting agent.

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

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

  Moreover, as an ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. You can use what you want. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used.

  As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. As the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

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

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

  As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is formed on one side of the transparent polymer film. It becomes possible to easily suppress curling of the gas barrier film in the case where it is provided.

<Layer with silicon compound>
The gas barrier film in the present invention is formed by laminating a layer having a silicon compound by applying a sputtering method, an ion assist method, a plasma CVD method described later, a plasma CVD method under atmospheric pressure or a pressure close to atmospheric pressure described later, and the like. In particular, the method using atmospheric pressure plasma CVD is preferable because it does not require a decompression chamber or the like, enables high-speed film formation, and has high productivity. This is because a gas barrier layer having a higher gas barrier property can be easily formed by additionally forming the layer having the silicon compound by plasma CVD.

  The sputtering method, ion assist method, and plasma CVD method can form a film having a high barrier property. On the other hand, fine particles called particles are generated in the film forming process, and defects attached to or on the gas barrier layer are likely to occur. There is a defect.

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

  The thickness of the layer having these silicon compounds in the present invention is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 1 to 2000 nm.

  When the thickness of the layer having a silicon compound is 1 nm or more, a uniform film is easily obtained, film defects are reduced, and moisture resistance and gas barrier properties are easily improved. In addition, by setting the thickness of the layer having a silicon compound to 2000 nm or less, it is easy to maintain flexibility in the gas barrier film, and the gas barrier film is cracked by external factors such as bending and pulling after film formation. It becomes difficult to improve moisture resistance and gas barrier properties.

  In the present invention, the layer having the silicon compound is preferably transparent. This is because the gas barrier film can be made transparent by being transparent, and can be used for various purposes. As the light transmittance of the gas barrier film, for example, when the wavelength of the test light is 550 nm, the transmittance is preferably 80% or more, and more preferably 90% or more.

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

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

  As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. In addition, since these dilution solvents are decomposed | disassembled into molecular form and atomic form during a plasma discharge process, the influence can be disregarded almost.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples thereof include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

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

  A discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas to 50% or more of the entire mixed gas.

In the layer having a silicon compound according to the present invention, the inorganic compound contained is SiO _x C _y (x = 1.5 to 2.0, y = 0 to 0.5) or SiO _x , SiN _y or SiO. _{xN y} (x = 1 to 2, y = 0 to 1) is preferable, and SiO _x is preferable from the viewpoint of light transmittance and suitability for atmospheric pressure plasma CVD described later.

  The inorganic compound contained in the layer having a silicon compound according to the present invention is, for example, a combination of the above-mentioned organosilicon compound with oxygen gas or nitrogen gas at a predetermined ratio, and at least one of O atom and N atom and Si atom. A membrane containing it can be obtained.

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

(Atmospheric pressure plasma CVD method)
Next, the atmospheric pressure plasma CVD method that can be suitably used for forming the layer having a silicon compound according to the present invention in the method for producing a gas barrier film of the present invention will be described in more detail.

  CVD (chemical vapor deposition) is a method in which a volatilized and sublimated organometallic compound adheres to the surface of a high-temperature support and undergoes a decomposition reaction due to heat, producing a thermally stable inorganic thin film. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and is difficult to use for film formation on a plastic support.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the support to generate a space (plasma space) where a gas in a plasma state exists, and the volatilized / sublimated organometallic compound is introduced into the plasma space. By spraying on the support after the decomposition reaction has occurred, an inorganic thin film is formed.

  In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions or radicals, the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support on which the inorganic material is formed and can sufficiently form the film on the resin film support.

  Also, according to this method, a thin film having a dense film density and a stable performance when the layer having the silicon compound is formed on the resin film can be obtained.

  Next, an example of a method for laminating a layer having the silicon compound using a plasma CVD method at or near atmospheric pressure will be described.

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

  As described above, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an atmospheric pressure plasma discharge treatment apparatus applicable to the present invention, for example, atmospheric pressure plasma discharge treatment described in JP-A-2004-68143, 2003-49272, International Patent No. 02/48428, etc. An apparatus can be mentioned.

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

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

(Organic photoelectric conversion element)
The gas barrier film in this invention can be used for an organic photoelectric conversion element, for example. Since the gas barrier film is transparent when used in an organic photoelectric conversion element, it can be configured to receive sunlight from this side using this gas barrier film as a support.

  That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the support is used as an anode, a porous semiconductor layer is provided thereon, a cathode made of a metal film is further formed to form an organic photoelectric conversion element, and another seal is formed thereon. The organic photoelectric conversion element can be sealed by stacking a 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 forming a transparent conductive film on the gas barrier layer of the gas barrier film thus formed. The transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.

  As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 to 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 formed will be described.

(Sealing film and its manufacturing method)
The present invention is characterized in that the gas barrier film is used as a substrate.

  In the gas barrier film, a transparent conductive film is further formed on the gas barrier layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated thereon using this as an anode, and another layer is further formed thereon. The gas barrier film is used as a sealing film, and sealing is performed by repeated adhesion.

  In addition, 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-reducing 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 formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. Point to.

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

  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.

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

As the inert gas, a rare gas such as He and Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 99.9. It is preferable that it is volume%. Preservability is improved by sealing in an environment purged with an inert gas.

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

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

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm. However, if the amount of adhesive applied is too large, tunneling, seepage, shrinkage, etc. may occur, so the amount of adhesive is preferably adjusted to 3-5 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 to 50 μm. Commonly used base resins for hot melt adhesives include EVA, EEA, polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. as tackifiers, wax etc. It is added as an agent.

  The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 to 50 μm. 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 the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to this. There is no restriction | limiting in particular as an organic photoelectric conversion element, A photoelectric conversion part (a layer in which a p-type semiconductor and an n-type semiconductor are mixed, a bulk heterojunction layer, or an i layer) sandwiched between the anode and the cathode is at least 1 Any element that has more than one layer and generates current when irradiated with light may be used.

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

(I) Anode / photoelectric conversion part / cathode (ii) Anode / hole transport layer / photoelectric conversion part / cathode (iii) Anode / hole transport layer / photoelectric conversion part / electron transport layer / cathode (iv) Anode / positive Hole transport layer / p-type semiconductor layer / photoelectric conversion part / n-type semiconductor layer / electron transport layer / cathode (v) Anode / hole transport layer / first light emitting layer / electron transport layer / intermediate electrode / hole transport layer / Second light emitting layer / electron transport layer / cathode.

  Here, the photoelectric conversion portion needs to contain a p-type semiconductor material that can transport holes and an n-type semiconductor material that can transport electrons, and these substantially form a heterojunction in two layers. Alternatively, a bulk heterojunction that is in a mixed state in one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the photoelectric conversion portion will be described later.

  Since the organic EL device is sandwiched between the hole transport layer and the electron transport layer, the efficiency of taking out holes and electrons to the anode / cathode can be increased, so that the structure has them ((ii), (iii)) Is preferred. Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the photoelectric conversion unit itself is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (iv). Such 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 photoelectric conversion unit may be employed.

  Instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 1 for the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), a hole transport layer 17 and an electron transport layer 18 are respectively formed on a pair of comb-like electrodes. A back contact type organic photoelectric conversion element in which the photoelectric conversion unit 14 is disposed thereon can be configured.

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

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

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

  The photoelectric conversion unit 14 is a layer that converts light energy into electric 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 photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor. A hole-electron pair (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes.

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

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

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

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

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

  Below, the material which comprises these layers is described.

(Organic photoelectric conversion element material)
(P-type semiconductor material)
Examples of the p-type semiconductor material used in the photoelectric conversion part (bulk heterojunction layer) according to the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

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

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

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in 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, not polymer materials, include thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

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

  Moreover, when forming an electron transport layer on a photoelectric conversion part by application | coating, since there exists a subject that an electron transport layer solution will melt | dissolve a photoelectric conversion part, it uses the material which can be insolubilized after apply | coating with a solution process. Also good.

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

(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), etc. 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. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

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

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, 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. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

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

(Transparent electrode (first electrode))
In the transparent electrode according to the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element configuration, but preferably the transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires, and carbon nanotubes can be used.

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

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

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

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

(Intermediate electrode)
In addition, the intermediate electrode material required in the case of the tandem structure as shown in FIG. 3 is preferably a layer using a compound having both transparency and conductivity, such as the material used in the transparent electrode ( Transparent metal oxides such as ITO, AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS and 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 combining and laminating. Is preferable.

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

  In general, 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.

  The metal nanowire according to the present invention preferably has an average length of 3 μm or more in order to form a long conductive path with one metal nanowire and to exhibit appropriate light scattering properties. 3-500 micrometers is preferable and it is especially preferable that it is 3-300 micrometers. In addition, the relative standard deviation of the length is preferably 40% or less.

  Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity.

  In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.

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

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

(Optical function layer)
The organic photoelectric conversion element of the present invention may have various optical functional 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 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 forming method / Surface treatment method)
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a vapor deposition method and a coating method (including a cast method and a spin coat method). Among these, examples of the method for forming the bulk heterojunction layer include a vapor deposition method and a coating method (including a casting method and a spin coating method).

  Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. 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 photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

(Patterning)
There is no restriction | limiting in particular in the method and process of patterning the electrode which concerns on this invention, a photoelectric conversion part, a positive hole transport layer, an electron carrying layer, etc., A well-known method can be applied suitably.

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

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

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

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

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

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

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

  The maximum cross-sectional height Rt (p) at this time was 16 nm.

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

<< Preparation of Sample 1 >>
(Formation of gas barrier layer)
Next, a gas barrier layer was formed on the smooth layer of the sample provided with the smooth layer and the bleed-out prevention layer under the following conditions.

  A 20% by weight dibutyl ether solution of perhydroxypolysilazane (PHPS) (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was applied with a wireless bar so that the film thickness after drying was 0.3 μm. A sample was obtained.

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

<Second step; dehumidification treatment>
The dried sample was further dehumidified by being held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.). When the water ratio in the polysilazane film of the obtained sample was measured, it was 0.4%.

<Plasma treatment A>
The sample subjected to the dehumidification treatment was subjected to plasma treatment under the following conditions to form a gas barrier layer.

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

  Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film transport direction, gas and power are supplied to each electrode part, and appropriate treatment is performed so that the coating surface is irradiated with plasma for 30 seconds as follows. went.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 0.5 mm. The metal base material coated with the dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz 4 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ² .

<< Preparation of Sample 2 >>
Sample 2 was obtained in the same manner except that the dehumidification treatment in Sample 1 was changed as follows.

(Second step; dehumidification treatment)
The dried sample was further held for 30 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification. When the water ratio in the polysilazane film of Sample 2 obtained was measured, it was 0.1%.

<< Preparation of Sample 3 >>
Sample 3 was obtained in the same manner except that the dehumidification treatment in Sample 1 was changed as follows.

(Second step; dehumidification treatment)
The dried sample was further dehumidified by being held for 30 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 1% RH (dew point temperature of −31 ° C.). When the water content in the polysilazane film of Sample 3 obtained was measured, it was 0.01%.

<< Preparation of Sample 4 >>
Sample 4 was obtained in the same manner except that the dehumidification treatment in Sample 1 was changed as follows.

(Second step; dehumidification treatment)
The dried sample was further held for 120 minutes in an atmosphere of a temperature of 10 ° C. and a humidity of 1% RH (dew point temperature of −36 ° C.) to perform dehumidification. When the water ratio in the polysilazane film of Sample 4 obtained was measured, it was 0% (below the detection limit).

<< Preparation of Sample 5 >>
Sample 5 was obtained in the same manner except that the plasma treatment in Sample 2 was changed as follows.

(Plasma treatment B)
Japanese Unexamined Patent Application Publication No. 2007-237588, vacuum plasma processing conditions of Example 1.

<< Preparation of Sample 6 >>
Sample 6 was obtained in the same manner except that the plasma treatment in Sample 2 was changed as follows.

(Plasma treatment C)
Japanese Patent Application Laid-Open No. 2007-237588, atmospheric pressure plasma treatment conditions of Example 11.

<< Preparation of Sample 7 >>
Sample 7 was obtained in the same manner except that the first step in Sample 1 was changed as follows.

(First step; drying treatment)
The obtained coated sample was treated in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH for 30 minutes to obtain a dried sample. When the water ratio in the polysilazane film of Sample 7 obtained was measured, it was 0.3%.

<< Preparation of Sample 8 >>
Sample 8 was obtained in the same manner except that the second step (dehumidification treatment) before the plasma treatment in Sample 1 was not performed. When the water ratio in the polysilazane film before the plasma treatment was measured, it was 1.2%.

<< Preparation of Sample 9 >>
Sample 8 was obtained in the same manner except that the second step (dehumidification treatment) before the plasma treatment in Sample 6 was not performed. When the moisture ratio in the polysilazane film before the plasma treatment was measured, it was 1.1%.

<< Preparation of Sample 10 >>
Sample 10 was obtained in the same manner except that the first step (drying treatment) after applying polysilazane in Sample 1 was not performed. When the water ratio in the polysilazane film before the plasma treatment was measured, it was 0.5%.

<< Preparation of Sample 11 >>
Sample 10 was obtained in the same manner except that the first step (drying treatment) and the second step (dehumidification treatment) were not performed on sample 1. When the water ratio in the polysilazane film before the plasma treatment was measured, it was 3.0%.

  The water vapor barrier evaluation of the obtained samples 1 to 11 was performed by the following method.

(Evaluation of water vapor barrier properties (water vapor permeability))
The following measurement methods were used for evaluation.

<apparatus>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic Force Microscope (AFM): DI3100 from Digital Instruments
<raw materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3 to 5 mm, granular).

(Preparation of water vapor barrier property evaluation cell)
Gas barrier film sample No. Other than the part (12mm x 12mm 9 locations) where the gas barrier film sample before applying the transparent conductive film is to be deposited on the surface of the gas barrier layer 1 to 11 using a vacuum deposition device (JEOL vacuum deposition device JEE-400) Was masked and metal calcium was deposited. 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 under high temperature and high humidity of 60 ° C. and 90% RH, and moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in Japanese Patent Application Laid-Open No. 2005-283561. The amount was calculated.

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

  It turned out that the samples 1-7 of this invention are excellent in water vapor | steam barrier property. Particularly, the water vapor content in the polysilazane film before the plasma treatment was 0% (below the detection limit), and the sample 4 which was subjected to the nitrogen two-frequency atmospheric pressure plasma treatment showed the most excellent water vapor barrier performance.

Example 2
<< Preparation of Sample 12 >>
Sample 12 was prepared in the same manner except that Sample 3 in Example 1 was changed to the following plasma treatment conditions.

(Plasma treatment D)
The sample which performed the 2nd process (dehumidification process) was plasma-processed on condition of the following, and the gas barrier layer was formed.

  The support holding temperature during film formation was 130 ° C.

  Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film conveyance direction, and gas and power are supplied to each electrode portion, and processing is appropriately performed so that the coating surface is irradiated with plasma for 60 seconds as follows. went.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 0.5 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 3% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz, 6 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ² .

The N ₄ ⁺ ion density value under the plasma treatment D condition was estimated from the method described in JP-A-2006-253118, and found to be 8.5 × 10 ¹⁶ [m ⁻³ ].

<< Preparation of Sample 13 >>
Sample 13 was produced in the same manner except that the plasma treatment of sample 12 was changed as follows.

(Plasma treatment E)
The sample which performed the 2nd process (dehumidification process) was plasma-processed on condition of the following, and the gas barrier layer was formed.

  The support holding temperature during film formation was 130 ° C.

  Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film conveyance direction, and gas and power are supplied to each electrode portion, and processing is appropriately performed so that the coating surface is irradiated with plasma for 60 seconds as follows. went.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 0.5 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 8% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz, 9 W / cm ²
High frequency side power supply power: 13.56 MHz is 12 W / cm ² .

The N ₄ ⁺ ion density value in the plasma treatment E condition was estimated to be 2.0 × 10 ¹⁷ [m ⁻³ ].

<< Preparation of Sample 14 >>
A sample 14 was produced in the same manner except that the plasma treatment of the sample 12 was changed as follows.

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

  The support holding temperature during film formation was 130 ° C.

  Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film transport direction, gas and power are supplied to each electrode part, and appropriate treatment is performed so that the coating surface is irradiated with plasma for 60 seconds as follows. went.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 0.5 mm. The metal base material coated with the dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 0% of oxygen gas to the total gas
Low frequency side power supply power: 100 kHz 3 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ² .

The N ₄ ⁺ ion density value in the plasma treatment F condition was estimated to be 5.0 × 10 ¹⁶ [m ⁻³ ].

<< Preparation of Sample 15 >>
Sample 15 was produced in the same manner except that the plasma treatment of sample 12 was changed as follows.

(Plasma treatment G)
The sample subjected to the dehumidification treatment was subjected to plasma treatment under the following conditions to form a gas barrier layer. The conditions in which the output is replaced with 100 kHz in the atmospheric pressure plasma processing conditions of JP2007-237588A and Example 11.

The N ₄ ⁺ ion density value under the plasma treatment G condition was estimated to be 4.0 × 10 ¹⁵ [m ⁻³ ].

  The obtained samples 12 to 15 were evaluated for water vapor barrier performance in the same manner as in Example 1.

Among Samples 12 to 15 of the present invention, Sample 13 having the highest N ₄ ⁺ ion density showed excellent barrier performance.

<< Preparation of Sample 16 >>
Sample No. 1 of Example 1 described in JP-A-2004-84027. A 200 nm SiON film corresponding to 5 was prepared by atmospheric pressure plasma CVD. It was 1.0 * 10 < ^-3 > [g / m < ² > / day] when the water vapor | steam barrier performance as described in Example 1 was evaluated.

Example 3
[Production of organic photoelectric conversion element]
Samples 1 to 16 above each having a 150 nm thick indium tin oxide (ITO) transparent conductive film deposited (sheet resistance 10 Ω / □) are patterned to a width of 2 mm using normal photolithography and wet etching. A first electrode was formed. The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

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

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

First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Then, chlorobenzene P3HT (plectrovirus Toro Nix Ltd. regioregular poly-3-hexylthiophene) and PCBM (Frontier Carbon: 6,6-phenyl _{-C 61} - butyric acid methyl ester) consisting of 3.0 wt% Thus, a liquid mixed at 1: 0.8 was prepared, applied to a film thickness of 100 nm while being filtered through a filter, and allowed to dry at room temperature. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate on which the series of functional layers is formed is moved into the vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then the substrate is fed at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium fluoride, then continue through a shadow mask with a width of 2 mm (vapor deposition is performed so that the light receiving part is 2 × 2 mm), and deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec. A second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

  In an environment purged with nitrogen gas (inert gas), two gas barrier film samples 1 to 16 were used, and an epoxy photocurable adhesive was applied as a sealing material to the surface provided with the gas barrier layer. After the organic photoelectric conversion elements corresponding to the samples 1 to 16 obtained by the method described above are sandwiched between the adhesive application surfaces of the two gas barrier film samples 1 to 16 coated with the adhesive, The organic photoelectric conversion elements 1 to 16 were cured by irradiating UV light from one side of the substrate.

[Evaluation of durability of organic photoelectric conversion elements]
<Evaluation of energy conversion efficiency>
About the produced photoelectric conversion element, the light of the intensity | strength of 100 mW / cm < ² > of a solar simulator (AM1.5G filter) is irradiated, the mask which made the effective area 4.0mm < ² > is piled up on a light-receiving part, and IV characteristic is evaluated. Thus, the short-circuit current density Jsc (mA / cm ² ), the open-circuit voltage Voc (V), and the fill factor FF (%) are respectively measured at the four light receiving portions formed on the same element, and obtained according to the following formula 1. The four-point average value of the energy conversion efficiency PCE (%) was estimated.

(Formula 1) PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial battery characteristics was measured, and the degree of deterioration over time was evaluated by the conversion efficiency remaining rate after the acceleration test stored for 1000 hours in a temperature 60 ° C., humidity 90% RH environment.

Ratio of conversion efficiency / initial conversion efficiency after acceleration test 5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20%.

  The respective evaluation results are shown in Table 3.

  As is apparent from Table 3, the gas barrier film of the present invention has a low water vapor transmission rate, and the organic photoelectric conversion device produced using the gas barrier film of the present invention suffers from performance deterioration under harsh environments. hard.

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

Claims (6)

  In the method for producing a gas barrier film in which a polysilazane film is applied to at least one surface of a substrate and a gas barrier layer is formed by performing a plasma treatment, a first step of removing the solvent during the application of the polysilazane film before the plasma treatment; The manufacturing method of the gas barrier film characterized by including the 2nd process of removing a water | moisture content following it.   The method for producing a gas barrier film according to claim 1, wherein the water content of the polysilazane film after the second step is 0.1% or less.   The method for producing a gas barrier film according to claim 1, wherein the plasma treatment is an atmospheric pressure plasma treatment.   The method for producing a gas barrier film according to claim 3, wherein the atmospheric pressure plasma treatment is nitrogen two-frequency discharge. 5. The gas barrier film according to claim 3, which is a plasma treatment containing N ₄ ⁺ ions having a time average density of 8.0 × 10 ¹⁶ [m ⁻³ ] or more in the atmospheric pressure plasma treatment. Manufacturing method.   It has a gas barrier film formed by the manufacturing method of the gas barrier film of any one of Claims 1-5, The organic photoelectric conversion element characterized by the above-mentioned.

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