JP5861376B2 - Gas barrier film, method for producing gas barrier film, and electronic device having gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film, a method for producing a gas barrier film, and an electronic device having the gas barrier film.

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

  As a method for producing such a gas barrier film, a physical vapor deposition method (PVD method) in which a metal, an oxide, or the like is evaporated to form a film on a substrate, or a raw material gas containing a target thin film component (for example, tetraethoxy). For example, metal Si is vaporized using a chemical vapor deposition method (CVD method) in which a film is deposited by a chemical reaction in the surface of the substrate or in the gas phase, and a semiconductor laser. In addition, a sputtering method for depositing on a substrate in the presence of oxygen is known.

  CVD methods include thermal CVD methods that use heat to control chemical reactions, and plasma CVD methods that use plasma to excite and react the atoms and molecules of the source gas. It can be said that a plasma CVD method capable of forming a film at a high speed is more general. In particular, the atmospheric pressure plasma CVD method in which plasma is generated under atmospheric pressure and a film is formed under atmospheric pressure is attracting attention as a method capable of improving productivity more than in a vacuum process.

  An inorganic film formed by such an evaporation method is a highly stable film with little compositional change over time, but it has poor smoothness and includes defects such as pinholes. It has been difficult to obtain.

  For such problems, Patent Documents 1 to 5 disclose techniques aiming at planarization and defect repair by laminating a coating-type polysilazane conversion film on a vapor deposition film.

  However, in any known example, polysilazane is converted by heating, and the resulting inorganic film is probably a silica film containing a large amount of silanol groups, so that it is considered that sufficient barrier properties cannot be obtained. Therefore, it is considered that the polysilazane conversion film functions mainly as a planarization protective layer.

  Therefore, it is considered that the vapor deposition film is responsible for the substantial barrier layer. However, in order to obtain the denseness necessary for obtaining a sufficient barrier property with the vapor deposition film, an ultra-low speed and a certain level or more are required. Deposition with a film thickness is required, and cost reduction is extremely difficult.

On the other hand, a barrier layer obtained by converting a polysilazane coating film by irradiation with vacuum ultraviolet light (VUV light) has a dense and high barrier property, and has fewer defects than a film formed by a CVD method or the like, and can be flattened. In recent years, a method for forming a film has been studied.
For example, Patent Document 6 discloses a technique for forming a gas barrier film by laminating a barrier layer obtained by converting a polysilazane coating film by vacuum ultraviolet treatment.

  However, in the disclosed production method, it is necessary to repeatedly apply and irradiate the vacuum ultraviolet ray irradiation time per layer as 1 to 5 minutes, and continuous production such as roll-to-roll. Therefore, it cannot be said that productivity is very high, and cost reduction is extremely difficult. Furthermore, in Patent Document 6, since a polysilazane conversion film is directly provided on a resin base material, it cannot be said that stability such as wet heat stability and bending resistance is sufficient.

  In addition, the gas barrier film composed only of the polysilazane conversion film starts to permeate water vapor, and at a certain point, the barrier property rapidly deteriorates and loses the barrier property. It has been confirmed by the barrier property evaluation by the method and the organic device element evaluation, which is a big problem in obtaining a stable gas barrier film.

  In order to obtain a stable gas barrier film in which the barrier property does not deteriorate rapidly, a layer structure that can stably hold a polysilazane conversion barrier layer modified with good film quality on a flexible resin substrate is required. The reality is that it has not been fully studied so far.

Japanese Patent Laid-Open No. 2003-118030 JP 2008-235165 A Japanese Patent Laid-Open No. 8-281186 JP-A-9-70917 Japanese Patent Laid-Open No. 11-151774 JP 2009-255040 A

  The present invention has been made in view of the above problems, and its purpose is to provide a gas barrier film capable of achieving high gas barrier performance and high gas barrier performance stability (wet heat resistance, bending resistance), a method for producing the gas barrier film, and An object of the present invention is to provide an electronic device using the gas barrier film.

The above object of the present invention is achieved by the following configurations.
1. When the relative etching rate on the resin base material in the film thickness direction by sputtering is 1.0, the etching rate of the polysilazane thermal oxide film is 1.0. A first stress relaxation layer made of a vapor deposition film that is 0 or less; 2) a barrier layer that is a modification of a coating film containing polysilazane that is 1.1 to 2.5; and 3) 1.0 and a protective layer is equal to or greater than 3.0 or less possess in this order,
The thermal oxidation film of the polysilazane is a 20 mass% dibutyl ether solution of perhydropolysilazane (PHPS), AQUAMICA NN120-20 manufactured by AZ Electronic Materials Co., Ltd., and an amine catalyst (N, N, N ′, N ′). -By mixing with NAX120-20 containing 5% by mass of tetramethyl-1,6-diaminohexane), the amine catalyst content becomes 1.0% by mass with respect to the perhydropolysilazane (PHPS) concentration. After adjusting so that the coating film was applied by spin coating using a solution diluted to 10% by mass with a dibutyl ether solvent, the resulting coating film was dried at 80 ° C. for 1 minute, and after drying, a film thickness of 150 nm was obtained. A hydropolysilazane-containing layer was prepared, and the perhydropolysilazane-containing layer after drying was treated at 80 ° C. for 5 minutes under a humidity of 90% RH. A gas barrier film characterized in that it is a layer in which polysilazane is converted into a film mainly composed of silicon oxide by further drying in a vacuum oven at 100 ° C. for 8 hours .
2. The relative etching rate of the first stress relaxation layer is 1.5 or more and 3.0 or less, and the relative etching rate in contact with the first stress relaxation layer and the barrier layer is 1.0 or more and 1 The gas barrier film as described in 1 above, having a second stress relaxation layer of .4 or less.
3. When the etching rate of the thermal oxidation film of polysilazane is 1.0 on the basis of the relative etching rate when the resin base material is etched in the film thickness direction by sputtering, 1) 1.0 or more. A step of forming a first stress relaxation layer of 0 or less by vapor deposition, and 2) a step of forming a barrier layer of 1.1 or more and 2.5 or less by modifying a coating film containing polysilazane. If, possess and forming a protective layer is 3) 1.0 to 3.0 in this order,
The thermal oxidation film of the polysilazane is a 20 mass% dibutyl ether solution of perhydropolysilazane (PHPS), AQUAMICA NN120-20 manufactured by AZ Electronic Materials Co., Ltd., and an amine catalyst (N, N, N ′, N ′). -By mixing with NAX120-20 containing 5% by mass of tetramethyl-1,6-diaminohexane), the amine catalyst content becomes 1.0% by mass with respect to the perhydropolysilazane (PHPS) concentration. After adjusting so that the coating film was applied by spin coating using a solution diluted to 10% by mass with a dibutyl ether solvent, the resulting coating film was dried at 80 ° C. for 1 minute, and after drying, a film thickness of 150 nm was obtained. A hydropolysilazane-containing layer was prepared, and the perhydropolysilazane-containing layer after drying was treated at 80 ° C. for 5 minutes under a humidity of 90% RH. Then, the manufacturing method of the gas-barrier film which is a layer by which polysilazane was converted into the film | membrane which has a silicon oxide as a main component by further drying in a 100 degreeC vacuum oven for 8 hours .
4. The relative etching rate of the first stress relaxation layer is 1.5 or more and 3.0 or less, and after the step of forming the first stress relaxation layer, the relative etching rate is 1.0 or more. 4. The method for producing a gas barrier film as described in 3 above, further comprising a step of forming a second stress relaxation layer of 1.4 or less by vapor deposition.
5, In the method for producing a gas barrier film according to 3 or 4,
5. The gas barrier film according to 3 or 4 above, wherein a film formation rate at the time of vapor deposition when forming the first or second stress relaxation layer is 0.1 nm / second to 30 nm / second. Production method.
6. The method for producing a gas barrier film as described in 3 to 5 above, wherein the modification treatment of the coating film containing polysilazane is a vacuum ultraviolet ray irradiation treatment. Manufacturing method.
7. The method for producing a gas barrier film according to 3 to 6, wherein the first or second stress relaxation layer is formed by a CVD method in the method for producing a gas barrier film according to 3 to 6. Production method.
8. An organic electronic device characterized by being sealed with the gas barrier film described in 1-2 above.

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

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

Hereinafter, the present invention will be described in detail.
In order to obtain a stable gas barrier film that does not rapidly deteriorate in gas barrier properties, it is essential to have a structure that can stably hold a polysilazane conversion barrier layer modified with good film quality on a flexible resin substrate. However, it was found by the inventors' investigation.

  As such a configuration, the stress relaxation layer has good adhesion to the base material and the barrier layer, relaxes internal stress accumulated in the barrier layer, and can appropriately block moisture from the base material side when forming the barrier layer. It has been found that a protective layer that protects against stress applied to the barrier layer at the time of bending under heat and humidity, the element manufacturing process, etc. is essential, and that these functions are not deteriorated even under wet heat.

Therefore, in order to obtain a highly stable barrier film, as in the present invention, a stress relaxation layer composed of a vapor deposition film is provided in the lower layer of the polysilazane conversion barrier layer, and a protective layer is provided in the upper layer. However, the reason is not clear, but the stress relaxation has a specific value when the etching rate of the SiO ₂ thermal oxide film is set to 1.0 when the etching is performed in the film thickness direction by the sputtering method. It has been found that a layer, a barrier layer, and a protective layer may be provided.

Since the stress relaxation layer or protective layer made of the vapor deposition film of the present invention can be deposited at high speed, the cost can be reduced.
Hereinafter, the present invention, its components, and embodiments for carrying out the present invention will be described in detail.

<< Gas barrier film and method for producing gas barrier film >>
The gas barrier film of the present invention and the method for producing the gas barrier film will be described.
The gas barrier film of the present invention is 1) when the etching rate of the SiO ₂ thermal oxide film is 1.0 on the resin base material when the etching is performed in the film thickness direction by sputtering. A stress relaxation layer made of a vapor deposition film that is 1.0 or more and 3.0 or less, 2) a barrier layer obtained by modifying a coating film containing polysilazane that is 1.1 or more and 2.5 or less, and 3) It has the protective layer which is 1.0 or more and 3.0 or less in this order.

As a method for producing a gas barrier film of the present invention, in the formation of a gas barrier layer, a coating film containing polysilazane, preferably perhydropolysilazane, is provided on the stress relaxation layer made of the deposited film, and then subjected to a modification treatment (conversion). A barrier layer is formed by applying a treatment).
Furthermore, the modification treatment is preferably an ultraviolet irradiation treatment.
The step of modifying the coating after the step of forming a coating by applying a solution containing perhydropolysilazane will be described in detail later.

Moreover, the stress relaxation layer which consists of a vapor deposition film of this invention is formed by a vapor deposition method on the resin base material, It is characterized by the above-mentioned.
The step of providing the stress relaxation layer comprising the vapor deposition film of the present invention on the resin substrate by the vapor deposition method will be described in detail later.

The protective layer of the present invention is characterized in that it is provided on a barrier layer obtained by modifying the coating film containing the polysilazane.
The protective layer of the present invention will also be described in detail later.

[Gas barrier properties]
The gas barrier property referred to in the present invention is a water vapor permeability (60 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 3 × 10 ^−3. g / (m ² · 24h) or less, the oxygen permeability measured in compliance with the method provided in JIS K 7126-1987 is, the ^{1 × 10 -3 ml / m 2} · 24h · atm or less (1 atm, 1 .01325 × 10 ⁵ Pa).

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

  In the present invention, a gas barrier film having a structure having a stress relaxation layer made of a vapor deposition film, a barrier layer obtained by modifying a coating film containing polysilazane, and a protective layer in this order on a resin substrate. It can be expected to suppress the deformation of the base material such as curling that occurs during the device manufacturing process such as the cleaning process, but the curl balance adjustment and device manufacturing process are performed on the back side of the base material opposite to the side where the barrier layer is provided. A back coat layer may be further provided for the purpose of improving resistance, handling suitability and the like.

[Gas barrier layer]
(Formation of gas barrier layer)
In the gas barrier layer of the present invention, the coating liquid of the composition containing polysilazane, preferably perhydropolysilazane, is applied on the stress relaxation layer made of the deposited film in the present invention, and then subjected to a modification treatment, whereby the inorganic substance is obtained. A barrier layer is formed.

Specific examples of inorganic substances include silicon oxide, silicon nitride, and silicon oxynitride.
Regarding the fact that the coating film containing polysilazane in the present invention is converted into a barrier layer made of an inorganic film by performing a modification treatment, each atomic composition of Si atoms, N atoms, O atoms, and the like is determined by XPS surface analysis. This can be confirmed by determining the ratio.

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

  In the present invention, the barrier layer is formed by subjecting a coating film of perhydropolysilazane to irradiation with vacuum ultraviolet rays in an appropriate oxidizing gas atmosphere and a low humidity environment as described later, and a stress relaxation layer comprising the deposited film of the present invention. By adopting a structure provided in the lower layer, it can be formed efficiently.

(Film quality of gas barrier layer)
The gas barrier layer in the present invention is formed by modifying a coating film containing polysilazane, and the relative etching rate when etching in the film thickness direction by the sputtering method is the etching rate of the SiO ₂ thermal oxide film. When 1.0, it is 1.1 or more and 2.5 or less.

  The etching rate of the gas barrier layer in the present invention can be determined by the same method as the stress relaxation layer of the present invention described later.

The reason why the etching rate of the gas barrier layer in the present invention is larger than that of the SiO ₂ thermal oxide film or the SiO ₂ film formed by the vapor deposition method is that the barrier layer of the present invention is not made of SiO ₂ alone but is an acid containing N atoms. This is thought to be because it is made of a film containing a large amount of silicon nitride.

  A thin film formed from polysilazane can be completely converted into silicon dioxide under, for example, wet heat conditions, but a silicon oxynitride film containing N atoms is more preferable than a silica film containing silicon dioxide as a main component. It has been found by the inventors' investigation that a high barrier property is exhibited.

(Formation of coating film containing polysilazane)
<Application method>
The coating film containing polysilazane according to the present invention is produced by applying a coating solution containing at least one polysilazane compound on a substrate.
Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

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

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

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

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

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

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

<Coating liquid for composition containing polysilazane>
“Polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N _4, and an intermediate solid solution SiO _x N _{y of} both. Such as a ceramic precursor inorganic polymer.

In order not to damage the film base material, it is converted to silica by being ceramicized at a relatively low temperature as represented by the following general formula (1) described in JP-A-8-112879. Compounds are preferred.
General formula (1)
—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
In the present invention, perhydropolysilazane (also referred to as PHPS) in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a gas barrier layer 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 commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as a perhydropolysilazane-containing coating solution.

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

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

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

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

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

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

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

(Modification of coating film containing perhydropolysilazane)
<Modification treatment by UV irradiation>
The modification treatment (conversion treatment) in the present invention applied to the coating film containing perhydropolysilazane is performed by irradiating ultraviolet rays in an appropriate oxidizing gas atmosphere and a low humidity environment.
Irradiation with ultraviolet light generates active oxygen and ozone, and an oxidation reaction proceeds, whereby an inorganic film having a desired composition can be obtained.

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

The reforming treatment in the present invention is more preferably performed in combination with heat treatment.
Further, ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion for the shortage of reactive ozone and introduced into the ultraviolet irradiation portion.
Although the wavelength of the ultraviolet light irradiated at this time is not particularly limited, the wavelength of the ultraviolet light is preferably 100 to 450 nm, and more preferably vacuum ultraviolet light (VUV light) of about 100 to 300 nm is irradiated.

As the light source, a low-pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. The output of the lamp ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, preferably 10 to 10000 mJ / cm ² as irradiation energy, 100~8000mJ / cm ² is more preferable. In addition, the illuminance upon ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² .

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

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

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

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

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

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

  VUV light irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a substrate provided with a coating film formed from a composition containing perhydropolysilazane can be processed in a vacuum ultraviolet ray baking furnace equipped with a vacuum ultraviolet ray generation source. The vacuum ultraviolet baking furnace itself is generally known, and for example, Ushio Electric Co., Ltd. can be used. Moreover, when the base material provided with the coating film formed from the composition containing perhydropolysilazane is in the form of a long film, in the drying zone equipped with the vacuum ultraviolet ray generation source as described above while transporting it. By continuously irradiating with vacuum ultraviolet rays, the surface can be ceramicized.

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

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

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

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

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

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

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

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

The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.
The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

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

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

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

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

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

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

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

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

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

[First stress relaxation layer made of vapor-deposited film]
In the present invention, the relative etching rate when the etching is performed on the resin base material in the film thickness direction by the sputtering method is 1.0 or more when the etching rate of the SiO ₂ thermal oxide film is 1.0. It has the 1st stress relaxation layer which consists of a vapor deposition film which is 0 or less.
Hereinafter, the 1st stress relaxation layer in this invention is demonstrated in detail.

(Relative etching rate)
In the present invention, the first stress relaxation layer has a relative etching rate of 1.0 or more when the etching rate of the SiO ₂ thermal oxide film is 1.0 when etching is performed in the film thickness direction by a sputtering method. It is 3.0 or less.

  Etching by sputtering is a method of etching by ion beam irradiation and is also called sputter etching. When the sample surface is irradiated with an ion beam, atoms on the sample surface are ejected, and the substance can be removed from the sample. Etching the sample surface using this phenomenon is called sputter etching. By this sputtering method, the thin film is etched from the surface.

In the present invention, a SiO ₂ thermal oxide film formed on a silicon wafer by a thermal oxidation method is used as a reference for the etching rate. A silicon wafer with a thermal oxide film is commercially available, and a commercially available product can be obtained and used.

If such a commercially available silicon wafer with a thermal oxide film is used, since the film thickness of the SiO ₂ film is known in advance, there is a certain etching time from the time when the entire SiO ₂ film is etched under a certain condition. The etching rate under a certain condition can be obtained.
Whether the entire SiO ₂ film has been etched can be confirmed by performing the XPS surface analysis described above while etching the film, so that the respective atomic composition ratios of Si atoms and O atoms can be obtained for each etching unit time. it can.

  Similarly, the etching rate of the first stress relaxation layer can also be obtained from the time required for etching the actual film thickness and the total film thickness of the first stress relaxation layer.

  The actual film thickness of the first stress relaxation layer can be confirmed by a clear interface with the adjacent layer being seen from a cross-sectional photograph of a TEM (Transmission Electron Microscope).

The relative etching rate (ER) of the first stress relaxation layer in the present invention can be obtained by the following equation.
ER = etching rate of the first stress relaxation layer (nm / min) / etching rate of the SiO ₂ thermal oxide film (nm / min)

(Formation of first stress relaxation layer by vapor deposition)
The first stress relaxation layer of the present invention is formed by a vapor deposition method.
There are two types of vapor deposition methods: physical vapor deposition and chemical vapor deposition. In the present invention, chemical vapor deposition (CVD) is more effective in that a denser thin film can be formed at low temperature and at high speed. preferable.

Chemical vapor deposition methods include thermal CVD method, photo CVD method, plasma CVD method, epitaxial CVD method, atomic layer CVD method, MOCVD method (metal organic chemical vapor deposition method). The plasma CVD method is more preferable in that high-speed film formation is possible.
The plasma CVD method includes a vacuum process and an atmospheric pressure process, both of which can be preferably used. However, the atmospheric pressure process is preferable in that the process load can be reduced because all processes can be performed under atmospheric pressure.

In the plasma CVD method, a high-frequency gas is applied to the source gas to turn the gas into plasma, and the atoms and molecules of the source gas are excited and reacted to form an inorganic film such as SiO ₂ on the substrate in an active state. It is a method of depositing.

Examples of the inorganic film to be obtained include a silicon oxide film, a silicon oxynitride film, a silicon nitride film, a silicon carbide film, and a silicon oxide carbide film. However, the inorganic film may contain a small amount of organic material derived from the raw material.
Hereinafter, the atmospheric pressure plasma CVD method which is a more preferable embodiment will be described.

(Atmospheric pressure plasma CVD method)
The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, nitrogen gas or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon or the like is used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

<Atmospheric pressure plasma treatment with two or more electric fields of different frequencies>
Next, a preferable embodiment for the atmospheric pressure plasma treatment will be described. Specifically, the atmospheric pressure plasma treatment is one in which two or more electric fields having different frequencies are formed in the discharge space as described in the specification of International Publication No. 2007-026545. It is preferable to use a method in which an electric field is formed by superimposing two high-frequency electric fields.

Specifically, 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 The relationship with the starting electric field strength IV is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is preferably 1 W / cm ² or more.

  By adopting such discharge conditions, for example, even with a discharge gas having a high discharge starting electric field strength such as nitrogen gas, the discharge can be started and a high density and stable plasma state can be maintained, and a high performance thin film can be formed. It can be carried out.

When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field intensity IV (1/2 V _pp ) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field intensity is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

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

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

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

  The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to 110 kPa, and 93 kPa to 104 kPa is preferable in order to obtain a good effect described in the present invention.

  The excited gas as used in the present invention means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy. Excited gas molecules, radicalized gas molecules A gas containing ionized gas molecules corresponds to this.

  In the present invention, for example, when the first stress relaxation layer is formed on the base material, a source gas containing, for example, silicon (tetraethoxy) in a discharge space where a high-frequency electric field is generated under atmospheric pressure or a pressure in the vicinity thereof. A gas containing silane, hexamethyldisiloxane, or the like) is mixed with an excited discharge gas to form a secondary excitation gas, and an inorganic film is formed by exposing the substrate to the secondary excitation gas.

  That is, as a first step, the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure near it, a discharge gas is introduced between the counter electrodes, a high frequency voltage is applied between the counter electrodes, and the discharge gas is converted into plasma. Then, the discharge gas and the raw material gas that are in a plasma state are mixed outside the discharge space, and the base material is exposed to the mixed gas (secondary excitation gas). A stress relaxation layer is formed.

<Raw material (gas) used for atmospheric pressure plasma method>
In the atmospheric pressure plasma method, silicon oxide, a metal oxide mainly composed of silicon oxide, or a metal oxide, which is a raw material (also referred to as a raw material), decomposition gas, decomposition temperature, input power, and the like are selected. In addition, the composition of metal carbides, metal nitrides, metal sulfides, metal halides and the like (metal oxynitrides, metal oxyhalides, etc.) can be made differently.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if silazane or the like is used as a raw material compound, silicon oxynitride is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As a raw material for forming such a ceramic layer, as long as it is a silicon compound, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

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

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

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

  In the atmospheric pressure plasma method, a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to a plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed and supplied to an atmospheric pressure plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

(Deposition rate during deposition)
The film formation rate during vapor deposition in the present invention is expressed in units of nm / second.
As the film formation rate is lower, a dense thin film can be formed. However, if the film formation rate is too low, the cost increases. Therefore, in the present invention, the film thickness is preferably 0.1 to 30 nm / second.

  By controlling the film formation rate, it is possible to make a thin film having a desired etching rate.

(Function of stress relaxation layer)
In order to obtain a stable coating-type gas barrier film that does not rapidly deteriorate its barrier properties, it is essential to have a structure that can stably hold a polysilazane conversion barrier layer modified with good film quality on a flexible resin substrate. There is something as described above.

  As one of such structural requirements, the stress relaxation layer in the present invention is based on adhesion between the base material and the barrier layer, relaxation of internal stress and shrinkage stress accumulated in the barrier layer, and the basis at the time of barrier layer formation. It is considered to have functions such as moisture adjustment from the material side.

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

  Once the hydrolysis reaction proceeds before the reforming process and a large amount of Si-OH is formed in the film, the barrier layer can be used for the reforming process by irradiating VUV light thereafter. It becomes difficult to form a layer that exhibits the barrier properties of the invention.

  Therefore, in the present invention, as described above, the barrier layer of the present invention is formed by irradiating VUV light in an optimum low oxygen concentration atmosphere and in a low humidity environment, and allowing only direct oxidation by active oxygen to proceed. It is important to form.

  It has also been found that simply optimizing the environment at the time of reform is insufficient to obtain stable barrier performance. This is because when the base material, the hard coat layer, the flattening layer, the adhesion layer, etc. are mainly composed of a resin component, if the barrier layer is formed in contact with them, for example, the moisture contained in the resin base material or the resin layer itself In addition, it is presumed that the quality of the polysilazane modified film is deteriorated due to moisture entering from the outside air through them.

  Thus, it has been found that when the stress relaxation layer of the present invention is provided as a lower layer for forming the polysilazane modified film, silanol groups and the like are hardly generated and the modification of polysilazane can be made efficient.

[Second stress relaxation layer]
In the present invention, it is preferable to further have a second stress relaxation layer provided adjacent to the barrier layer on the first stress relaxation layer.

The relative etching rate of the second stress relaxation layer in the present invention is 1.0 or more and 1.4 or less when the etching rate of the SiO ₂ thermal oxide film is 1.0.

  The etching rate of the second stress relaxation layer of the present invention can be determined by the same method as that for the first stress relaxation layer.

  However, in the TEM cross-sectional photograph when determining the actual film thickness, when it is difficult to determine the interface with the first stress relaxation layer, under the same conditions as the film formation conditions for forming the second stress relaxation layer, Separately, the etching rate may be obtained by preparing a second stress relaxation layer on a substrate having a clearly different composition so that the interface can be clearly seen, and confirming the actual film thickness.

  Alternatively, if the film quality difference between the first stress relaxation layer and the second stress relaxation layer is large to some extent, the film quality difference reflected in the shading of the photograph is further clarified by irradiating the electron beam excessively. , It may be easier to judge.

  In the present invention, a second stress relaxation layer having a lower relative etching rate, that is, a film quality strength closer to that of a thermal oxide film is provided in the lower layer of the barrier layer, and further, a lower relative stress is provided in the lower layer of the second stress relaxation layer. By providing the first stress relaxation layer having a higher etching rate, that is, a softer layer, the function of relieving stress such as internal stress and shrinkage stress applied to the barrier layer is further enhanced, and the breakdown of the barrier layer cannot be suppressed. I think.

  The film quality of the second stress relaxation layer can be adjusted by controlling the film formation speed after selecting the optimal raw materials and film formation conditions so that impurities such as organic components do not remain in the film.

  The second stress relaxation layer is formed by vapor deposition in the same manner as the first stress relaxation layer. The film formation rate of the second stress relaxation layer is 0.1 to 10 nm / second, more preferably 0.1 to 2 nm / second.

[Protective layer]
In the present invention, the protective layer has a relative etching rate of 1.0 or more and 3.0 or less when the etching rate of the SiO ₂ thermal oxide film is 1.0 when etching is performed in the film thickness direction by sputtering. Is provided on the barrier layer.

  The etching rate of the protective layer in this invention can be calculated | required by the method similar to the stress relaxation layer of this invention mentioned above.

  The protective layer in the present invention is not only a role of a simple protective film that improves device fabrication process resistance, conveyance, winding process suitability, etc. by providing it on the upper layer of the barrier layer, but also rapidly deteriorates the barrier property. It has been found by the inventor's examination that the present invention is very effective for obtaining a stable barrier film. It is speculated that this may be because the barrier layer is thought to be able to suppress the degradation of the barrier property, which is thought to be caused by abrupt destruction during accelerated degradation due to wet heat, at the nano level. However, details are unknown.

(Method for forming protective layer)
The method for forming the protective layer of the present invention is not particularly limited, but the vapor deposition methods mentioned above as methods for forming the stress relaxation layer can be preferably used.
Moreover, it can also form by the apply | coating method by selecting an appropriate material.

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

(Material for forming protective layer by coating method)
In the present invention, the material for forming the protective layer by a coating method includes polysiloxane and polysilsesquioxide from the viewpoints of film properties such as heat resistance and elastic modulus, and adhesion and affinity with adjacent barrier layers. A material containing oxane or the like as a main component is preferable.

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

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

  Specific compounds that can be used as a raw material for forming a protective layer by a coating method include, for example, methyl hydropolysiloxane, methylsilsesquioxane, hydrosilsesquioxane (manufactured by Konishi Chemical), tetra Examples include cage-like organic silsesquioxane such as silanophenyl POSS, polydiethoxysiloxane, diethoxysiloxane-ethyl titanate copolymer, polydibutyl titanate, and organic polysilazane.

  Commercially available materials can also be applied as the organic polysiloxane that forms the protective layer.

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

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

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

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

[Resin substrate (also called support)]
The resin substrate (support) in the present invention is not particularly limited as long as it can hold the stress relaxation layer, gas barrier layer and protective layer of the present invention, but mass production such as roll-to-roll. A plastic film is preferable in that it is easy to handle and can be reduced in cost.

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

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

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

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

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

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

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

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

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

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

  The anchor coat layer is not particularly limited as long as it improves the adhesion between the plastic film and the stress relaxation layer. However, since the stress relaxation layer of the present invention is a film mainly composed of an inorganic material, an organic-inorganic hybrid is used. A material having both organic and inorganic properties such as a material is preferably used.

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

  Further, in the present invention, a stress relaxation layer made of resin or the like on the support, a smoothing layer for smoothing the surface of the resin support, a bleed-out prevention layer for preventing bleed-out from the resin support, etc. May be provided separately.

(Smooth layer)
The smooth layer on the support flattens the rough surface of the transparent resin film support on which protrusions and the like exist, or fills irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions on the transparent resin film support. Provided for flattening. 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.

  The composition of the photosensitive resin may contain a photopolymerization initiator.

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

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

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

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

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

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

  Moreover, as a photosensitive resin, what adjusted solid content by mixing a general purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle size of the reactive silica particles is preferably 0.001 μm to 0.1 μm. By making the average particle diameter in such a range, by using it in combination with a matting agent composed of inorganic particles having an average particle diameter of 1 μm to 10 μm, which will be described later, optical properties satisfying a good balance between anti-glare properties and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties.

  Further, it is more preferable to use an average particle size of 0.001 μm to 0.01 μm.

  Improves adhesion between the smooth layer and the gas barrier layer, prevents bending of the base material, prevents cracks when heat-treated, and provides optical properties such as transparency and refractive index of the gas barrier film From the viewpoint of maintaining good physical properties, the smooth layer preferably contains the inorganic particles as described above in a mass ratio of 20% to 60%.

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

  Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxysilyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl 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.

  As the thickness of the smooth layer used in the present invention, the smoothness of the support is improved, and the balance of the optical properties of the support is easily adjusted, and the smooth layer is provided only on one surface of the support. From the viewpoint of preventing curling of the smooth film in the case, the range of 1 μm to 10 μm is preferable, and the range of 2 μm to 7 μm is more preferable.

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

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

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

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

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the bleed-out prevention layer. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

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

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

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

  The thickness of the bleed-out prevention layer improves the heat resistance of the support, makes it easier to adjust the balance of the optical properties of the support, and the bleed-out prevention layer is provided only on one side of the substrate. From the viewpoint of preventing the support from curling, a range of 1 to 10 μm is preferable, and a range of 2 to 7 μm is more preferable.

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

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

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

Here, “transparent” means that the light transmittance of visible light (400 nm to 700 nm) is 80% or more.
That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the support is used as an anode, a porous semiconductor layer is provided thereon, and a cathode made of a metal film is prepared to produce an organic photoelectric conversion element. The organic photoelectric conversion element can be sealed by stacking a stop material (although it may be the same), adhering the gas barrier film support and the periphery, and encapsulating the element. The influence on the element due to can be sealed.

The resin support for organic photoelectric conversion elements is obtained by producing a transparent conductive film on the gas barrier layer (also simply referred to as a barrier layer) of the gas barrier film produced in this manner. The transparent conductive film can be produced by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.
As a film thickness of a transparent conductive film, the range of 0.1 nm-1000 nm is preferable.
Next, an organic photoelectric conversion element using these gas barrier films and a resin support for an organic photoelectric conversion element on which a transparent conductive film is produced will be described.

[Sealing film and manufacturing method thereof]
In the present invention, a gas barrier film having the gas barrier layer (also simply referred to as a barrier layer) is preferably used as the substrate.
In the gas barrier film having the barrier layer, a transparent conductive film is further formed on the barrier layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated on the transparent conductive film. Further, another gas barrier film is sealed as a sealing film by overlapping.

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

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

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

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

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

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

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

[Preferred embodiment of sealing of organic photoelectric conversion element]
The preferable aspect of sealing used for the organic photoelectric conversion element which is one of the organic electronic devices of this invention is demonstrated.
As an example of production of the organic photoelectric conversion device according to the present invention, a transparent conductive film is formed on the gas barrier film of the present invention having a barrier layer, and each layer of the organic photoelectric conversion device is formed on the resin support for the organic photoelectric conversion device. After the formation, the organic photoelectric conversion element can be sealed using the sealing film so as to cover the cathode surface with the sealing film in an environment purged with an inert gas.

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

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

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

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 μm to 2.5 μm. However, if the amount of adhesive applied is too large, tunneling, leaching, crimping, etc. may occur, so the amount of adhesive is preferably adjusted to 3 μm to 5 μm in dry film thickness. It is preferable to do.

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

The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 μm to 50 μm. As a resin used for the extrusion laminate, LDPE, EVA, PP, etc. are generally used.
Next, each layer (constituent layer) of the organic photoelectric conversion element material constituting the organic photoelectric conversion element will be described.

[Configuration of organic photoelectric conversion element and solar cell]
Although the preferable aspect of an organic photoelectric conversion element and a solar cell is demonstrated as an example of the electronic device which concerns on this invention, this invention is not limited to these.
In addition, although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated in detail hereafter, the solar cell which concerns on this invention has the organic photoelectric conversion element which concerns on this invention as the structure, and is preferable of a solar cell. The configuration can be similarly described.

The organic photoelectric conversion element is not particularly limited, and has at least one anode and cathode, and a power generation layer (also referred to as a p-type semiconductor and n-type semiconductor mixed layer, a bulk heterojunction layer, or an i layer) sandwiched therebetween. Any element that has more than one layer and generates current when irradiated with light may be used.
The preferable specific example of the layer structure of an organic photoelectric conversion element (The preferable layer structure of a solar cell is also the same) is shown below.
(I) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, and even if these layers form a heterojunction with substantially two layers. Alternatively, a bulk heterojunction in a mixed state in one layer may be manufactured, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.
Like the organic EL element, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer. Therefore, the structure having them ((ii), ( iii)) is preferred. Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (iv). A configuration (also referred to as a pin configuration) may be used. Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

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

Furthermore, the preferable aspect of the organic photoelectric conversion element which concerns on detailed this invention is demonstrated below.
FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element.
In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a bulk heterojunction power generation layer 14, an electron transport layer 18, and a cathode 13 in this order on one surface of a substrate 11. Are stacked.

  The substrate 11 is a member that holds the anode 12, the hole transport layer 17, the power generation layer 14, the electron transport layer 18, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction organic photoelectric conversion element 10 may be configured by forming the anode 12 and the cathode 13 on both surfaces of the power generation layer 14.

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

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

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

Although not shown in FIG. 1, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.
As a more preferable configuration, the power generation layer 14 has a so-called p-i-n three-layer configuration (FIG. 2). A normal bulk heterojunction layer is a single i layer (14i) in which a p-type semiconductor material and an n-type semiconductor layer are mixed. However, a p-layer (14p) made of a single p-type semiconductor material and a single n-type semiconductor material. By sandwiching between n layers (14n), the rectification of holes and electrons becomes higher, loss due to charge-separated hole-electron recombination is reduced, and higher photoelectric conversion efficiency can be obtained.

Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency).
FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second power generation layer 16, and then the counter electrode 13 are stacked. By stacking, a tandem structure can be obtained. The second power generation layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first power generation layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. Further, both the first power generation layer 14 ′ and the second power generation layer 16 may have the above-described three-layer structure of pin.
Below, the material which comprises these layers is described.

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

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

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, 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 as described in U.S. Pat. No. 2003/136964, J. Pat. Amer. Chem. Soc. , Vol127. No. 14.4986, J. Am. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

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

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

Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process is possible and that can produce a crystalline thin film and achieve high mobility after drying is preferable.
In addition, when the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .

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

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

  However, fullerene derivatives that can perform charge separation efficiently with various p-type semiconductor materials at high speed (˜50 fs) are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), 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. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. It is preferable to produce a coating film in the lower layer before producing the bulk heterojunction layer because it has the effect of leveling the application surface and reduces the influence of leakage and the like.

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

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

Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable.

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

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

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

(Counter electrode (second electrode))
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used.

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

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

The counter electrode can be produced by producing a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.
If a metal material is used as the conductive material of the counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer, and more photoelectric conversion is performed. Efficiency is improved and preferable.

Further, the counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a conductive fiber, a nanowire, or a nanostructure. A dispersion of nanowires is preferable because a transparent and highly conductive counter electrode can be produced by a coating method.
Moreover, when making the counter electrode side light-transmitting, for example, after forming a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound in a thin film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

(Intermediate electrode)
In addition, the material of the intermediate electrode required in the case of the tandem configuration as in (v) (or FIG. 3) is preferably a layer using a compound having both transparency and conductivity. Materials such as ITO, AZO, FTO, transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or nanoparticles / nanowires, layers containing conductive fibers, PEDOT: PSS, conductive polymer materials such as polyaniline, etc.) can be used.
In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately stacking them. Is preferable.

(Metal nanowires)
In the present invention, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used as the conductive fibers, but metal nanowires are preferred.
In general, a metal nanowire refers to a linear structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a linear structure having a diameter of nm size.

  As a metal nanowire, in order to produce a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 μm to 500 μm. In particular, the thickness is preferably 3 μm to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less.

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

  The metal composition of the metal nanowire is not particularly limited, and can be composed of one or more metals such as a noble metal element and a base metal element. Osmium etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity.

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

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

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

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

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

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

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

As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.
Examples of the light diffusion layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

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

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

After application, it is preferable to perform heating in order to cause removal of residual solvent, moisture, and gas and increase mobility and absorption longwave by crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
The power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be manufactured by using a material that can be insolubilized after coating as described above.

(Patterning)
In the present invention, the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like are not particularly limited, and known methods can be appropriately applied.
If it is a soluble material such as a bulk heterojunction layer 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, etching or lift-off. Alternatively, the pattern may be produced by transferring a pattern produced on another substrate.

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

Example 1
As described below, a first stress relaxation layer is formed on a resin base material (a second stress relaxation layer is further formed), a barrier layer is further formed thereon, and a protective layer is further formed thereon. By forming, the gas barrier films 1-14 of this invention were produced. 4 and 5 are cross-sectional views showing the configuration. In the figure, 4 represents a support, 3 represents a first stress relaxation layer, 3-2 represents a second stress relaxation layer, 2 represents a barrier layer, and 1 represents a protective layer.

<< Production of Gas Barrier Film 1 >>
[Production of resin base material]
(Support)
As a support, a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) with easy-adhesion processing on both sides is annealed at 170 ° C. for 30 minutes, and then a smooth layer is formed on the surface of the polyester film. (Omitted in FIGS. 4 and 5) used was provided with a bleed-out prevention layer (omitted in FIGS. 4 and 5) on the back side.

(Formation of smooth layer)
On the surface side of the polyester film, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied and applied with a wire bar so that the film thickness after drying was 4 μm. After drying for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing was performed under a curing condition of 1.0 J / cm ² to form a smooth layer (clear hard coat layer: CHC layer).

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

(Stress relaxation layer)
(Formation of first stress relaxation layer)
A first stress relaxation layer in the gas barrier film 1 was formed on the smooth layer side of the substrate by an atmospheric pressure plasma method (AGP method).
The first stress relaxation layer was formed under the following thin film forming conditions using an atmospheric pressure plasma film forming apparatus (described in FIG. 3 of JP 2008-56967 A, a roll-to-roll atmospheric pressure plasma CVD apparatus).
At this time, the film formation rate was adjusted to 0.5 nm / second.
(Mixed gas composition)
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
(Deposition conditions)
<First electrode side>
Power supply type: HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency: 100kHz
Output density: 10 W / cm ²
Electrode temperature: 120 ° C
<Second electrode side>
Power supply type: Pearl Industry 13.56MHz CF-5000-13M
Frequency: 13.56MHz
Output density: 10 W / cm ²
Electrode temperature: 90 ° C

(Relative etching rate of the first stress relaxation layer)
The actual film thickness of the first stress relaxation layer in the gas barrier film 1 was confirmed to be approximately 120 nm from a cross-sectional photograph of a TEM (Transmission Electron Microscope).
In addition, by combining the sputtering method and XPS surface analysis, while confirming each atomic composition ratio in the depth direction of the film thickness, sputtering was performed at a rate (etching rate) of 5 nm / min in terms of SiO ₂ thermal oxide film. Since the film thickness considered to be the stress relaxation layer of 1 was 125 nm (SiO ₂ thermal oxide film conversion value), the etching rate was determined to be 5.2 nm / min. Therefore, the relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 1 was determined to be 1.0.

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

[Barrier layer]
(Formation of barrier layer)
Next, a barrier layer was formed on the first stress relaxation layer by the following steps (a) and (b).

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

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

<Vacuum ultraviolet (VUV light) irradiation treatment conditions>
The irradiation conditions of vacuum ultraviolet rays (VUV light) were set and irradiated using the following apparatus so that the distance between the lamp and the sample (also referred to as Gap) was 3 mm. The irradiation time was changed by adjusting the movable speed of the movable stage.
In addition, the oxygen concentration during irradiation with vacuum ultraviolet rays (VUV light) is adjusted by measuring the flow rate of nitrogen gas and oxygen gas introduced into the irradiation chamber with a flow meter, and nitrogen gas / oxygen gas of the gas introduced into the chamber. The flow rate ratio was adjusted.
Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm ²
Stage temperature: 100 ° C
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1%
Stage moving speed: 10 times at 10mm / sec

(Relative etching rate of barrier layer)
When the relative etching rate (relative ER) of the barrier layer was determined in the same manner as the relative etching rate in the first stress relaxation layer, it was 1.4. At this time, the atomic composition of the entire region of the barrier layer is confirmed to be not constant in the depth direction by XPS surface analysis, and is obtained as an average relative etching rate of the barrier layer having various atomic compositions. ing.

[Protective layer]
(Formation of protective layer)
A gas barrier film 1 of the present invention was produced by forming a protective layer in the gas barrier film 1 on the barrier layer by the atmospheric pressure plasma method (AGP method) similar to that of the first stress relaxation layer.

(Mixed gas composition)
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Hexamethyldisiloxane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
(Relative etching rate of protective layer)
When the relative etching rate (relative ER) of the protective layer was determined in the same manner as the relative etching rate in the first stress relaxation layer, it was 2.0.

<< Production of Gas Barrier Film 2 >>
The production of the gas barrier film 1 is the same except that the film forming rate is adjusted to 0.7 nm / second when forming the first stress relaxation layer by the atmospheric pressure plasma method (AGP method). Thus, the gas barrier film 2 of the present invention was produced.
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 2 was determined to be 1.1.

<< Production of Gas Barrier Film 3 >>
The production of the gas barrier film 1 is the same except that the film forming rate when the first stress relaxation layer is formed is adjusted to 1.2 nm / second by the atmospheric pressure plasma method (AGP method). Thus, the gas barrier film 3 of the present invention was produced.
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 3 was determined to be 1.5.

<< Production of Gas Barrier Film 4 >>
In the production of the gas barrier film 1, the thin film forming gas (raw material gas) for forming the first stress relaxation layer by the atmospheric pressure plasma method (AGP method) is changed from tetraethoxysilane to hexamethyldisiloxane. A gas barrier film 4 of the present invention was produced in the same manner except that the film speed was adjusted to 10 nm / second.
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 4 was determined to be 2.0.

<< Production of Gas Barrier Film 5 >>
In the production of the gas barrier film 1, the gas barrier film 5 of the present invention was produced in the same manner except that the first stress relaxation layer was formed by a vacuum plasma CVD method instead of the atmospheric pressure plasma method (AGP method). .

(Formation of first stress relaxation layer)
The 1st stress relaxation layer of this invention was formed on the base material using the vacuum plasma CVD apparatus.
(Deposition conditions)
High frequency power supply: 27.12 MHz
Distance between electrodes: 20mm
Film substrate temperature: 100 ° C
Gas pressure: 200Pa
(Raw material gas)
Argon gas flow rate: 150 sccm
Silane gas flow rate: 7.5 sccm
Nitrous oxide gas flow rate: 130sccm
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 5 was determined to be 2.0.

<< Production of Gas Barrier Film 6 >>
In producing the gas barrier film 1, the gas barrier film 6 of the present invention was produced in the same manner except that the first stress relaxation layer was formed by sputtering instead of the atmospheric pressure plasma method (AGP method).

(Formation of first stress relaxation layer)
The 1st stress relaxation layer of this invention was formed on the base material by RF magnetron sputtering method.
(Deposition conditions)
Film substrate temperature: Room temperature Inert gas: Argon gas Target: Silicon dioxide The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 6 was determined to be 2.5.

<< Production of Gas Barrier Film 7 >>
In the production of the gas barrier film 1, the gas barrier film 7 of the present invention was produced in the same manner except that the first stress relaxation layer was formed by a vacuum deposition method instead of the atmospheric pressure plasma method (AGP method).
(Formation of first stress relaxation layer)
The 1st stress relaxation layer of this invention was formed on the base material using the vacuum evaporation system.
(Deposition conditions)
Film substrate temperature: 60 ° C
Degree of vacuum: 4 × 10 ⁻⁶ Pa
Deposition source: silicon dioxide The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 7 was determined to be 3.0.

<< Production of Gas Barrier Film 8 >>
In the production of the gas barrier film 3, the stage movable speed, which is one of the modification conditions (VUV light irradiation treatment conditions) of the barrier layer, is changed from “10 times transport at 10 mm / second” to “4 times transport at 10 mm / second”. A gas barrier film 8 of the present invention was produced in the same manner except for the change.
The relative etching rate (relative ER) of the barrier layer in the gas barrier film 8 was determined to be 2.5.

<< Production of Gas Barrier Film 9 >>
In the production of the gas barrier film 3, the present invention is similarly applied except that the oxygen concentration in the processing environment, which is one of the conditions for modifying the barrier layer (VUV light irradiation processing conditions), is changed from 0.1% to 1%. A gas barrier film 9 was prepared.
The relative etching rate (relative ER) of the barrier layer in the gas barrier film 9 was determined to be 1.1.

<< Production of Gas Barrier Film 10 >>
In the production of the gas barrier film 3, the gas barrier film 10 of the present invention was similarly produced except that the protective layer in the gas barrier film 10 was formed under the same conditions as the first stress relaxation layer in the gas barrier film 1. Was made.
The relative etching rate (relative ER) of the protective layer in the gas barrier film 10 was determined to be 1.0.

<< Production of Gas Barrier Film 11 >>
In the production of the gas barrier film 3, the gas barrier film 11 of the present invention was produced in the same manner except that the protective layer was formed as follows.
(Formation of protective layer)
A 10: 1 mixture of Grasca HPC7003 (main agent) and HPC404H (curing accelerator) (manufactured by JSR) was applied on the barrier layer under the condition that the film thickness after drying was about 600 nm, and then at 80 ° C. for 10 minutes. After drying, the protective layer in the gas barrier film 11 was formed by processing under the same VUV light irradiation conditions as the barrier layer modification process in the gas barrier film 8.
The relative etching rate (relative ER) of the protective layer in the gas barrier film 11 was determined to be 3.0.

<< Production of Gas Barrier Film 12 >>
In the production of the gas barrier film 4, a second stress relaxation layer is further formed on the first stress relaxation layer under the same conditions as the first stress relaxation layer in the gas barrier film 1 (however, the gas barrier film The gas barrier film 12 of the present invention was produced in the same manner except that the thickness of the second stress relaxation layer in No. 12 was about 20 nm.
The relative etching rate (relative ER) of the second stress relaxation layer in the gas barrier film 12 was determined to be 1.0.

<< Production of Gas Barrier Film 13 >>
The production of the gas barrier film 12 is the same as that except that the film forming rate is adjusted to 1.0 nm / second when the second stress relaxation layer is formed by the atmospheric pressure plasma method (AGP method). Thus, the gas barrier film 13 of the present invention was produced.
The relative etching rate (relative ER) of the second stress relaxation layer in the gas barrier film 13 was determined to be 1.4.

<< Production of Gas Barrier Film 14 >>
The production of the gas barrier film 12 is the same except that the film forming rate is adjusted to 1.2 nm / second when the second stress relaxation layer is formed by the atmospheric pressure plasma method (AGP method). Thus, the gas barrier film 14 of the present invention was produced.
The relative etching rate (relative ER) of the second stress relaxation layer in the gas barrier film 14 was determined to be 1.5.

<< Production of Gas Barrier Film 15 >>
In the production of the gas barrier film 12, the gas barrier film 15 of the present invention was produced in the same manner except that the first stress relaxation layer was formed under the same conditions as the first stress relaxation layer in the gas barrier film 3. did.
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 15 was determined to be 1.5.

<< Production of Gas Barrier Film 16 >>
In the production of the gas barrier film 12, the gas barrier film 16 of the present invention was produced in the same manner except that the first stress relaxation layer was formed under the same conditions as the first stress relaxation layer in the gas barrier film 7. did.
The relative etching rate (relative ER) of the first stress relaxation layer in the gas barrier film 16 was determined to be 3.0.

<< Production of Comparative Film 17 >>
In the production of the gas barrier film 1 of the present invention, a comparative film 17 was produced in the same manner except that the first stress relaxation layer and the protective layer were not formed.

<< Production of Comparative Film 18 >>
In the production of the gas barrier film 3 of the present invention, a comparative film 18 was produced in the same manner except that the protective layer was not formed.

<< Production of Comparative Film 19 >>
In the production of the comparative film 18, a comparative film 19 was produced in the same manner except that the barrier layer was formed as follows.
(Formation of barrier layer)
The dried perhydropolysilazane-containing layer is treated for 5 minutes at 80 ° C. under a humidity of 90% RH, and further dried in a vacuum oven at 100 ° C. for 8 hours, whereby the polysilazane is a film mainly composed of silicon oxide. A layer converted to was formed.
The relative etching rate (relative ER) of the barrier layer in the comparative film 19 was determined to be 1.0.

<< Production of Comparative Film 20 >>
In the production of the comparative film 19, a comparative film 20 was produced in the same manner as in the gas barrier film 1 of the present invention except that a protective layer was further provided.

<< Production of Comparative Film 21 >>
In the production of the gas barrier film 1 of the present invention, a comparative film 21 was produced in the same manner except that the first stress relaxation layer was formed as follows.
(Formation of first stress relaxation layer)
A first stress relaxation layer made of a diamond-like carbon (DLC) thin film was formed using a vacuum plasma CVD apparatus.
(Deposition conditions)
Film substrate temperature: 100 ° C
Inert gas: Argon gas Source gas: Acetylene gas The relative etching rate (relative ER) of the barrier layer in the comparative film 21 was determined to be 0.9.

<< Production of Comparative Film 22 >>
In the production of the gas barrier film 7 of the present invention, the relative etching rate (relative ER) of the first stress relaxation layer is 3 by adjusting the conditions for forming the first stress relaxation layer by vacuum deposition. A comparative film 22 was produced in the same manner except that the film was formed to have a thickness of 5.

<< Production of Comparative Film 23 >>
In the production of the gas barrier film 8 of the present invention, the stage moving speed, which is one of the conditions for modifying the barrier layer (VUV light irradiation treatment conditions), is transferred from “4 times transport at 10 mm / second” to “3 times at 10 mm / second”. A comparative film 23 was produced in the same manner except that it was changed to "".
The relative etching rate (relative ER) of the barrier layer in the comparative film 23 was determined to be 2.6.

<< Production of Comparative Film 24 >>
A comparative film 24 was produced in the same manner as in the production of the gas barrier film 3 of the present invention, except that the protective layer was formed in the same manner as the first stress relaxation layer in the comparative film 21.

<< Production of Comparative Film 25 >>
In the production of the gas barrier film 3 of the present invention, a comparative film 25 was produced in the same manner except that the protective layer was formed in the same manner as the first stress relaxation layer in the comparative film 22.

<< Evaluation of water vapor transmission rate (WVTR) characteristics of gas barrier film >>
[Evaluation 1: Evaluation of bending resistance (60 ° C., 90% RH)]
For the gas barrier films 1 to 16 of the present invention and the comparative films 17 to 25, in order to confirm the change in gas barrier properties before and after bending, the film is bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm in advance. For the gas barrier film subjected to the process of repeating the above and the gas barrier film not subjected to the above bending process, the water vapor transmission rate (WVTR) is measured according to the method described below, and the four-level rank evaluation is performed as shown below. The gas barrier properties were evaluated.

(Measurement device of water vapor transmission rate)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)

(Preparation of vapor barrier evaluation cell)
Using a vacuum vapor deposition apparatus (JEOL-made vacuum vapor deposition apparatus JEE-400), except for each film (gas barrier film 1-16, comparative film 17-25) the part (12 mm x 12 mm 9 places) which wants to vapor-deposit. Masked and vapor deposited metallic calcium.
Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample with both sides sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity, and moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount was calculated.
At this time, in the present invention, the WVTR obtained from the corrosion rate until the corrosion area of the cell reaches 1% is 1% WVTR, and the corrosion area is 100%, that is, the WVTR obtained from the corrosion rate until full corrosion occurs. It will be called 100% WVTR (also called average WVTR).
(Rank evaluation)
4: Less than 1 × 10 ⁻³ g / m ² / day 3: 1 × 10 ⁻³ g / m ² / day or more and less than 3 × 10 ⁻³ g / m ² / day 2: 3 × 10 ⁻³ g / day m ² / day or more, less than 1 × 10 ⁻¹ g / m ² / day 1: 1 × 10 ⁻¹ g / m ² / day or more

[Evaluation 2: Evaluation of resistance to high temperature and high humidity]
The obtained films 1 to 25 were stored in a high-temperature and high-humidity tank (constant temperature and humidity oven: Yamato Humidic Chamber IG47M) adjusted to 60 ° C. and 90% RH for 100 hours, and then evaluated 1 In the same manner, the water vapor transmission rate was measured with 100% WVTR, and the same rank evaluation was performed. When this evaluation item is good, it indicates that the heat resistance is high.

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

Similar to Evaluations 1 and 2, the following three ranks were evaluated.
However, in the present invention, the WVTR obtained from the corrosion rate until the corrosion area of the cell reaches 30% is referred to as 30% WVTR.
(Rank evaluation)
3: 1% WVTR is less than 3 × 10 ⁻³ g / m ² / day, and 100% WVTR / 30% WVTR is less than 10. 2: 1% WVTR is less than 3 × 10 ⁻³ g / m ² / day. And 100% WVTR / 30% WVTR is 10 or more and 100 or less 1: 1% WVTR is 3 × 10 ⁻³ g / m ² / day or more, and 100% WVTR / 30% WVTR is 100 or more.

<Evaluation of curl resistance of gas barrier film>
The gas barrier films 1 to 16 of the present invention and the comparative films 17 to 25 were evaluated for the maximum degree of deformation of the base material before and after the water washing treatment.
The maximum degree of deformation of the substrate is
The maximum degree of deformation of the substrate = the amount of deformation of the film after the washing treatment−the amount of deformation of the initial film.
The amount of deformation of the film was determined from the maximum value of the distance between the apex floating from the table by curling the film while the 10 cm × 10 cm film was allowed to stand on a flat table.
As shown below, four-level rank evaluation was performed to evaluate curl resistance.
(Rank evaluation)
4: Deformation degree of the substrate is 0 mm or more and less than 2 mm 3: Deformation degree of the substrate is 2 mm or more and less than 3 mm 2: Deformation degree of the substrate is 3 mm or more and less than 10 mm 1: Deformation degree of the substrate is obtained by 10 mm or more The results are shown in Table 1.

  As is apparent from the results shown in Table 1, each of the gas barrier films 1 to 16 of the present invention has a high gas barrier property (low water vapor permeability) compared to the comparative gas barrier films 17 to 25, and the gas barrier layer Sudden deterioration is suppressed, excellent barrier properties are maintained even when stored at high temperature and high humidity (time stability), and flexibility (cracking resistance) and curl resistance (element fabrication process resistance) are also excellent. Is clear.

Example 2
<< Production of Organic Photoelectric Conversion Elements 1-25 >>
150 nm of indium tin oxide (ITO) transparent conductive film deposited on the gas barrier films 1 to 16 of the present invention prepared in Example 1 and comparative films 17 to 25 (sheet resistance 10Ω / □) (conductive film) The first electrode was fabricated by patterning the film that had been heat-treated before formation) into a width of 2 mm using a normal photolithography technique and wet etching.
The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. .

Thereafter, the substrate was brought into a nitrogen chamber and manufactured in a nitrogen atmosphere.
First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Co., Ltd .: 6,6-phenyl-C61-butyric acid methyl ester) are added to 3.0% by mass of chlorobenzene. A liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at room temperature and dried. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.
Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed.

Each obtained organic photoelectric conversion element is moved to a nitrogen chamber, and sealing is performed using a sealing cap and a UV curable resin, thereby producing organic photoelectric conversion elements 1 to 25 having a light receiving portion of 2 × 2 mm size. did.
Subsequently, the gas barrier film sample for sealing and the organic photoelectric conversion element were sealed according to the following method.
In an environment purged with nitrogen gas (inert gas), each of two gas barrier films 1 to 25 is used, and an epoxy-based photocurable adhesive is applied as a sealing material to the surface provided with the gas barrier layer. Each of the corresponding organic photoelectric conversion elements 1 to 25 was produced as a sealing film 1 to 25.

  Next, the organic photoelectric conversion elements 1 to 25 are sandwiched and adhered between the adhesive application surfaces of the two gas barrier film samples coated with the adhesive, and then irradiated with UV light from one substrate side. Then, the organic photoelectric conversion elements 1 to 25 were sealed to obtain the organic photoelectric conversion elements 1 to 16 of the present invention and comparative organic photoelectric conversion elements 17 to 25.

<< Production of solar cells and evaluation of energy conversion efficiency >>
Evaluation of the organic photoelectric conversion elements 1 to 16 obtained above and the comparative organic photoelectric conversion elements 17 to 25 is performed by using the respective elements to produce solar cells 1 to 16 and comparative solar cells 17 to 25, respectively. The energy conversion efficiency was obtained, and the durability as an element was evaluated for each.
In addition, each evaluation of the organic photoelectric conversion elements 1-16 and the comparative organic photoelectric conversion elements 17-25 irradiates the light of the intensity | strength of 100 mW / cm < ² > of a solar simulator (AM1.5G filter), and the effective area is 4 A mask having a thickness of 0.0 mm ² was placed on the light receiving portion, and the IV characteristics of the solar cells 1 to 16 and the comparative solar cells 17 to 25 were evaluated.

Specifically, the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%) were measured for each of the four light receiving portions formed on the element, and according to the following formula 1. A four-point average value of the obtained energy conversion efficiency PCE (%) was estimated.
Formula 1
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as an initial battery characteristic obtained was measured, and the degree of deterioration over time was measured as the conversion efficiency remaining rate after the forced deterioration test stored for 2000 hours in a temperature 60 ° C., humidity 90% RH environment. It calculated | required as ratio of the conversion efficiency after a test / initial conversion efficiency, and durability was evaluated according to the following reference | standard (OPV element performance).
3: The conversion efficiency remaining rate is 70% or more 2: The conversion efficiency remaining rate is 40% or more and less than 70% 1: The conversion efficiency remaining rate is less than 40%. is there.
The obtained results are shown in Table 1.

  As is clear from the results shown in Table 1, the organic photovoltaics prepared using the gas barrier film of the present invention for the comparative solar cells 17 to 25 provided with the organic photoelectric conversion elements 17 to 25 prepared using the comparative film. It turned out that the solar cells 1-16 of this invention provided with the conversion elements 1-16 show very high durability also in the very severe environment (high temperature, high humidity conditions) of 60 degreeC and 90% RH.

DESCRIPTION OF SYMBOLS 1 Protective layer 2 Barrier layer 3 1st stress relaxation layer 3-2 2nd stress relaxation layer 4 Resin base material 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Anode 13 Cathode 14 Power generation layer 14 ′ First power generation Layer 14i i layer in which p-type semiconductor material and n-type semiconductor layer are mixed 14p p layer made of p-type semiconductor material alone 14n n layer made of n-type semiconductor material 15 charge recombination layer 16 second power generation layer 17 hole Transport layer 18 Electron transport layer

Claims (8)

When the etching rate of the thermal oxidation film of polysilazane is 1.0 on the basis of the relative etching rate when etching on the resin substrate in the film thickness direction by sputtering, 1) 1.0 or more and 3.0 or less A first stress relaxation layer made of a vapor-deposited film, 2) a barrier layer obtained by modifying a coating film containing polysilazane that is 1.1 to 2.5, and 3) 1.0 to 3 and a protective layer is 2.0 or less possess in this order,
The thermal oxidation film of the polysilazane is a 20 mass% dibutyl ether solution of perhydropolysilazane (PHPS), AQUAMICA NN120-20 manufactured by AZ Electronic Materials Co., Ltd., and an amine catalyst (N, N, N ′, N ′). -By mixing with NAX120-20 containing 5% by mass of tetramethyl-1,6-diaminohexane), the amine catalyst content becomes 1.0% by mass with respect to the perhydropolysilazane (PHPS) concentration. After adjusting so that the coating film was applied by spin coating using a solution diluted to 10% by mass with a dibutyl ether solvent, the resulting coating film was dried at 80 ° C. for 1 minute, and after drying, a film thickness of 150 nm was obtained. A hydropolysilazane-containing layer was prepared, and the perhydropolysilazane-containing layer after drying was treated at 80 ° C. for 5 minutes under a humidity of 90% RH. A gas barrier film characterized in that it is a layer in which polysilazane is converted into a film mainly composed of silicon oxide by further drying in a vacuum oven at 100 ° C. for 8 hours .   The relative etching rate of the first stress relaxation layer is 1.5 or more and 3.0 or less, and the relative etching rate in contact with the first stress relaxation layer and the barrier layer is 1.0 or more and 1.4. The gas barrier film according to claim 1, comprising a second stress relaxation layer which is the following. When the etching rate of the thermal oxidation film of polysilazane is 1.0 on the basis of the relative etching rate when etching on the resin substrate in the film thickness direction by sputtering, 1) 1.0 or more and 3.0 or less A step of forming the first stress relaxation layer by vapor deposition, and 2) a step of forming a barrier layer of 1.1 to 2.5 by modifying the coating film containing polysilazane, 3) a step of forming a protective layer is 1.0 to 3.0 possess in this order,
The thermal oxidation film of the polysilazane is a 20 mass% dibutyl ether solution of perhydropolysilazane (PHPS), AQUAMICA NN120-20 manufactured by AZ Electronic Materials Co., Ltd., and an amine catalyst (N, N, N ′, N ′). -By mixing with NAX120-20 containing 5% by mass of tetramethyl-1,6-diaminohexane), the amine catalyst content becomes 1.0% by mass with respect to the perhydropolysilazane (PHPS) concentration. After adjusting so that the coating film was applied by spin coating using a solution diluted to 10% by mass with a dibutyl ether solvent, the resulting coating film was dried at 80 ° C. for 1 minute, and after drying, a film thickness of 150 nm was obtained. A hydropolysilazane-containing layer was prepared, and the perhydropolysilazane-containing layer after drying was treated at 80 ° C. for 5 minutes under a humidity of 90% RH. Then, the manufacturing method of the gas-barrier film which is a layer by which polysilazane was converted into the film | membrane which has a silicon oxide as a main component by further drying in a 100 degreeC vacuum oven for 8 hours .   The relative etching rate of the first stress relaxation layer is 1.5 or more and 3.0 or less, and after the step of forming the first stress relaxation layer, the relative etching rate is 1.0 or more and 1. 4. The method for producing a gas barrier film according to claim 3, further comprising a step of forming a second stress relaxation layer of 4 or less by vapor deposition. In the manufacturing method of the gas-barrier film of Claim 3 or 4,
5. The gas barrier film according to claim 3, wherein a film formation rate during vapor deposition when forming the first or second stress relaxation layer is 0.1 nm / second to 30 nm / second. 6. Manufacturing method.   The method for producing a gas barrier film according to any one of claims 3 to 5, wherein the modification treatment of the coating film containing polysilazane is a vacuum ultraviolet ray irradiation treatment. Manufacturing method.   The method for producing a gas barrier film according to any one of claims 3 to 6, wherein the first or second stress relaxation layer is formed by a CVD method. Production method.   An organic electronic device sealed with the gas barrier film according to claim 1.

Images