JP5397064B2 - Method for producing antireflection layer and organic electronics element using antireflection layer - Google Patents

Description

  The present invention relates to a method for producing an antireflection layer comprising fine particles, and more specifically, after applying a fine particle dispersion to a resin substrate, by prompting the arrangement and fixation of fine particles by an external stimulus, not only the antireflection function, The present invention relates to a method for producing an antireflection layer composed of fine particles capable of improving the antifouling property and suppressing cracking due to bending.

  The main application fields are useful for various organic electronics elements, such as organic EL elements, organic solar cell elements, organic photoelectric conversion elements, display elements, etc., characterized by using a flexible and transparent resin substrate. In particular, the present invention is effective for an organic solar cell element exposed to sunlight.

  The antireflection film is the most basic in the optical field and is a structure used in various applications. In the display field where the technological progress is still continuing, and in the organic electronics field, which has recently attracted attention, there is a further need for a highly functional substrate having an antireflection function and other additional functions, particularly on a flexible transparent resin substrate.

  In the organic electronics field, for example, organic EL elements, organic solar cell elements, organic photoelectric conversion elements, etc., which are mainly composed of organic matter, there is a possibility of high productivity by coating and printing. It is especially noted as.

  In particular, organic solar cells can be formed on a flexible resin substrate by a coating method, and thus are actively studied by many research institutions. As an advantage of the coating method, since it can be produced by a continuous process such as roll-to-roll, the cost merit obtained by making it in large quantities is great. In addition, since it can be wound and stored in a roll shape, easy management in the process is a great merit for cost reduction.

  In many thin-film solar cells, since the power generation layer is a thin film, it has been found that a technology that effectively uses incident sunlight light directly contributes to high efficiency. As such a light incident loss, about 10% of the incident light may be reflected by the Fresnel loss due to the difference in refractive index on the surface of the base material (generally glass), and may not reach the power generation layer.

  In order to reduce the loss of light incidence, an antireflection layer is generally formed on the outermost surface, but many of them are coated with a low refractive index coating agent and dried from the viewpoint of cost effectiveness. In addition, the antireflection function is low and the antifouling property does not last, and if it is coated on a resin substrate, cracks are likely to occur due to bending, and as a flexible solar cell antireflection layer It was not preferable.

  As a useful method for controlling the refractive index, for example, an antireflection layer having a continuous refractive index change on a semiconductor substrate has been proposed as disclosed in Patent Document 1. Patent Document 2 discloses a method of forming a continuous refractive index change by laminating a high refractive index layer and a low refractive index layer using hollow silica on a resin base material. Similarly, Patent Document 3 introduces a technique for obtaining an antireflection function by fixing fine particles to a substrate surface.

  Any of these methods is a method for forming a continuous refractive index. For example, the antireflective layer made of fine particles is coated on the surface of the base material to change the refractive index and obtain an antireflection function. . However, the antireflection layer composed of fine particles is not a technique that achieves both high transmittance and antifouling properties because the fine particles themselves have no antifouling effect.

  On the other hand, Patent Document 4 discloses an antifouling layer comprising an ultrafine particle composite of a conductor and a dielectric or semiconductor. This is a technology that shows an antifouling effect by mixing amorphous titanium oxide that does not exhibit photocatalytic properties and a conductor, but when applied on a resin substrate as described above, the antifouling property is obtained. In addition, the antireflection function due to the formation of the fine particles is low, and cracks due to bending are generated, which causes practical problems when used in flexible solar cells.

JP 2005-277181 A JP 2005-183546 A JP 2006-208726 A WO05 / 108056 pamphlet

  In the conventional technology as described above, in particular, when an antireflection film made of fine particles is formed on a flexible resin substrate, since the high temperature process cannot be performed, the arrangement and fixing of the fine particles are insufficient, and thus the antireflection function is provided. Not only was it low, but the problem was deterioration of antifouling properties and generation of cracks due to bending.

  The present invention solves the above problems, and more specifically, a manufacturing method for obtaining an antireflection layer composed of fine particles, which has a high antireflection function and antifouling property and is less susceptible to cracking due to bending, by a low temperature process, and this reflection. An object of the present invention is to provide an organic electronic device using a prevention layer.

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

  1. A method for producing an antireflection layer comprising at least a step of applying a dispersion containing fine particles whose surface is peroxidized on at least one surface of a resin base material, and a step of fixing the fine particles by an external stimulus treatment .

  2. 2. The method for producing an antireflection layer as described in 1 above, wherein the dispersion contains at least a conductor and fine particles comprising a dielectric or a semiconductor.

  3. 3. The antireflection according to 1 or 2, wherein the dispersion contains at least fine particles made of a metal or metal oxide that absorbs microwaves, and the external stimulation treatment is a microwave irradiation treatment. Layer manufacturing method.

  4). 3. The method for producing an antireflection layer according to 1 or 2, wherein the external stimulation treatment is a treatment selected from plasma discharge treatment, microwave irradiation treatment, and ultraviolet irradiation treatment.

  5. 5. The method for producing an antireflection layer as described in 4 above, wherein the external stimulation treatment is a plasma discharge treatment performed in the presence of oxygen at atmospheric pressure or near atmospheric pressure.

  6). 5. The method for producing an antireflection layer as described in 4 above, wherein the external stimulation treatment is an ultraviolet irradiation treatment performed under conditions where the oxygen concentration in the atmosphere is 18% by volume or more and 50% by volume.

  7). 7. The method for producing an antireflection layer according to any one of 1 to 6, wherein the resin base material is a flexible base material.

  8). 8. An organic electronic device comprising an antireflection layer produced by the method for producing an antireflection layer according to any one of 1 to 7 above.

  9. 9. The organic electronics element as described in 8 above, wherein the antireflection layer is formed on both surfaces of the resin base material.

  According to the present invention, there are provided a manufacturing method for obtaining an antireflection layer composed of fine particles having a high antireflection function and antifouling property and less cracking due to bending by a low-temperature process, and an organic electronic device using the antireflection layer. I was able to.

1 is a schematic cross-sectional view of an atmospheric pressure plasma processing apparatus that can be used in the present invention. It is the schematic of the square tube type electrode of an atmospheric pressure plasma processing apparatus.

  As a result of intensive studies in view of the above problems, the present inventor fixed the fine particles by applying a dispersion liquid containing fine particles whose surface is peroxidized on at least one surface of the resin base material, and by external stimulation treatment. And a method for producing an antireflection layer comprising at least a process, and a method for obtaining an antireflection layer composed of fine particles having a high antireflection function and antifouling property and less cracking due to bending by a low temperature process. The present invention has been reached.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a method for producing an antireflection layer comprising fine particles, the step of applying a dispersion containing fine particles whose surface is peroxidized on at least one surface of a flexible substrate, and the peroxidation by external stimulation treatment. And a step of fixing the formed fine particles.

  When forming such an antireflection layer made of fine particles, an optimal porous structure is formed depending on the coating conditions, drying conditions, and external stimulus processing conditions, and the antireflection structure has an apparent continuous refractive index change. Is formed.

  Further, another effect of the present invention is imparting antifouling properties. The antireflection layer according to the present invention is preferably a composite containing at least a conductor and fine particles made of a dielectric or semiconductor. In this way, by combining a conductor and a dielectric or semiconductor, a positive charge is generated on the surface of the layer, so that the adhesion of contaminants is suppressed by electrostatic repulsion as described below, At the same time, when rain water or the like is applied, the contaminants can be easily washed away.

  Moreover, the organic solar cell which is one of the organic electronics elements using this antireflection layer improves the antireflection property of incident light and improves the photoelectric conversion efficiency.

  Contaminants that are one of the causes of discoloration or discoloration of the substrate surface are caused by the gradual deposition of inorganic substances such as carbon and / or organic substances such as oil floating on the substrate surface. Adhere.

  It is said that pollutants, especially oil, which are mainly floating in the outdoor air, are in an “oxidized” state due to the so-called photooxidation reaction caused by various electromagnetic waves including sunlight.

The photo-oxidation reaction is the action of electromagnetic waves such as sunlight, and water (H ₂ O) and oxygen (O ₂ ) on the surface of organic or inorganic matter to hydroxyl radical (.OH) and singlet oxygen ( ¹ O ₂ ). Is a phenomenon in which electrons (e ⁻ ) are extracted from an organic or inorganic substance and oxidized. Due to this oxidation, the molecular structure of the organic substance is changed, and a discoloration or embrittlement phenomenon called deterioration is observed, and rust is generated in the inorganic substance, particularly metal. These “oxidized” organic or inorganic surfaces are positively charged by the extraction of electrons (e ⁻ ).

[Fine particles]
The fine particles used in the antireflection layer composed of the fine particles of the present invention are fine particles having a particle diameter of 100 nm or less made of metal, metal salt, metal oxide, carbon material, silane material, compound semiconductor, organic conductive material, and the like. A particle diameter of preferably 1 to 50 nm is preferable because high transmittance can be obtained without light scattering. As the shape of the particles, any shape can be preferably used as long as the reflected light by light scattering is small, and shapes such as a sphere, an ellipse, a polygon, a rod, a wire, and a disk can be used. The refractive index is preferably about 1.1 to 2.5, more preferably about 1.1 to 2.0.

  In addition, the fine particles used in the present invention are characterized by having at least fine particles active on the external stimulus treatment whose surface is peroxidized. Fine particles can be fixed without damaging them.

  The method for peroxidizing the surface of the fine particles will be described later using titanium oxide fine particles as an example. The surface of fine particles other than titanium oxide can be peroxidized in the same manner.

  In the present invention, by applying a positive charge to the substrate surface, the organic substance or inorganic substance is naturally released from the substrate surface using electrostatic repulsion. As a method for imparting a positive charge to the substrate surface, in the present invention, it is preferable to use a composite of a conductor and a dielectric or semiconductor. The conductor constituting the composite is preferably a metal from the viewpoint of durability, such as aluminum, tin, cesium, indium, cerium, selenium chromium, nickel, antimony, iron, silver, copper, manganese, platinum, tungsten, zirconium, zinc, etc. These metals are mentioned.

(conductor)
A metal salt of some metals can also be used as the conductor. Specifically, aluminum chloride, first and second tin chlorides, chromium chloride, nickel chloride, first and second antimony chlorides, first and second iron chlorides, silver nitrate, cesium chloride, indium trichloride, first chloride chloride Various metal salts such as cerium, selenium tetrachloride, cupric chloride, manganese chloride, platinum chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, gold chloride, zirconium oxychloride, zinc chloride, etc. It can be illustrated. Further, hydroxides or oxides such as indium hydroxide and silicotungstic acid can also be used.

  As conductors, polyaniline, polypyrrole, polythiophene, polythiophene vinylon, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene vinylon, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyphenylene oxide Conductive polymers such as anthracene, polynaphthalene, polypyrene, and polyazulene can also be used.

(semiconductor)
Examples of the semiconductor include C, Si, Ge, Sn, GaAs, InP, GeN, ZnSe, and PbSnTe, and semiconductor metal oxide, photo semiconductor metal, and photo semiconductor metal oxide can also be used. Preferably, besides titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _2, etc. are used, and those in which the photocatalytic ability is inactivated with Na or the like are desirable.

(Dielectric)
As dielectrics, barium titanate (PZT), which is a ferroelectric material, so-called SBT, BLT, PLZT- (Pb, La) (Zr, Ti) O ₃ , SBT, SBTN-SrBi ₂ (Ta, Nb) described below. ) ₂ O ₉ , BST- (Ba, Sr) TiO ₃ , LSCO- (La, Sr) CoO ₃ , BLT, BIT- (Bi, La) ₄ Ti ₃ O ₁₂ , BSO-Bi ₂ SiO _5, etc. Can be used. Also, silane compounds, silicone compounds, so-called organic modified silica compounds, which are organosilicon compounds, organic polymer insulating films, arylene ether-based polymers, benzocyclobutene, fluorine-based polymer parylene N, or F, fluorinated amorphous carbon, etc. Various low dielectric materials can also be used.

As a composite of a conductor and a dielectric or semiconductor, any combination of conductor and dielectric or semiconductor can be used as long as it can impart a positive charge to the surface of the base. In terms of hydrophilization and self-cleaning, it is preferable to use metal-doped titanium oxide. The metal is preferably at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc, and the titanium oxide may be TiO ₂ , TiO ₃ , TiO, TiO ₃ / nH ₂ O, or the like. These various oxides and peroxides can be used. In particular, titanium peroxide having a peroxo group is preferable. The titanium oxide may be any of amorphous type, anatase type, brookite type, and rutile type, and these may be mixed, but amorphous type titanium oxide is preferred.

  Amorphous titanium oxide does not have a photocatalytic function. On the other hand, anatase-type, brookite-type and rutile-type titanium oxides have a photocatalytic function, but the photocatalytic function is lost when copper, manganese, nickel, cobalt, iron or zinc is combined at a certain concentration or more. Therefore, the metal-doped titanium oxide does not have a photocatalytic function. Amorphous titanium oxide is converted to anatase titanium oxide over time by heating with sunlight, etc., but when combined with copper, manganese, nickel, cobalt, iron, or zinc, anatase titanium oxide loses its photocatalytic function. Therefore, after all, the metal-doped titanium oxide does not exhibit a photocatalytic function over time.

  As a method for producing the metal-doped titanium oxide, a general method for producing titanium dioxide powder can be used. Moreover, the metal dope described above can be combined with an oxide in any process in the manufacturing stage.

(Method for producing fine particles of titanium oxide whose surface is peroxidized)
Although the preferable example of the manufacturing method of the titanium oxide microparticles | fine-particles whose surface is peroxidized is shown below, if the function mentioned above is acquired in this invention, a composition and manufacturing method of microparticles | fine-particles will not be restricted to this.

  First, a titanium hydroxide is formed by reacting a tetravalent titanium compound such as titanium tetrachloride with a base such as ammonia. Next, this titanium hydroxide is peroxo-oxidized with an oxidizing agent to form ultrafine particles of amorphous titanium peroxide. This reaction is preferably carried out in an aqueous medium. Furthermore, it is also possible to transfer to anatase-type titanium peroxide by arbitrary heat treatment. In any of the above steps, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.

  The peroxidation oxidizing agent is not particularly limited, and various agents can be used as long as they can form a titanium peroxo compound, that is, titanium peroxide, but hydrogen peroxide is preferred. When hydrogen peroxide is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but is preferably 30 to 40%. It is preferred to cool the titanium hydroxide before peroxolation. The cooling temperature at that time is preferably 1 to 5 ° C.

  The metal and titanium hydroxides thus obtained are washed with pure water, cooled to around 5 ° C., and then peroxoated with hydrogen peroxide. Thereby, an aqueous dispersion containing titanium oxide fine particles having amorphous peroxo groups doped with metal, that is, an aqueous dispersion containing metal-doped titanium oxide can be produced.

As the above-mentioned tetravalent titanium compound, various titanium compounds can be used as long as they can form titanium hydroxide also called orthotitanic acid (H ₄ TiO ₄ ) when reacted with a base. There are water-soluble inorganic acid salts of titanium such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate. In addition, water-soluble organic acid salts of titanium such as titanium oxalate can be used. Of these various titanium compounds, titanium tetrachloride is preferred because it is particularly excellent in water solubility and no components other than titanium remain in the dispersion of metal-doped titanium oxide.

  When a tetravalent titanium compound solution is used, the solution concentration is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution is preferable. Specifically, the solution concentration of the tetravalent titanium compound is preferably 10 to 0.01% by mass, more preferably 7 to 0.3% by mass.

  As the base to be reacted with the tetravalent titanium compound, various bases can be used as long as they can react with the tetravalent titanium compound to form titanium hydroxide, and include ammonia, caustic soda, sodium carbonate, Although caustic potash and the like can be exemplified, ammonia is most preferable.

  When the above base solution is used, the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution is preferable. Specifically, the concentration of the base solution is preferably 10 to 0.01% by mass, and more preferably 7 to 0.1% by mass.

  Further, as a different production method, a method using a sol-gel method can be mentioned. This is a mixture of titanium alkoxide and a solvent such as water and alcohol, an acid or a base catalyst, and the titanium alkoxide is hydrolyzed to produce a sol solution of ultrafine titanium oxide. Before or after the hydrolysis, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed. The titanium oxide thus obtained is an amorphous type having a peroxo group.

As the titanium alkoxide, a compound represented by the general formula: Ti (OR ′) ₄ (where R ′ is an alkyl group), or one or two alkoxide groups (OR ′) in the general formula is a carboxyl group. Alternatively, a compound substituted with a β-dicarbonyl group or a mixture thereof is preferable.

Specific examples of the titanium alkoxide include Ti (O-iso-C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (O—CH ₂ CH (C ₂ H ₅ ) C _{4. H 9) 4, Ti (O} -C 17 H 35) 4, Ti (O-iso-C 3 H 7) 2 [CO (CH 3) CHCOCH 3] 2, Ti (O-n-C 4 H 9) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ , Ti (OH) ₂ [OCH (CH ₃ ) COOH] ₂ , Ti (OCH ₂ CH (C ₂ H ₅ ) CH (OH) C _{3 H 7) 4, Ti (O} -n-C 4 H 9) 2 (OCOC 17 H 35) , and the like.

Examples of the above-mentioned compounds of copper, manganese, nickel, cobalt, iron or zinc include Ni compound: Ni (OH) ₂ , NiCl ₂ , Co compound: Co (OH) NO ₃ , Co (OH) ₂ , CoSO ₄ , CoCl ₂ , Cu compound: Cu (OH) ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ , Cu (CH ₃ COO) ₂ , Mn compound: MnNO ₃ , MnSO ₄ , MnCl ₂ , Fe compound: Fe ( _{OH) 2, Fe (OH)} 3, FeCl 3, Zn _{compounds: Zn (NO 3) 2,} ZnSO 4, can be cited ZnCl ₂ or the like.

  Moreover, 0.05-15 mass% is preferable with respect to the illustrated titanium peroxide density | concentration, and, as for content in the case of carrying out metal dope, 0.1-5 mass% is more preferable. Further, the blending amount of copper, manganese, nickel, cobalt, iron, and zinc is preferably 1: 1 from the present invention in terms of the molar ratio of titanium to the metal component, but 1: 0 from the stability of the aqueous dispersion. .01 to 1: 0.5 is preferable, and 1: 0.03 to 1: 0.1 is more preferable.

  The peroxidation treatment of the fine particle surface can be evaluated using an apparatus such as X-ray photoelectron spectroscopy (XPS) or Fourier transform infrared absorption spectrum (FT-IR). In addition, a tetrabutylammonium solution having a known concentration as a base agent is added to the fine particle dispersion, and the base agent is adsorbed on the surface of the fine particles, and then the amount of the base agent remaining in the solution is reduced with an acid agent such as perchloric acid. The amount of the peroxidation treatment can be evaluated from the surface area of fine particles identified by the titration method used and separately obtained (observation by TEM method, calculation by BET method or the like).

In the case of titanium oxide, 0.5 to 30 μmol / m ² is preferable from the viewpoint of reactivity due to external stimulation as a preferable amount of surface treatment with peroxide for the surface area of the fine particles.

(Formation of antireflection layer)
In the present invention, it is preferable to prepare a dispersion in which the prepared fine particles are dispersed in the presence of a surfactant or a dispersant, and form a film on the substrate in the coating step.

  Examples of the coating means include known coating methods such as spray coating, dip coating, flow coating, spin coating, and die coating, and screen printing, roll screen printing, offset printing, flexographic printing, gravure printing, inkjet printing, and the like. It can also be applied using any printing method.

  It is a feature of the present invention that after the coating film formation, the drying treatment is performed below the softening point of the substrate so as not to damage the substrate.

  The thickness of the coating film is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and particularly preferably 0.5 to 10 μm in terms of dry film thickness.

  As the surfactant or dispersant, various organosilicon compounds can be used. As the organosilicon compound, various silane compounds and various silicone oils, silicone rubbers, and silicone resins can be used. Those having an alkyl silicate structure or a polyether structure in the molecule, or having an alkyl silicate structure and a polyether structure. It is desirable to have both.

  Here, the alkyl silicate structure refers to a structure in which an alkyl group is bonded to a silicon atom of a siloxane skeleton. On the other hand, the polyether structure is not limited to these, but specifically, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide block copolymer, polyethylene polytetramethylene glycol. Examples of the molecular structure include a copolymer and a polytetramethylene glycol-polypropylene oxide copolymer. Among these, a polyethylene oxide-polypropylene oxide block copolymer is further preferable from the viewpoint of controlling wettability depending on the degree of block and the molecular weight.

  An organic substance having both an alkyl silicate structure and a polyether structure in the molecule is particularly preferred. Specifically, polyether-modified silicone such as polyether-modified polydimethylsiloxane is suitable. This can be produced by a known method, for example, by the synthesis examples 1, 2, 3, 4 described in JP-A-4-242499, the method described in Reference Example of JP-A-9-165318, etc. Can be manufactured. In particular, polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane obtained by reacting both terminal methallyl polyethylene oxide-polypropylene oxide block copolymers with dihydropolydimethylsiloxane is preferred.

  Specifically, TSF4445, TSF4446 (manufactured by GE Toshiba Silicone Co., Ltd.), SH200 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KP series (manufactured by Shin-Etsu Chemical Co., Ltd.), and DC3PA, ST869A, SH3746, SH3746M (Toray Dow Corning Silicone Co., Ltd.) can be used. Although these are additives for paints, they can be used as appropriate as long as they can provide these performances other than for paints.

  Originally, these organosilicon compounds are used for the stabilization of the substrate surface and composites. After the surface treatment of the substrate, the hydrophilic part is usually lost by rain, running water, and heating. is there. However, in the present invention, since the surface of the substrate is positively charged, there is a phenomenon in which the hydrophilic performance is restored again by moisture in the atmosphere even after the hydrophilic portion is lost.

  Using this function, products that make use of the “antifouling / antifogging function” can be realized. This can be applied to any substrate, but can be effectively used particularly for transparent organic substrates such as glass, metal, acrylic resin and polycarbonate resin, polished metal plates having high cosmetic properties, and stone substrates.

  In addition, when a composite layer is formed on a substrate by adding a silicone or modified silicone having an alkyl silicate structure or a polyether structure, or both, to the metal-doped titanium oxide, the surface of the composite layer No photocatalytic function is exhibited, and antifouling, antibacterial, gas decomposition and water purification by decomposition of organic compounds are not recognized. Therefore, by using this metal-doped titanium oxide as a composite, it becomes possible to prevent photooxidation degradation of the substrate.

(Formation of intermediate layer)
In the present invention, an intermediate layer may exist between the substrate surface and the composite. In particular, when forming a composite layer containing an organosilicon compound on the substrate surface, it is preferable to form an intermediate layer containing a silane compound on the substrate in advance. Since this intermediate layer contains a large amount of Si—O bonds, it is possible to improve the strength of the composite layer and the adhesion to the substrate. The intermediate layer also has a function of preventing moisture from entering the substrate.

  Examples of the silane compound include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. Various alkoxysilanes can be used as the hydrolyzable silane, and specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane. Of these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be mixed and used as necessary. Moreover, you may mix | blend various organopolysiloxane with these silane compounds. As an intermediate layer forming agent containing such a silane compound, there is Dry Seal S (made by Toray Dow Corning Silicone Co., Ltd.).

  In addition, room temperature curable silicone resins such as methyl silicone resin and methyl phenyl silicone resin may be used as the intermediate layer forming agent. Examples of such room temperature curable silicone resins include AY42-170, SR2510, SR2406, SR2410, SR2405, and SR2411 (manufactured by Toray Dow Corning Silicone Co., Ltd.).

  When the intermediate layer is made of a silane compound or a silicone resin, the mixing ratio (mass ratio) of these silane compound or silicone resin and the pigment is preferably in the range of 1: 2 to 1: 0.05, and 1: 1 to A range of 1: 0.1 is more preferred.

  The intermediate layer may further contain additives such as a dispersant, a stabilizer, and a leveling agent. These additives have an effect of facilitating the formation of the intermediate layer. Further, when a colorant such as a pigment / dye is blended, it is possible to add a binder for fixing the colorant. As the binder in this case, various binders for coatings mainly composed of an acrylic ester or an acrylic ester copolymer resin having excellent weather resistance can be used. For example, Polysol AP-3720 (Showa Polymer Co., Ltd.) Product), Polysol AP-609 (manufactured by Showa Polymer Co., Ltd.) and the like.

  The intermediate layer can be formed as follows, for example. An intermediate layer forming agent composed of a silane compound or a silicone resin in a volatile solvent, and a solution containing the colorant, the additive and the binder, if necessary, has a thickness of about 2 to 5 mm on the substrate surface. Apply as follows. If necessary, the intermediate layer is formed on the substrate by heating to evaporate the volatile solvent. The colored intermediate layer can be imparted with colored cosmetics to the substrate by being integrated with the substrate.

  The thickness of the intermediate layer formed as described above is not particularly limited, but is preferably 0.01 to 1.0 μm, and more preferably 0.05 to 0.3 μm. Moreover, when a coloring agent, an additive, and a binder are added, 1.0-100 micrometers is preferable and 10-50 micrometers is more preferable.

  As the method for forming the intermediate layer on the substrate, any known method can be used. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, brush coating, sponge coating Etc. are possible. In order to improve the physical performance such as the hardness of the intermediate layer and the adhesion to the substrate, it is preferable to heat them at a temperature within an allowable range after the formation of the intermediate layer on the substrate.

[External stimulus processing]
As the external stimulation treatment that can be preferably used in the present invention, any external stimulation treatment can be preferably used as long as it is a method for fixing the above-mentioned active fine particles. However, in the present invention, the flexible substrate is damaged. In order to prevent this, it is characterized by using a method capable of locally applying energy to the antireflection layer made of fine particles formed on the substrate. That is, the conventional heating means using an oven, a hot plate or the like is not preferable because the base material is heated in the same manner in order to form the antireflection layer, and the base material is damaged.

  In the present invention, for example, plasma discharge treatment, microwave irradiation treatment, ultraviolet irradiation treatment, electromagnetic wave irradiation treatment, pressure treatment and the like can be mentioned, preferably plasma discharge treatment, microwave irradiation treatment and ultraviolet irradiation treatment. More specifically, it is preferable to perform oxygen plasma treatment, microwave irradiation treatment, ultraviolet irradiation ozone treatment, or a combination of these treatments.

  Hereinafter, the external stimulus processing that can be preferably used in the present invention will be exemplified.

(Plasma discharge treatment)
The plasma treatment that can be preferably used in the present invention will be described, but the present invention is not limited to this. In the present invention, the flame treatment, the corona discharge treatment, the atmospheric pressure plasma treatment, and the plasma treatment are targeted as the plasma treatment. Hereinafter, the atmospheric pressure plasma treatment will be described as a representative of the plasma treatment.

  The plasma processing step according to the present invention is characterized in that it is performed at or near atmospheric pressure, but it is possible to perform the subsequent coating step quickly by setting it to atmospheric pressure plasma processing that is possible at atmospheric pressure. Etc. from the viewpoint of productivity. The specific pressure is preferably 70 to 130 kPa, and most preferably atmospheric pressure without any pressure reduction or pressurization.

  In order to generate plasma, it is necessary to discharge in an atmosphere of an inert gas as a carrier gas. Here, the inert gas refers to a group 18 element of the periodic table, so-called rare gas, helium, neon , Argon, krypton, xenon, radon or the like, and further in a nitrogen gas atmosphere, argon or helium is particularly preferably used. However, it is most preferable to use nitrogen gas from the viewpoint of manufacturing cost.

  As a preferred embodiment of the present invention, it is preferable to contain 0.01 to 30% by volume of a reactive gas together with an inert gas, more preferably 0.1 to 20% by volume, most preferably 1 to 15% by volume of reaction. It is more preferable in the practice of the present invention to contain a sex gas.

  A plurality of reactive gases used in the present invention can be used, but at least one kind is preferably one that contains a component that is in a plasma state in the discharge space and can treat the surface of the object.

  As a preferable example of the reactive gas, a gas such as oxygen, carbon dioxide, nitrogen (except in the case of a nitrogen atmosphere), hydrogen, or the like may be included. Moreover, in order to positively modify the surface, it is also a preferred embodiment in the present invention to use methane, ammonia, various organometallic compounds, fluorine compounds, or the like as the reactive gas.

  In the present invention, oxygen plasma treatment using oxygen gas in combination with the above-described reactive gas is most preferable from the viewpoint of reactivity. Furthermore, by using together with the peroxidized fine particles of the present invention, adhesion between particles is promoted, which is further preferable.

  When plasma treatment is performed under atmospheric pressure, the starting voltage rises. To suppress this, a dielectric is sandwiched between the discharge electrodes, the atmospheric gas is helium, argon, or nitrogen, and AC or high frequency is used as a power source. Is preferably used.

The frequency is preferably 1 kHz to 1 GHz. The power to be applied varies depending on the composition of the target sample, surface characteristics, and the like, and it is necessary to optimize the conditions. However, the power in the range of 0.01 to 10 W / cm ² is used in the range of 0.1 to several tens. Discharge treatment is performed in the range of seconds. If the applied power is too high, the smoothness of the surface may be impaired and problems such as contamination of scattered substances due to discharge may occur.

  An example of an atmospheric pressure plasma processing apparatus that can be used in the present invention will be described with reference to FIG.

  FIG. 1 shows an example of a plasma processing apparatus by so-called roll-to-roll, which can be applied to a flexible film substrate transport process. In FIG. 1, an atmospheric pressure plasma processing apparatus 30 is an apparatus having an electric field applying means 40 having two power sources, a gas supply means 50, and an electrode temperature adjusting means 60.

  An organometallic compound gas and / or oxygen supplied from the gas supply means 50 between the opposing electrodes (discharge space) 32 of the roll electrode (first electrode) 35 and the plurality of rectangular tube electrodes (second electrodes) 36. A mixture G of gas and a discharge gas such as nitrogen is supplied, activated here and introduced onto the substrate F.

  A discharge space (between the counter electrodes) 32 between the roll rotating electrode (first electrode) 35 and the square tube electrode (second electrode) 36 is connected to the roll rotating electrode (first electrode) 35 from the first power source 41. The first high-frequency electric field having the frequency ω1, the electric field strength V1, and the current I1 is supplied to the square tube electrode (second electrode) 36, and the second high-frequency electric field having the frequency ω2, the electric field strength V2, and the current I2 is supplied from the second power source 42. It comes to apply.

  A first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes current from the first power supply 41 to the first electrode. The current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass. In addition, a second filter 44 is provided between the square tube electrode (second electrode) 36 and the second power source 42, and the second filter 44 is a current from the second power source 42 to the second electrode. It is designed to make it difficult to pass the current from the first power supply 41 to the second power supply by grounding the current from the first power supply 41.

  In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube electrode 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. The current I1 of the first high-frequency electric field is preferably 0.3 to 20 mA / cm ² , more preferably 1.0 to 20 mA / cm ² . The current I2 of the second high-frequency electric field is preferably 10 to 100 mA / cm ² , more preferably 20 to 100 mA / cm ² .

  In the gas supply means 50, the reactive gas G generated by the gas generator 51 is introduced into the atmospheric pressure plasma processing container 31 from the air supply port 52 while controlling the flow rate.

  The base material F is unwound from the original winding (not shown) and conveyed, or is conveyed from the previous process, and the air entrained by the base material by the nip roll 65 via the guide roll 64 is blocked. While being in contact with the roll rotation electrode 35, it is transferred between the roll tube electrode 36 and the square tube electrode 36, and an electric field is generated from both the roll rotation electrode (first electrode) 35 and the square tube electrode (second electrode) 36. Then, discharge plasma is generated between the counter electrodes (discharge space) 32. The substrate F is treated with a plasma state gas while being wound while being in contact with the roll rotating electrode 35. The base material F is transferred to the next process through the nip roll 66 and the guide roll 67.

  The treated exhaust G ′ after the discharge treatment is discharged from the exhaust port 53.

  In order to heat or cool the roll rotating electrode (first electrode) 35 and the rectangular tube electrode (second electrode) 36 during the formation of the thin film, the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is fed by the liquid feed pump P. It sends to both electrodes through the piping 61, and temperature is adjusted from the inside of an electrode.

  Reference numerals 68 and 69 denote partition plates that partition the atmospheric pressure plasma processing vessel 31 from the outside.

  Each square tube electrode 36 shown in FIG. 1 has an effect of widening a discharge range (discharge area) as compared with a cylindrical electrode, and thus is preferably used in the present invention. Further, as shown in FIG. 2, it is preferable to cover the surface of the metallic base material 36A with a dielectric 36B to form a rectangular tube electrode 36a in order to discharge at atmospheric pressure.

  The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. In other words, when a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.

  The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of carrying out, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

  As the atmospheric pressure plasma processing container 31, a processing container made of Pyrex (registered trademark) glass or the like is preferably used. However, it is also possible to use a metal made as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to achieve insulation.

  Hereinafter, a high frequency power source applicable to the atmospheric pressure plasma processing apparatus according to the present invention will be exemplified.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Manufacturer Frequency Product name Shinko Electric 3kHz SPG3-4500
Shinko Electric 5kHz SPG5-4500
Kasuga Electric 15kHz AGI-023
Shinko Electric 50kHz SPG50-4500
HEIDEN Laboratory 100kHz * PHF-6k
Pearl industry 200kHz CF-2000-200k
Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Manufacturer Frequency Product name Pearl Industry 800kHz CF-2000-800k
Pearl industry 2MHz CF-2000-2M
Pearl Industry 13.56MHz CF-5000-13M
Pearl industry 27MHz CF-2000-27M
Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode).

  Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma processing apparatus.

In the present invention, the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm ² or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The target sample surface is processed.

The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . In addition, discharge area (cm < ² >) points out the area of the range which discharge occurs in an electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. be able to. More preferably, it is 5 W / cm ² or more. Moreover, the upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Thereby, the further uniform high-density plasma can be produced | generated, and the improvement of the further process speed and processability can be compatible.

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high frequency electric field is more preferably a continuous sine wave.

  The atmospheric pressure plasma processing apparatus shown in FIG. 1 is an apparatus having electrode temperature adjusting means 60.

  The plasma discharge treatment is preferably performed at as high a temperature as possible from the viewpoint of reactivity. In the present invention, the plasma discharge treatment may be performed at a temperature lower than the softening point of the substrate so as not to damage the substrate. Preferably, the preferable temperature range of the roll rotating electrode (first electrode) is most preferably 50 ° C. or higher and 100 ° C. or lower.

  The plasma irradiation time can be controlled by the conveyance speed of the substrate F, and is appropriately adjusted according to the irradiation time. A preferable irradiation time is 0.1 to 100 seconds, more preferably 0.2 to 30 seconds, and most preferably 0.5 to 20 seconds. Although the effect of the present invention is easily exhibited as the irradiation is continued for a long time, it is preferable to process in a shorter time in consideration of productivity.

<Microwave irradiation treatment>
As a preferable microwave processing used in the present invention, it is preferable to use a microwave having a frequency of 0.3 GHz to 50 GHz. 0.8 GHz and 1.5 GHz band, 2 GHz band, amateur radio, aircraft used in mobile communication The 1.2 GHz band used for radar, 2.4 GHz band used for microwave ovens, local radio, VICS, 3 GHz band used for ship radar, etc., and 5.6 GHz used for other ETC communications are all electromagnetic waves. An electromagnetic wave or the like that falls within a category is preferable, but a microwave (frequency of 0.3 GHz to 50 GHz) is more preferable.

  The most commonly used microwave is the microwave of 2.45 GHz among the above-described microwaves. For example, a microwave reactor manufactured by Shikoku Keiki Kogyo Co., Ltd. can be used.

  Furthermore, in the present invention, a substance having an electromagnetic wave absorbing ability is combined with the above-described fine particles, and the substance selectively absorbs microwaves, whereby local heat treatment can be performed, which is preferable in the present invention. It is an aspect.

  The power of the microwave irradiation treatment is preferably 300 to 800W, more preferably 400 to 600W. The irradiation time can be arbitrarily selected depending on the reactivity, but preferably it can be processed within 10 minutes, more preferably within 2 minutes. Moreover, in order to reduce the damage to a base material, you may perform a microwave irradiation intermittently, In that case, it is preferable to process by the total irradiation time which has irradiated.

  The substance having the ability to absorb electromagnetic waves (substance that absorbs electromagnetic waves) is more preferably fine particles having a sufficiently small particle diameter that does not cause light scattering, like the active fine particles described above. From the viewpoint of suppressing light scattering typified by Mie scattering, fine particles having an average diameter of 1 to 100 nm are preferable, and a diameter of 1 to 50 nm is more preferable.

  The above-mentioned substance having electromagnetic wave absorbing ability absorbs the irradiated electromagnetic wave and converts it into heat, so that the substance itself generates heat and becomes a heat source, so that dielectric loss or resistance loss is taken so as not to damage the substrate. It is preferable to use a material that is large and efficiently generates heat and can be locally heated.

  As the material having electromagnetic wave absorbing ability, metal oxide or metal is preferable.

  The metal oxide is preferably an oxide of copper, nickel, zinc, tin, or indium. In the case where a metal oxide is oxidized by irradiation with electromagnetic waves in the presence of oxygen, a metal salt, halide, or organometallic compound containing a metal atom can also be used. Metals of metal salts, metal oxides, organometallic compounds, halogen metal compounds, metal hydrides include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl , Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like. Among them, it is preferable to contain any of copper, nickel, Zn (zinc), Sn (tin), and In (indium), and they may be used in combination.

  Examples of the metal having electromagnetic wave absorbing ability that can be preferably used in the present invention include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, Aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium , Potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver Compound, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, can be used lithium / aluminum mixtures.

<Ultraviolet irradiation treatment>
Examples of the external stimulus treatment that can be preferably used in the present invention include an ultraviolet irradiation treatment. The ultraviolet irradiation method may be any device such as a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a deuterium lamp, an LED lamp, or an excimer lamp. Preferably, ultraviolet light having a wavelength of 150 to 400 nm is used. It is preferable to use an apparatus capable of irradiating light including light, and more preferable is an apparatus capable of irradiating light including ultraviolet light of 180 to 365 nm. More preferably, the above-mentioned light is centered on ultraviolet rays, and a lamp in which the object irradiated by other light is not heated is preferable, and a high-pressure mercury lamp, an LED lamp, an excimer lamp, or the like is more preferable.

  By treating in an atmosphere where oxygen is present at the same time as the irradiation with ultraviolet light, ozone generated by the ultraviolet light has an effect of promoting adhesion between the peroxidized active fine particles, which is a more preferable embodiment. A preferable oxygen concentration is 18 to 50% by volume, and more preferably 20 to 30% by volume.

  In the irradiation treatment described above, the treatment is performed by exposing to ozone together with ultraviolet light irradiation. The treatment time is preferably 0.5 to 30 minutes, more preferably 2 to 15 minutes.

  As an application of the antireflection layer comprising the fine particles of the present invention, for example, as an outermost layer member of a flat panel display such as a liquid crystal display, a plasma display, an organic EL display, etc. In particular, it can be preferably used in the field of optoelectronics such as an organic solar cell element used for an organic thin film solar cell and an organic photoelectric conversion element.

  Among the applications described above, an organic solar cell element will be described below as an example. In the present application, an antireflection layer made of fine particles may be formed in advance on the organic solar cell substrate described later, or the antireflection layer may be formed after the organic solar cell element is formed.

[Configuration of organic solar cell element]
The organic solar cell element (organic PV element) according to the present invention includes a p-type semiconductor material and an n-type semiconductor material as a photoelectric conversion layer sandwiched between the first electrode and the second electrode. It is an element that has a layer and generates an electromotive force by excitons moving to the p / n interface by light irradiation and charge separation into carriers.

  In order to increase the p / n interface between the p-type semiconductor material and the n-type semiconductor material, the photoelectric conversion layer preferably forms a so-called bulk heterojunction structure in which both semiconductor materials are mixed (hereinafter referred to as a bulk heterojunction layer or BHJ). Layer and i layer).

  In a general element structure, a hole transport / electron block layer / photoelectric conversion layer / electron transport / hole block layer is laminated as an organic material layer on a first electrode (anode layer), and then a second layer is formed from above. However, the present invention is not limited to this, and the photoelectric conversion layer is a layer made of a p-type semiconductor material and an n-type semiconductor material, and the above-described bulk heterojunction layer is sandwiched between them. Such a configuration, a so-called pin configuration may be applied. As a result, the rectification of holes and electrons as generated carriers becomes higher, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

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

  Examples of the condensed polycyclic aromatic low molecular compound include pentacene and derivatives thereof, porphyrin and phthalocyanine, copper phthalocyanine and derivatives thereof.

  Examples of the conjugated polymer include polythiophene such as poly-3-hexylthiophene (P3HT) and oligomers thereof, polythiophene-thienothiophene copolymer, polythiophene-diketopyrrolopyrrole copolymer, polythiophene-thiazolothiazole copolymer, Nature Mat. , Vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

(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, fullerene, octaazaporphyrin and the like, p-type semiconductor perfluoro products (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene, etc. Examples thereof include aromatic carboxylic acid anhydrides such as tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.

(Hole injection / transport layer, electron block layer)
Materials used for the hole injection / transport layer and electron blocking layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), etc. Represented polymer materials such as conductive polymers are also used for the light emitting layer, for example, carbazole-based light emitting materials such as 4,4'-dicarbazolylbiphenyl, 1,3-dicarbazolylbenzene, etc. , (Di) azacarbazoles, low molecular light emitting materials represented by pyrene-based light emitting materials such as 1,3,5-tripyrenylbenzene, polyphenylene vinylenes, polyfluorenes, polyvinylcarbazoles represented by high Examples thereof include molecular light emitting materials.

  In the present invention, a hole injection layer and a hole transport layer may be laminated according to the purpose, and an optimum material may be selected for the hole transport property and the bonding between the electrodes.

  In the present invention, a material that has a function of blocking electrons as reverse carriers and improves the selectivity of charges may be selected.

  The preferred film thickness of each layer is preferably 0.1 to 100 nm, more preferably 5 to 70 nm, and most preferably 10 to 50 nm.

(Electron injection / transport layer, hole blocking layer)
Various n-type materials can be used as the electron injection / transport layer material. Examples of materials that can be preferably used in the organic electronic device of the present invention include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinato) zinc, or the following nitrogen-containing five-membered rings. There are derivatives. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  In addition to the above-mentioned compounds, fullerenes, carbon nanotubes, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), and n-type inorganic oxides such as titanium oxide, zinc oxide, gallium oxide, etc. It is also preferable in the present invention to use.

  In the present invention, an electron injection layer and an electron transport layer may be laminated according to the purpose, and an optimal material may be selected in connection with electron transport properties and electrodes.

  In the present invention, a material that has a function of blocking electrons as reverse carriers and improves the selectivity of charges may be selected.

  The preferred film thickness range of each layer is preferably 0.1 to 100 nm, more preferably 5 to 80 nm, and most preferably 10 to 60 nm.

  The electron injection layer (buffer layer) has a structure in which halides containing ions such as lithium, potassium, sodium, and cesium, for example, lithium fluoride, potassium fluoride, and the like are stacked to improve the bonding with the electrode. Particularly preferred in the invention.

  When using an electron injection material made of these inorganic materials, it is preferable to form a film by patterning mainly by vapor deposition through a shadow mask. However, if it can be formed as a solution, it should be formed by coating in terms of productivity. Is more preferable.

  In the case of a vapor deposition method, the manufacturing method which forms a vapor deposition film after performing the wiping patterning mentioned above is especially preferable in this invention.

(Film forming method / Surface treatment method)
As a method for forming each organic material layer (functional layer), it can be formed by vapor deposition or the like, but application and printing are preferable from the viewpoint of film formation 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 ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

  After coating, it is preferable to perform heat drying annealing in order to remove residual solvent and moisture, gas, and improve the mobility of the semiconductor material.

  Each organic material has its own solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different from each other, the concentration cannot be generally determined. However, the type of the solvent used in the present invention should be suitable for the above conditions depending on the organic material to be formed into a film. May be selected from known solvents, for example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, dioxane, etc. , Ether solvents such as anisole, alcohol solvents such as methanol, ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, glycerin, benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbon solvents, paraffin solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amide solvents such as methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, sulfur such as thiophene and carbon disulfide And system solvents.

  In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Of these, preferable examples of the good solvent for the material used in the organic electronics element include, for example, an aromatic solvent, a halogen solvent, an ether solvent, and preferably an aromatic solvent and an ether solvent. is there. In addition, examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  In addition, when laminating | stacking these organic substance layers by application | coating etc., it is necessary to select a material and a solvent so that a lower layer may not be melt | dissolved.

  For this reason, a structure in which the material of the organic layer is insolubilized by positively crosslinking the material can be preferably used. For example, a polymer having a polymerizable group such as a vinyl group or a cross-linking group, and forming a polymer or a cross-linked structure having the above structural units by heating or light irradiation can be used. As a result, dissolution of the film due to the multilayer, disturbance of the interface, and the like can be suppressed.

(First electrode (transparent electrode))
In the first 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 a transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. A material having a work function larger (deep) than 4 eV is suitable. For example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, and metal thin films such as gold, silver and platinum Metal nanowires, carbon nanotubes, and the like can be used.

(Second electrode (counter electrode))
The second electrode according to the present invention is not particularly limited to a cathode and an anode, and can be selected depending on the element structure, but preferably a transparent electrode is used as the anode. For example, when used as a cathode, it is preferable to use a metal, an alloy, an electrically conductive compound having a work function of 4 eV or less (shallow), and a mixture thereof as an electrode material. 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 electrical bonding with the organic layer and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger (deeper) work function than this metal. For example, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum alone and the like are suitable.

  The second electrode can be produced by forming 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 to 200 nm.

  If a highly reflective metal material is used as the second electrode, for example, in an organic EL element, a part of the emitted light can be reflected and extracted to the outside. In the organic solar cell element, a photoelectric conversion layer The effect of increasing the optical path length is obtained by reflecting the light that has passed through and returning again to the photoelectric conversion layer, and in any case, an improvement in external quantum efficiency can be expected.

  Furthermore, it may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.) or a nanoparticle, nanowire, or nanostructure made of carbon. A highly dispersible paste is preferable because a transparent and highly conductive counter electrode can be formed by a coating method or a printing 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-transmitting material mentioned in the description of the transparent electrode, a light-transmitting electrode can be obtained.

(Base material)
The base material (hereinafter also referred to as a substrate) used in the organic electronics element of the present invention is a member that can transmit light for generating electromotive force, that is, is transparent to the wavelength of incident light. It is preferable. Examples of the base material that can be used in the present invention are characterized by being a flexible base material, and preferred examples include a resin substrate and a metal foil, but a transparent resin film from the viewpoint of lightness and flexibility. It is desirable to use

  There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent substrate by this invention, The material, a shape, a structure, thickness, etc. can be suitably selected from well-known things. For example, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at ~800nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesiveness of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.

  In order to suppress the permeation of oxygen and water vapor, a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer is formed in advance on the side where the transparent conductive layer is formed or on the opposite side. It may be.

(Sealing)
In order to prevent the produced organic photoelectric conversion element from being deteriorated by oxygen, moisture, etc. in the atmosphere, it is preferable to seal the organic EL element and the organic solar cell element by a known method. For example, a method of sealing and bonding a plastic film on which a gas barrier layer such as a thin film of aluminum, silicon oxide, or aluminum oxide is formed and an organic electronics element with an adhesive, UV curable / thermosetting resin, etc. Spin coating of high organic polymer materials (polyvinyl alcohol, etc.), inorganic thin films (silicon oxide, aluminum oxide, etc.) or organic films (parylene, etc.) with high gas barrier properties under vacuum or air, sputtering, CVD, etc. And a method of laminating them in a composite manner.

  Furthermore, in the present invention, from the viewpoint of improving the lifetime of the element, the entire element including the substrate may be laminated and sealed with two substrates with a barrier, and preferably the structure including a moisture getter or the like is included. Is more preferable.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the aspect of this invention is not limited to this.

Example 1
<< Preparation of Substrate S-101 with Antireflection Layer >>
Titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) was slowly dropped into pure water that was vigorously stirred to prepare 1000 ml of a 5% by mass aqueous solution. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. After stirring at room temperature for 15 hours, 3 g of Shin-Etsu Silicone Co., Ltd. activator KF-6013 was subsequently added to obtain a fine particle dispersion Em01.

  As a substrate, a 180 mm width polyethylene naphthalate (PEN) sheet (75 μm thickness) surface-treated by corona discharge treatment is prepared, and the above dispersion Em01 is dried using a wire bar so that the dry film thickness becomes 2 μm. It apply | coated and dried for 15 minutes at 150 degreeC, and board | substrate S-101 with an antireflection layer was obtained.

<< Preparation of Substrate S-102 with Antireflection Layer >>
In the production of the substrate S-101 with an antireflection layer, the dispersion Em01 was similarly applied using a wire bar, and then the substrate was kept at 150 ° C. and irradiated with a 100 W high-pressure mercury lamp for 2 minutes in the same manner. Thus, a substrate S-102 with an antireflection layer was produced.

<< Preparation of substrate S-103 with antireflection layer >>
In the production of the substrate S-101 with the antireflection layer, after applying the dispersion liquid Em01 in the same manner using a wire bar, the plasma irradiation treatment was performed according to the following plasma irradiation condition 1 while keeping the substrate at 80 ° C. in advance. Produced a substrate S-103 with an antireflection layer in the same manner.

(Plasma irradiation condition 1)
Plasma irradiation apparatus: The apparatus shown in FIG. 2 is used. First power supply: HEIDEN Laboratory PHF-6k (100 kHz)
Second power supply: Pearl Industrial CF-5000-13M (13.56 MHz)
Carrier gas: Nitrogen (under atmospheric pressure)
Reactive gas: Oxygen (5% by volume with respect to nitrogen)
Applied output: 1.0 W / cm ²
Electrode temperature control: 80 ° C
Processing time: 20 seconds << Preparation of substrate S-104 with antireflection layer >>
An aqueous solution in which 0.6% by mass of tin (II) chloride dihydrate (manufactured by Kanto Chemical Co., Ltd.) was dissolved was prepared, and titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) was slowly added dropwise with vigorous stirring to 5% by mass. A 1000 ml aqueous solution was prepared. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. After stirring at room temperature for 15 hours, 3 g of an active agent KF-6013 manufactured by Shin-Etsu Silicone Co., Ltd. was subsequently added to obtain a fine particle dispersion Em02 containing tin oxide.

  Similarly to the production of the substrate S-101 with the antireflection layer, the dispersion liquid Em02 was applied in the same manner using a wire bar, and then the 2.45 GHz microwave irradiation apparatus while keeping the substrate at 150 ° C. or lower. The antireflection layer was prepared in the same manner as the production of the substrate S-101 with the antireflection layer, except that (irradiation was intermittently performed using a microwave reactor manufactured by Shikoku Sangyo Kogyo Co., Ltd.) with an output of 500 W so that the integration time was 2 minutes. Attached substrate S-104 was produced.

<< Production of Substrate S-105 with Antireflection Layer >>
Titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) was slowly dropped into pure water that was vigorously stirred to prepare 1000 ml of a 5% by mass aqueous solution. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. Next, the dispersion was cooled to around 5 ° C., 30 ml of 35% by mass hydrogen peroxide was slowly added with stirring, and allowed to react for 15 hours, and 3 g of Shin-Etsu Silicone Co., Ltd. KF-6013 was added. Oxidized fine particle dispersion Em03 was obtained.

  As a substrate, a 180 mm width polyethylene naphthalate (PEN) sheet (75 μm thickness) surface-treated by corona discharge treatment is prepared, and the above dispersion Em01 is dried using a wire bar so that the dry film thickness becomes 2 μm. It apply | coated and dried at 150 degreeC for 15 minute (s), and board | substrate S-105 with an antireflection layer was obtained.

<< Production of Substrate S-106 with Antireflection Layer >>
In the production of the substrate S-105 with an antireflection layer, the dispersion liquid Em03 was similarly applied using a wire bar, and then the substrate was kept at 150 ° C. and irradiated with a 100 W high pressure mercury lamp for 2 minutes in the same manner. Thus, a substrate S-106 with an antireflection layer was produced.

<< Preparation of Substrate S-107 with Antireflection Layer >>
In the production of the substrate S-105 with the antireflection layer, the dispersion Em03 was applied in the same manner using a wire bar, and then the plasma irradiation treatment was performed according to the following plasma irradiation condition 2 while keeping the substrate at 80 ° C. in advance. Produced a substrate S-107 with an antireflection layer in the same manner.

(Plasma irradiation condition 2)
Plasma irradiation apparatus: The apparatus shown in FIG. 2 is used. First power supply: HEIDEN Laboratory PHF-6k (100 kHz)
Second power supply: Pearl Industrial CF-5000-13M (13.56 MHz)
Carrier gas: Nitrogen (under atmospheric pressure)
Reactive gas: Oxygen (5% by volume with respect to nitrogen)
Applied output: 1.0 W / cm ²
Electrode temperature control: 80 ° C
Processing time: 20 seconds << Preparation of substrate S-108 with antireflection layer >>
An aqueous solution in which 0.6% by mass of tin (II) chloride dihydrate (manufactured by Kanto Chemical Co., Ltd.) was dissolved was prepared, and titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) was slowly added dropwise with vigorous stirring to 5% by mass. A 1000 ml aqueous solution was prepared. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. Next, the dispersion was cooled to around 5 ° C., 30 ml of 35% by mass hydrogen peroxide was slowly added while stirring, and allowed to react for 15 hours as it was, and then 3 g of Shin-Etsu Silicone activator KF-6013 was added and oxidized. A peroxidized fine particle dispersion Em04 containing tin was obtained.

  Similarly to the production of the substrate S-105 with an antireflection layer, the dispersion liquid Em04 was applied in the same manner using a wire bar, and then a 2.45 GHz microwave irradiation apparatus (with the substrate kept at 150 ° C. or lower) ( With the use of an anti-reflective layer in the same manner as the production of the substrate S-105 with an anti-reflective layer, except that a microwave reaction device manufactured by Shikoku Keiki Kogyo Co., Ltd. was used and intermittent irradiation was performed so that the accumulated time was 2 minutes at an output of 500 W. Substrate S-108 was produced.

<< Preparation of substrate S-109 with antireflection layer >>
Prepare an aqueous solution in which 0.5% by mass of copper (II) chloride dihydrate (manufactured by Kanto Chemical Co., Ltd.) is dissolved, and slowly add titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) dropwise with vigorous stirring. A 1000 ml aqueous solution was prepared. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. Next, the dispersion was cooled to around 5 ° C., 30 ml of 35% by mass hydrogen peroxide was slowly added while stirring, and allowed to react for 15 hours as it was, and then 3 g of Shin-Etsu Silicone activator KF-6013 was added and oxidized. A dispersion em05 of peroxidized fine particles containing copper was obtained.

  Similarly to the production of the substrate S-105 with an antireflection layer, the dispersion Em05 was similarly applied using a wire bar, and then dried at 150 ° C. for 15 minutes to obtain a substrate S-109 with an antireflection layer. .

<< Production of Substrate S-110 with Antireflection Layer >>
In the production of the substrate S-109 with an antireflection layer, the dispersion Em05 was similarly applied using a wire bar, and then the substrate was kept at 150 ° C. and irradiated with a 100 W high pressure mercury lamp for 2 minutes in the same manner. Thus, a substrate S-110 with an antireflection layer was produced.

<< Preparation of Substrate S-111 with Antireflection Layer >>
In the production of the substrate S-109 with an antireflection layer, the dispersion liquid Em05 was applied in the same manner using a wire bar, and then subjected to plasma irradiation treatment according to the following plasma irradiation condition 3 while keeping the substrate at 80 ° C. in advance. Produced a substrate S-111 with an antireflection layer in the same manner.

(Plasma irradiation condition 3)
Plasma irradiation apparatus: The apparatus shown in FIG. 1 is used. First power supply: HEIDEN Laboratory PHF-6k (100 kHz)
Second power supply: Pearl Industrial CF-5000-13M (13.56 MHz)
Carrier gas: Nitrogen (under atmospheric pressure)
Reactive gas: Oxygen (5% by volume with respect to nitrogen)
Applied output: 1.0 W / cm ²
Electrode temperature control: 80 ° C
Processing time: 20 seconds << Preparation of substrate S-112 with antireflection layer >>
Prepare an aqueous solution in which 0.5% by mass of copper (II) chloride dihydrate (manufactured by Kanto Chemical Co., Ltd.) and 0.6% by mass of tin (II) chloride dihydrate (manufactured by Kanto Chemical) are mixed and dissolved. While stirring vigorously, titanium tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade) was slowly added dropwise to prepare 1000 ml of a 5% by mass aqueous solution. The pH was adjusted to 7.0 while slowly dropping 5% by mass of aqueous ammonia, and the liquid containing the precipitate was washed three times with pure water to obtain 500 ml of a dispersion. Next, the dispersion was cooled to around 5 ° C., 30 ml of 35% by mass hydrogen peroxide was slowly added while stirring, and allowed to react for 15 hours as it was, and then 3 g of Shin-Etsu Silicone activator KF-6013 was added and oxidized. A peroxidized fine particle dispersion Em06 containing copper and tin oxide was obtained.

  Similarly to the production of the substrate S-109 with an antireflection layer, the dispersion Em06 was similarly applied using a wire bar, and then a 2.45 GHz microwave irradiation apparatus (with a substrate kept at 150 ° C. or lower) ( With the use of a microwave reactor manufactured by Shikoku Keisoku Kogyo Co., Ltd., with an antireflection layer in the same manner as the production of the substrate S-109 with an antireflection layer, except that intermittent irradiation was performed with an output of 500 W so that the integration time was 2 minutes. Substrate S-112 was produced.

<< Preparation of Substrate S-113 with Antireflection Layer >>
In the production of the substrate S-111 with an antireflection layer, after forming the antireflection layer on one side of the PEN sheet, by forming the antireflection layer in the same manner on the opposite surface different from that, A substrate S-113 with an antireflection layer was produced in the same manner except that antireflection layers were formed on both sides.

<< Evaluation of substrate with antireflection layer >>
The following evaluation was performed about the produced board | substrates S-101 to S-113 with an antireflection layer.

(Transmittance)
The transmittance was substituted for the reflectance evaluation method. It shows that antireflection property is so high that the transmittance | permeability is high. Using a spectral transmittance measuring device (UVPC-3000: manufactured by Shimadzu Corporation), the linear transmittance in the thickness direction with respect to light having a wavelength of 550 nm at room temperature was measured.

(Anti-fouling property)
The prepared substrate with antireflection layer is vertically attached from the outdoor ground to a height of 1500 mm at the lower end, exposed outdoors in Tokyo for 3 months from April to June, and then transmitted in the same manner as the transmittance evaluation described above. The rate was measured.

(Bending durability)
Prepare a paper core of 3 inches φ, wind up 50 sets of the prepared antireflection layer substrate with the front and back as one set, and visually check for cracks for a length of 1 m. Evaluated by criteria.

○: No cracks Δ: Cracks are found in 1 to 5 places ×: Cracks are seen in 6 or more places Table 1 shows the evaluation results.

  From Table 1, it can be seen that the substrate with an antireflection layer produced by the method for producing an antireflection layer of the present invention has a high antireflection function and antifouling property, and is less prone to cracking due to bending.

Example 2
<< Production of Organic Solar Cell Panel OPV-1 >>
[Formation of first electrode]
After forming a barrier layer on the opposite surface of the antireflection layer of the antireflection layer substrate S-105 produced in Example 1, a 140 nm thick ITO (indium tin oxide) film was formed by sputtering under vacuum environment conditions. The first electrodes having a size of 10 mm × 100 mm were formed in 12 rows at regular intervals.

[Formation of organic layer]
(Formation of hole transport layer)
Polyethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) diluted with 30% by mass of pure water and 30% by mass of isopropanol with respect to 40% by mass, coating solution for forming a hole transport layer As mentioned above, it apply | coated on the PEN board | substrate containing the 1st electrode mentioned above. Coating was performed using a slit coater so that the thickness after drying was 30 nm, followed by drying and heat treatment at 150 ° C. for 30 minutes to form a hole transport layer.

(Formation of photoelectric conversion layer)
On the hole transport layer, P3HT in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and A solution mixed at 1: 0.8 so as to be 3.0% by mass was prepared, applied using a slit coater so that the dry film thickness was 90 nm, and allowed to dry at room temperature. A wiping member was brought into contact with and wiped off between the first electrodes produced at regular intervals, followed by heat treatment at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

[Formation of cathode buffer layer]
The produced substrate was transferred to a vacuum deposition chamber, and LiF (Sigma Aldrich) was deposited to a thickness of 0.6 nm under vacuum conditions reduced to 5 × 10 ⁻⁴ Pa, and a cathode buffer layer (electron injection) Layer).

[Formation of second electrode]
Subsequently, with the same degree of vacuum, a mask pattern was formed by vapor deposition, and a second electrode (cathode) made of aluminum having a thickness of 100 nm was formed using aluminum.

[Pasting of sealing member]
Next, in the fabricated element, the portion of the leftmost first electrode connected in series in 12 columns (the region where the organic layer was removed by patterning) and the lead portion connected to the rightmost second electrode, In this region, an ultraviolet curable liquid adhesive (epoxy resin) was dropped from a plurality of nozzles and applied.

A sealing film (manufactured by Toppan Printing Co., Ltd., GX film: thickness 100 μm) was bonded to the above-mentioned adhesive-coated surface by a roll laminator method, and after pressure-bonding at a pressure of 0.1 MPa under atmospheric pressure, 100 W The high-pressure mercury lamp was sealed by being irradiated and fixed for 1 minute at an irradiation intensity of 5 to ²⁰ mW / cm ² and a distance of 5 to 15 mm.

  An organic solar cell panel OPV-1 was produced by the series of production methods described above.

<< Production of Organic Solar Cell Panels OPV-2 to OPV-9 >>
In the production of the organic solar cell panel OPV-1, the organic solar cell was similarly obtained except that the substrate S-105 with antireflection layer was replaced with the substrates S-106 to S-113 with antireflection layer prepared in Example 1. Panels OPV-2 to OPV-9 were prepared.

<< Evaluation of organic solar panel >>
About the produced organic solar cell panel, using a solar simulator, an AM 1.5G filter, light of 100 mW / cm ² intensity is irradiated, the IV characteristics are evaluated, and the short circuit current density Jsc (mA / mA) is evaluated. cm ² ), open circuit voltage Voc (V), and fill factor ff, energy conversion efficiency η (%) was obtained using Equation 1. The energy conversion efficiency is expressed as a relative value where the energy conversion efficiency of OPV-1 is 100. In addition, the short circuit current density was normalized and calculated with the area equivalent to the effective power generation part of an organic solar cell panel.

Formula 1 η (%) = Jsc (mA / cm ² ) × Voc (V) × ff
The evaluation results are shown in Table 2.

  From Table 2, it can be seen that the organic solar cell panel of the present invention has high energy conversion efficiency because of its high antireflection function.

DESCRIPTION OF SYMBOLS 30 Atmospheric pressure plasma processing apparatus 31 Atmospheric pressure plasma processing container 32 Discharge space 36 Square tube electrode 40 Electric field application means 41 1st power supply 42 2nd power supply 43 1st filter 44 2nd filter 50 Gas supply means 51 Gas generator 52 Supply Air outlet 53 Air outlet 60 Electrode temperature adjusting means 64 Guide roll 65 Nip roll 68, 69 Partition plate F Substrate G 'Processing exhaust port 36a Square tube electrode 36A Metal base 36B Dielectric coating layer

Claims (9)

  A method for producing an antireflection layer comprising at least a step of applying a dispersion containing fine particles whose surface is peroxidized on at least one surface of a resin base material, and a step of fixing the fine particles by an external stimulus treatment .   The method for producing an antireflection layer according to claim 1, wherein the dispersion liquid contains at least a conductor and fine particles made of a dielectric or a semiconductor.   The reflection according to claim 1, wherein the dispersion contains at least fine particles made of a metal or metal oxide that absorbs microwaves, and the external stimulation treatment is a microwave irradiation treatment. Manufacturing method of prevention layer.   The method for producing an antireflection layer according to claim 1, wherein the external stimulation treatment is a treatment selected from plasma discharge treatment, microwave irradiation treatment, and ultraviolet irradiation treatment.   The method for producing an antireflection layer according to claim 4, wherein the external stimulation treatment is a plasma discharge treatment performed in the presence of oxygen at atmospheric pressure or an atmospheric pressure close to atmospheric pressure.   5. The method for producing an antireflection layer according to claim 4, wherein the external stimulation treatment is an ultraviolet irradiation treatment performed under a condition where an oxygen concentration in an atmosphere is 18 volume% or more and 50 volume%.   The method for producing an antireflection layer according to any one of claims 1 to 6, wherein the resin base material is a flexible base material.   An organic electronics element comprising an antireflection layer produced by the method for producing an antireflection layer according to claim 1.   9. The organic electronic device according to claim 8, wherein the antireflection layer is formed on both surfaces of the resin base material.

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