JP2020104084A - Supporting method of dye, and manufacturing method of electronic device or electronic component - Google Patents

Abstract

To provide a new deposition method which can uniformly and suitably support dye on a substrate while significantly improving a support speed.SOLUTION: In a method of supporting dye on a substrate by contacting the dye with the substrate 14, the substrate includes a porous layer with an average pore diameter 100 nm or less on an entire or a part of a surface. The dye is smaller than the average pore diameter and is contacted by supporting the dye in pores of the porous layer by immersing the substrate with a raw material solution 18 containing the dye and a solvent under a reduced pressure to make the substrate support the dye.SELECTED DRAWING: Figure 2

Description

The present invention relates to a method for supporting a dye on a substrate by impregnating the substrate with a raw material solution containing the dye.

In recent years, a solar cell has been attracting attention as a photoelectric conversion element that converts light energy into electric power. Among them, dye-sensitized solar cells can be expected to be lighter than silicon-type solar cells, can generate power stably over a wide illuminance range, and do not require large-scale equipment, and are relatively inexpensive. It has attracted attention because it can be manufactured using materials.

Here, the dye-sensitized solar cell is usually a cell having a structure in which a photoelectrode including a porous semiconductor layer having a sensitizing dye adsorbed, an electrolyte layer, and a counter electrode including a catalyst layer are arranged in this order. It consists of multiple connections.

Conventionally, in order to increase the photoelectric conversion efficiency of a dye-sensitized solar cell, a manufacturing method has been proposed in which the amount of a sensitizing dye (hereinafter, also simply referred to as “dye”) to be adsorbed on a porous semiconductor layer is increased. Specifically, on a semiconductor layer formed on a base material and made of a porous material, on a semiconductor layer having a contact angle with the porous semiconductor layer of 6° or less and a boiling point of 80° C. or more. , A dye solution in which a dye is dissolved in 5 mM or more is applied to a solvent having a contact angle with the porous semiconductor layer of 6° or less and a boiling point of 80° C. or more, and the dye is supported on the semiconductor layer. A method for producing a dye-sensitized solar cell has been proposed (see, for example, Patent Document 1). However, the method described in Patent Document 1 is still not sufficiently satisfactory in terms of loading efficiency and loading amount.

Under such circumstances, the mist CVD method has been studied in recent years. Non-Patent Document 1 describes film formation of a ZnO transparent conductive film using a mist CVD method. Then, Patent Document 1 describes that a regrowth step is performed by a mist CVD method for forming a ZnO-based single crystal thin film.

Further, recently, it has been studied to form a fullerene on a substrate by using mist CVD (Patent Document 2). Fullerene is expected to be used as a suitable heat protection film as compared with a normal carbon film. Further, since it has a very low electric conductivity, it is expected to be used as an insulating film and as a high resistance black matrix of a color filter. On the other hand, for example, when forming a film of a fullerene on a porous body such as titanium oxide, it is difficult to sufficiently support the fullerene on the substrate. There was a problem of being restricted by. The loading amount was still insufficient, the thickness of the loading layer was thin, and the loading rate was not satisfactory for industrial application.

As described above, in recent years, the mist CVD method has attracted particular attention as a method capable of producing a new functional material, but it has not been satisfactory in the supporting process. Further, the impregnation method which has been conventionally used has the same problem. Therefore, there has been a long-felt need for a method capable of supporting a dye more easily and more efficiently.

JP2012-3955A JP, 2018-118175, A

Toshiyuki Kawahara, “Study on Mist CVD Method and Its Application to Zinc Oxide Thin Film Growth”, Kyoto University Doctoral Thesis, March 2008

It is an object of the present invention to provide a novel dye-supporting method capable of industrially supporting a dye on a substrate.

The present inventors have conducted extensive studies to achieve the above object, and as a result, a method of supporting the dye on the substrate by bringing the dye into contact with the substrate, wherein the substrate has an average on a part or all of the surface. A porous layer having a pore size of 100 nm or less, the dye is smaller than the average pore size, and the contact is performed by impregnating the substrate with a raw material solution containing the dye and a solvent under reduced pressure to form pores in the porous layer. Surprisingly, when the above-mentioned dye is carried inside, compared with the case where the conventional mist CVD or the impregnation method is used, not only the carrying speed is significantly improved, but also the porosity having fine pores is increased. It has been found that the dye can be uniformly and satisfactorily carried in the pores of the texture layer, and it has been found that such a dye carrying method can solve the above-mentioned conventional problems all at once.
In addition, the present inventors have completed the present invention after further studying after obtaining the above-mentioned findings.

That is, the present invention relates to the following inventions.
[1] A method of supporting the dye on the substrate by bringing the dye into contact with the substrate, wherein the substrate includes a porous layer having an average pore diameter of 100 nm or less on a part or all of the surface, and the dye is It is smaller than the average pore diameter, and the contact is performed by impregnating the substrate with a raw material solution containing the dye and a solvent under reduced pressure to carry the dye in the pores of the porous layer. how to.
[2] The method according to [1], wherein the impregnation is performed by immersing the substrate in the raw material solution and then reducing the pressure.
[3] The method according to [1] or [2], wherein the dye is an organic dye or a metal complex dye.
[4] The method according to any one of [1] to [3], wherein the dye is a metal complex dye.
[5] The method according to any one of [1] to [4] above, wherein the dye is a metal complex dye containing a Group 8 metal of the periodic table.
[6] The method according to any one of [1] to [5] above, wherein the solvent is an aprotic polar solvent.
[7] The method according to any one of [1] to [6], wherein the boiling point of the solvent is 160° C. or lower.
[8] The method according to any one of [1] to [7], wherein the porous layer is a porous semiconductor layer.
[9] The method according to [8], wherein the porous semiconductor layer is composed of semiconductor fine particles.
[10] The method according to any one of [1] to [9], wherein the base is a substrate.
[11] The method according to any one of [1] to [10] above, wherein the impregnation is performed under a reduced pressure of 100 Pa to 90000 Pa.
[12] A method of manufacturing an electronic device or an electronic component including a step of supporting a dye on a substrate, characterized in that the method according to any one of [1] to [11] is used in the step. Production method.
[13] A method for producing a dye-sensitized solar cell using at least a photoelectrode composed of a dye-supported substrate, an electrolyte layer and a counter electrode, wherein A method for producing a dye, which is formed by supporting a dye on a substrate using the method according to any one of the above.
[14] A method of adsorbing the dye on the substrate by bringing the dye into contact with the substrate, wherein the substrate contains a porous layer having an average pore diameter of 100 nm or less on a part or all of the surface thereof. It is smaller than the average pore diameter, and the contact is performed by impregnating the substrate with a raw material solution containing the dye and a solvent under reduced pressure to adsorb the dye in the pores of the porous layer. how to.

According to the method for supporting a dye of the present invention, the dye can be supported on the substrate industrially advantageously.

An example of the schematic block diagram of the impregnation apparatus used in the Example is shown. It is a schematic block diagram of the film-forming apparatus (mist CVD) used in the comparative example. An example of the schematic block diagram of the impregnation apparatus used in the Example is shown. 3 is a photograph of the appearance of both front and back surfaces of a substrate for each impregnation time in Examples and Comparative Examples. (A) shows the results of Example 1 and (b) shows the results of Comparative Example 1. 3 is a photograph of the appearance of both front and back surfaces of a substrate for each impregnation time in Examples and Comparative Examples. (A) shows the results of Example 1 and (b) shows the results of Comparative Example 2. 3 is a photograph of the appearance of the back surface of the substrate for each impregnation time in Examples and Comparative Examples.

The method for supporting a dye according to the present invention is a method for supporting the dye on the substrate by bringing the dye into contact with a substrate, wherein the substrate has a porous layer having an average pore diameter of 100 nm or less on a part or all of the surface. And the dye is smaller than the average pore size, and the contact is carried out by impregnating the substrate with a raw material solution containing the dye and a solvent under reduced pressure to carry the dye in the pores of the porous layer. It is characterized by performing by. In addition, in the present invention, “support” includes adsorption and may be temporary support.

(Raw material solution)
The raw material solution is in the form of a solution containing a dye and a solvent, and is not particularly limited as long as the dye can be supported on the substrate, and may contain an inorganic material or an organic material. You may stay. Further, the raw material solution may contain both an inorganic material and an organic material.

The dye is not particularly limited as long as it is smaller than the average pore size. The size of the dye is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 100 nm or less, more preferably 10 nm or less. In the present invention, the dye is preferably a compound (sensitizing dye) that can be excited by light to emit an electron. Examples of the dyes include cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, organic dyes such as perylene dyes, or iron, copper, phthalocyanine complexes of metals such as ruthenium, and the like. Examples thereof include metal complex dyes such as porphyrin complexes. In the present invention, the dye is preferably a metal complex dye, more preferably a metal complex dye containing a Group 8 metal of the periodic table (for example, iron, ruthenium, osmium, etc.), and a ruthenium complex. Most preferably it is a dye. The ruthenium complex is preferably, for example, a ruthenium polypyridine-based complex or the like, and more preferably, a ruthenium complex or the like represented by the formula: Ru(L)(L′)(X) _2. Where L is 4,4′-dicarboxy-2,2′-bipyridine, a quaternary ammonium salt thereof, or a polypyridine-based ligand having a carboxyl group introduced, and L′ is the same as L. , Or 4,4′-substituted 2,2′-bipyridine. Examples of the substituents at the 4'and 4'positions of L'include long-chain alkyl groups (alkyl groups having 6 to 20 carbon atoms), alkyl-substituted vinyl thienyl groups, alkyl- or alkoxy-substituted styryl groups, thienyl group derivatives and the like. To be Further, X is SCN, Cl, or CN. More specifically, bis(4,4′-dicarboxy-2,2′-bipyridine)diisothiocyanate ruthenium complex and the like can be mentioned. Specific examples of the dye include, for example, Z907, Z907Na, CYC-B1, CYC-B3, CYC-B5, CYC-B6S, CYC-B7, CYC-B11, C106, C101, K-19 or SK-1. Are listed. These dyes can be used alone or in combination of two or more.

The solvent is not particularly limited as long as it does not impair the object of the present invention, may be an inorganic solvent such as water, may be an organic solvent such as alcohol, or a mixture of an inorganic solvent and an organic solvent. It may be a solvent. More specifically, examples of the water include pure water, ultrapure water, tap water, well water, mineral water, mineral water, hot spring water, spring water, fresh water, and sea water. In the present invention, the solvent is preferably an organic solvent, and an aprotic polar solvent is more preferable because the dye can be more favorably supported on the solvent. Also, the boiling point of the solvent is not particularly limited, but in the present invention, it is preferably 210°C or lower, and more preferably 160°C or lower.

The aprotic polar solvent is difficult to donate a proton and is not particularly limited as long as it has polarity. Acetone, methyl ethyl ketone, cyclohexanone, isophorone, acetophenone, methyl isobutyl ketone, ketone solvents such as diethyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, γ-butyrolactone, γ-valerolactone, δ -Valerolactone, γ-caprolactone, ε-caprolactone, ethyl lactate, methyl formate, ester solvents such as propylene carbonate, pyridine, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methylpyrrolidone, Acetonitrile, nitromethane, 2-pyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N-methylpropionamide, methylimidazolidinone, 1,3-dimethyl -2-Imidazolidinone, benzonitrile, acetonitrile, propionitrile, butyronitrile, adiponitrile, and other nitrogen-containing compounds, tetrahydrofuran, dioxane, dioxolane, and other ether solvents (cyclic ethers, chain ethers), the sulfoxide compounds Examples of the solvent include sulfur-containing compounds such as dimethyl sulfoxide, diethyl sulfoxide, methylphenyl sulfoxide and tetramethylene sulfoxide. Among them, in the present invention, the aprotic polar solvent is preferably a hetero atom-containing organic solvent, an oxygen atom-containing organic solvent (ketone solvent, ester solvent or ether solvent) or nitrogen atom-containing organic solvent A (nitrogen-containing compound) is more preferable, and an oxygen atom-containing organic solvent is most preferable. By impregnating the substrate in the presence of such a preferable solvent and under reduced pressure, there is no limitation on the shape of the substrate, for example, when a substrate having a porous layer having fine pores (average pore diameter 100 nm) is used. Even if it exists, the dye can be more uniformly and favorably carried in the pores of the porous layer.

In the present invention, the solvent may be a mixed solvent containing two or more kinds of solvents. When the solvent is a mixed solvent, for example, it may contain two or more solvents selected from the solvents exemplified as the aprotic polar solvent, and the solvent exemplified as the aprotic polar solvent, and water. Inorganic solvent such as or an organic solvent such as alcohol may be included.

Further, the raw material solution may be mixed with an additive such as hydrohalic acid, an oxidizing agent, or an adsorbent. The size of the additive is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 100 nm or less, more preferably 10 nm or less. Examples of the hydrohalic acid include hydrobromic acid, hydrochloric acid, hydroiodic acid, and the like. Among them, hydrobromic acid or hydroiodic acid is preferable. Examples of the oxidizing agent include hydrogen peroxide (H ₂ O ₂ ), sodium peroxide (Na ₂ O ₂ ), barium peroxide (BaO ₂ ), benzoyl peroxide (C ₆ H ₅ CO) ₂ O _{2 and the} like. Examples thereof include perchloric acid, hypochlorous acid (HClO), perchloric acid, nitric acid, ozone water, organic peroxide such as peracetic acid and nitrobenzene. Examples of the adsorbent include coadsorbents having one or more acidic groups (preferably carboxyl or a salt thereof), and more specifically, compounds having a fatty acid or a steroid skeleton. .. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butanoic acid, hexanoic acid, octanoic acid, decanoic acid, hexadecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid. Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, and ursodeoxycholic acid.

(Base)
The substrate is not particularly limited as long as it includes a porous layer having an average pore size of 100 nm or less on a part or all of the surface. The material of the substrate is not particularly limited as long as it does not hinder the object of the present invention, and may be a known substrate, an organic compound or an inorganic compound. The "average pore diameter" is a value obtained by doubling the average pore radius r obtained according to JIS K1150, which is obtained using the mercury penetration method or the nitrogen adsorption isotherm. In the present invention, for example, the average pore size may be calculated by SEM observation for convenience. The porosity of the porous layer is also not particularly limited, but in the present invention, it is preferably 20% to 90%, more preferably 40% to 90%. The shape of the base body may be any shape, and is effective for all shapes, for example, plate shape such as flat plate or disk, fibrous shape, rod shape, cylindrical shape, prismatic shape, tubular shape. , Spiral shape, spherical shape, ring shape, etc., but a substrate is preferable in the present invention. The thickness of the substrate is not particularly limited in the present invention, but is preferably 0.5 μm to 100 mm, more preferably 1 μm to 10 mm.

The material of the porous layer is not particularly limited as long as it does not impair the object of the present invention, and may be an inorganic material or an organic material. Further, it may be a metal, a semiconductor, or an insulator. The porous material forming the porous layer, for example, titanium oxide, zirconium oxide, zinc oxide, vanadium oxide, niobium oxide, tantalum oxide, metal oxide semiconductors such as tungsten oxide, strontium titanate, calcium titanate, Complex metal oxide semiconductors such as magnesium titanate, barium titanate and potassium niobate, transition metal oxides such as magnesium oxide, strontium oxide, aluminum oxide, cobalt oxide, nickel oxide and manganese oxide, cerium oxide, gadolinium oxide and oxidation Examples thereof include lanthanoid oxides such as samarium and ytterbium oxide, and natural or synthetic silicic acid compounds represented by silica. These materials may be used alone or in combination of two or more. Further, the porous layer is preferably composed of semiconductor fine particles. Examples of the semiconductor fine particles include particles of metal oxides such as titanium oxide, zinc oxide and tin oxide. The particle size of the semiconductor fine particles (average particle size of primary particles) is not particularly limited, but is preferably 2 to 80 nm, more preferably 2 to 60 nm. Since the particle size is small, the resistance can be reduced. Furthermore, the thickness of the porous layer is not particularly limited, but is usually 1 μm to 1000 μm, and preferably 1 μm to 200 μm. The means for forming the former porous layer is not particularly limited and may be a known means. Examples of means for forming the porous layer include a pressing method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, a coating method, and a binder-free coating method.

The substrate is not particularly limited as long as it has a plate shape. It may be an insulator substrate, a semiconductor substrate, a metal substrate or a conductive substrate, or a transparent substrate such as a rigid substrate or a flexible substrate. Further, a substrate in which at least one kind of film of a metal film, a semiconductor film, a conductive film and an insulating film is formed on part or all of these surfaces can also be suitably used as the substrate. .. As the constituent metal of the metal film, for example, one selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel, cobalt, zinc, magnesium, calcium, silicon, yttrium, strontium and barium, or Examples include two or more metals. Examples of the constituent material of the semiconductor film include elemental elements such as silicon and germanium, compounds containing elements of Groups 3 to 5 and Groups 13 to 15 of the periodic table, metal oxides, and metal sulfides. , Metal selenides, metal nitrides, and the like. Examples of the constituent material of the conductive film include tin-doped indium oxide (ITO), fluorine-doped indium oxide (FTO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO). , Tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), tungsten oxide (WO ₃ ), and the like. In the present invention, a conductive film made of a conductive oxide is preferable, and tin-doped More preferably, it is an indium oxide (ITO) film. Examples of the constituent material of the insulating film include aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), silicon nitride (Si ₃ N ₄ ), and silicon oxynitride (Si _{4 ).} O ₅ N ₃ ) and the like.

The means for forming the metal film, the semiconductor film, the conductive film and the insulating film is not particularly limited and may be a known means. Examples of such forming means include mist CVD method, sputtering method, CVD method (vapor phase growth method), SPD method (spray pyrolysis deposition method), vapor deposition method, ALD (atomic layer deposition) method, coating method ( For example, dipping, dripping, doctor blade, inkjet, spin coating, brush coating, spray coating, roll coater, air knife coating, curtain coating, wire bar coating, gravure coating, inkjet coating, etc.) can be mentioned.

In the present invention, the substrate is preferably a transparent substrate (rigid substrate or flexible substrate). Examples of the rigid substrate include a glass substrate and an acrylic substrate. Examples of the flexible substrate include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin. Film, polyolefin resin film such as cyclic olefin resin, vinyl alcohol resin film, polyvinyl acetal resin film, vinyl resin film such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetal resin such as polyvinyl butyral (PVB) Film, polyetheretherketone (PEEK) resin film, polysulfone (PSF) resin film, polyphenylene sulfide resin film, polyethersulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin film , Polyimide resin film, polyether sulfone resin film, polyetherimide resin film, polyarylate resin film, acrylic resin film, cellulose resin film, triacetyl cellulose (TAC) resin film, etc. it can. In addition to these resin films, an inorganic glass film may be used as the substrate. Further, as the flexible substrate, for example, nanofibers such as carbon nanofibers, cellulose nanofibers, and cyclodextrin nanofibers may be used.

(Impregnation)
In the present invention, the dye is loaded on the substrate by impregnating the substrate with the raw material solution under reduced pressure. The dye may be carried on the substrate by impregnating the substrate with the raw material solution in the form of mist under reduced pressure. The depressurizing means is not particularly limited and may be a known means such as a vacuum pump. Further, the depressurization condition is not particularly limited as long as it does not impair the object of the present invention, and may be any of low vacuum, medium vacuum and high vacuum. In the present invention, the depressurization condition is preferably low vacuum, and more specifically 100 Pa to 90000 Pa. The impregnating means is not particularly limited, and a known impregnating means may be used. Examples of the impregnating means include a coating method, a dipping method, a spray method, a mist method, a brush coating method, a printing method, a potting method, a casting method and a spin coating method. In the present invention, since it is possible to more suitably express the effect of improving the loading rate in the presence of the above-mentioned preferred solvent under reduced pressure, the immersion method or the mist deposition method using a carrier gas is preferable, and the immersion method is More preferable. In the present invention, the impregnation may be performed while performing the decompression treatment by the decompression unit described above, or the impregnation may be performed after the decompression treatment is performed while maintaining a specific decompression condition. Further, in the present invention, it is preferable that the impregnation is performed by immersing the substrate in the raw material solution and then reducing the pressure. The treatment temperature of the impregnation is not particularly limited, but is preferably about 10°C to about 120°C. The impregnation time is not particularly limited, but is preferably about 10 seconds to about 10 minutes.

Further, in the present invention, the substrate may be directly supported, or may be supported through another layer such as a buffer layer (buffer layer) or a stress relaxation layer. The means for forming other layers such as the buffer layer (buffer layer) and the stress relaxation layer is not particularly limited and may be a known means, but in the present invention, it is preferably formed under reduced pressure. Further, in the present invention, a drying treatment may be carried out after the impregnation, if desired. The temperature of the drying treatment is not particularly limited in the present invention, but is preferably 200° C. or lower, and more preferably 100° C. or lower.

In the present invention, in a method for manufacturing an electronic device or an electronic component including a step of supporting a dye on a substrate, using the above-described method of supporting a dye of the present invention in the above step also makes it possible to obtain an electric property such as light conversion characteristics. This is preferable because an electronic device or electronic component having excellent characteristics can be obtained, and such a manufacturing method is also included in the present invention.

INDUSTRIAL APPLICABILITY The present invention can be suitably applied to the production of a functional film containing a metal or an organic substance. For example, in the case of producing a photoelectrode for a dye-sensitized solar cell, the dye (sensitizing dye) is used as the dye. For example, by using SK-1 and using chenodeoxycholic acid (CDCA) as the adsorbent, the dye-sensitized solar cell of good quality, which is excellent in light conversion characteristics and the like, can be preferably used while significantly improving the loading rate. A photoelectrode for a battery can be obtained. In addition, in the present invention, not only the photoelectrode for dye-sensitized solar cell, it is possible to obtain a functional material containing various metals or organic materials, for example, semiconductor materials, charge transport materials, conductive materials, photoconductive materials, A light emitting material, a coloring material, an insulating material, a semi-insulating material, etc. can be suitably obtained.

The material obtained by the method of the present invention is suitably used for electronic devices or electronic parts. Examples of the electronic device include a solar cell such as a dye-sensitized solar cell, a transistor, a diode, a photoelectric conversion element, and a light receiving element. Further, examples of the electronic device or electronic component include a television, a camera, a personal computer, a mobile phone, a smartphone, a display, an in-vehicle device, a household electric appliance, an industrial product, or a component thereof. The photoelectrode for a dye-sensitized solar cell is useful for a dye-sensitized solar cell. In the present invention, for example, when the photoelectrode for a dye-sensitized solar cell is used in a dye-sensitized solar cell or the like, a known means such as peeling the photoelectrode for the dye-sensitized solar cell from the substrate or the like is used. After that, it may be used for a dye-sensitized solar cell or the like, or may be used as it is for a dye-sensitized solar cell or the like.

Hereinafter, a suitable example in the case where the substrate supporting the dye by the method of the present invention is used in a dye-sensitized solar cell will be described.

When the substrate supporting the dye is used as a photoelectrode for a dye-sensitized solar cell in a dye-sensitized solar cell, in the method for supporting the dye, the substrate is preferably a transparent substrate, and has a surface. A transparent conductive substrate having a porous semiconductor layer formed thereon is more preferable. The transparent substrate has a light transmittance of preferably 10% or more, more preferably 50% or more, and most preferably 80 to 100% as measured according to JIS K 7361-1:1997. ..

As the transparent substrate, both a rigid substrate (for example, a glass substrate and an acrylic substrate) and a flexible substrate (for example, a film substrate) are preferably used. The rigid substrate is preferably a glass substrate in terms of heat resistance, and the type of glass is not particularly limited. Examples of the flexible substrate include those exemplified as the flexible substrate.

Further, when the substrate carrying the dye is used as a photoelectrode for a dye-sensitized solar cell in a dye-sensitized solar cell, the photoelectrode for the dye-sensitized solar cell (hereinafter, also referred to as "photoelectrode") A dye-sensitized solar cell can be manufactured by providing the counter electrode base material provided with an electrolyte layer and a counter electrode on it. Further, in such a method for producing a dye-sensitized solar cell, the dye-sensitized solar cell photoelectrode, using the method for supporting a dye of the present invention described above, an average pore diameter on a part or all of the surface is It is also preferable to use by forming a dye on a substrate including a porous layer of 100 nm or less, because a dye-sensitized solar cell excellent in light conversion characteristics can be industrially advantageously obtained. Furthermore, the dye-sensitized solar cell may include a conductive film between the substrate and the porous semiconductor layer and between the counter electrode and the counter electrode base material, respectively. Further, the conductive film is connected by a wiring, when the dye carried in the porous semiconductor layer by the method for producing a dye-sensitized solar cell of the present invention described below is excited by light to emit electrons, from the photoelectrode side. An electron flow that reaches the counter electrode side through the wiring and returns to the photoelectrode through the electrolyte layer is generated. In this way, the dye-sensitized solar cell converts light energy into electrical energy.

The electrolyte layer is a layer for separating the photoelectrode and the counter electrode and efficiently performing charge transfer. The electrolyte layer usually contains a supporting electrolyte, a redox couple (a pair of chemical species that can be reversibly converted to each other in the form of an oxidant and a reductant in a redox reaction), a solvent and the like.

Examples of the supporting electrolyte include salts containing cations such as lithium ions, imidazolium ions and quaternary ammonium ions.

The redox couple is not particularly limited as long as it can reduce the oxidized sensitizing dye, and known ones can be used. Examples of the redox couple include chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III)-thallium ion (I), ruthenium ion (III)-ruthenium ion (II), copper ion ( II)-copper ion (I), iron ion (III)-iron ion (II), cobalt ion (III)-cobalt ion (II), vanadium ion (III)-vanadium ion (II), manganate ion-peroxide Examples include manganate ion, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid and the like.

As the solvent for the electrolyte layer, those known as a solvent for forming an electrolyte layer of a solar cell can be used. Examples of the solvent for the electrolyte layer include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N,N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate and the like.

The electrolyte layer is prepared by applying the above-mentioned electrolytic solution (supporting electrolyte, redox couple and solvent) to the photoelectrode using a known method, or producing a cell having a photoelectrode and a counter electrode. It can be formed by injecting an electrolytic solution into the gap. Examples of the coating method include spin coating method, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method using a hopper, and multi-layer simultaneous coating. A method etc. can be adopted. In addition, heating may optionally be performed during the formation of the electrolyte layer.

The counter electrode is formed of, for example, a platinum layer or a carbon layer. In particular, the carbon layer can include fibrous carbon nanostructures. Here, the fibrous carbon nanostructure is not particularly limited, but, for example, carbon nanotube (CNT), vapor grown carbon fiber, or the like can be used. These may be used alone or in combination of two or more. Among them, as the fibrous carbon nanostructure, it is more preferable to use the fibrous carbon nanostructure containing CNT. Furthermore, nano-sized fine platinum or the like may be supported on the fibrous carbon nanostructure according to a conventional method. This is because the catalytic effect can be further improved.

The counter electrode base material is for supporting the counter electrode and is formed of, for example, the same material as that of the substrate. The counter electrode base material may be formed of a non-translucent material.

When the electrolyte layer is formed on the photoelectrode by coating, the counter electrode described above is placed on the formed electrolyte layer. As a method of installing the counter electrode, a known installation method using an adhesive resin or an adhesive sheet can be adopted.

(Conductive film)
The conductive film includes a metal such as platinum, gold, silver, copper, aluminum, indium, and titanium; a conductive metal oxide such as tin oxide and zinc oxide; indium-tin oxide (ITO) and indium-zinc oxide (IZO). ) Or the like; a fibrous carbon nanostructure, a carbon material such as fullerene; and a combination of two or more thereof; and the like. Note that the conductive film can be connected to a wiring.

The surface resistance value of the conductive film is preferably 500 Ω/sq. Or less, more preferably 150Ω/sq. Or less, more preferably 50Ω/sq. It is as follows. The conductive film can be formed by a known method such as a sputtering method or a coating method.

The photoelectric conversion element (dye-sensitized solar cell) obtained as described above is useful as a power generation means and can be applied to various uses. Specifically, it is provided with a photoelectric conversion element, and is further useful for a photoelectric conversion apparatus having a configuration including an inverter device for converting a direct current output from the photoelectric conversion device into an alternating current, an electric motor, a lighting fixture, and the like. There are solar cells and the like as suitable applications.

Examples of the present invention will be described below, but the present invention is not limited thereto.

(Production Example 1) Preparation of raw material solution SK-1 (pigment) and chenodeoxycholic acid (CDCA) were dissolved in tetrahydrofuran (THF) at 0.5 mmol/L and 5 mmol/L, respectively, to prepare a raw material solution. ..
(Example 1)
A dye-supported substrate was manufactured using the apparatus 11 shown in FIG.
That is, the raw material solution was placed in the impregnation chamber 12, and the substrate 14 was placed in the impregnation chamber 12. A vacuum pump 13a is connected to the impregnation chamber 12 via a vacuum valve 13b, the vacuum valve 13b is opened to operate the vacuum pump 13a, and the raw material solution containing the dye and the solvent is impregnated under reduced pressure to impregnate the substrate. The dye was supported in the pores of the porous layer. As the substrate 14, a polyethylene naphthalate (PEN) substrate having a porous layer (average pore diameter of 100 nm or less) made of titanium oxide particles on the surface was used.

(Comparative Example 1)
In the same manner as in Example 1 except that the pressure was not reduced during the impregnation, the dye was loaded on the PEN substrate having the porous layer on the surface.

(Comparative example 2)
1. Film Forming Apparatus The mist CVD apparatus 1 used in this comparative example will be described with reference to FIG. The mist CVD apparatus 1 includes a carrier gas source 2 for supplying a carrier gas, a flow rate control valve 3 for controlling the flow rate of the carrier gas sent from the carrier gas source 2, and a mist generation source 4 for accommodating a raw material solution 4a. A container 5 for containing water 5a, an ultrasonic transducer 6 attached to the bottom surface of the container 5, a film forming chamber 7, and a supply pipe 9 connecting the mist generation source 4 to the film forming chamber 7. The hot plate 8 installed in the film chamber 7 is provided. A substrate 10 is installed on the hot plate 8.

2. Preparation of Raw Material Solution SK-1 (dye) and chenodeoxycholic acid (CDCA) were dissolved in tetrahydrofuran (THF) at 0.5 mmol/L and 5 mmol/L, respectively, to prepare a raw material solution.

3. Preparation for film formation 2. The raw material solution 4a obtained in step 1 was housed in the mist generation source 4. Next, as the substrate 10, a polyethylene naphthalate (PEN) substrate having a porous layer made of titanium oxide particles (average pore diameter of 100 nm or less) formed on the surface thereof is placed on the hot plate 8 and the hot plate 8 is operated. The temperature inside the film forming chamber was raised to 40°C. Next, the flow rate control valve 3a is opened, the carrier gas is supplied from the carrier gas supply means 2a, which is a carrier gas source, into the film forming chamber 7, and the atmosphere in the film forming chamber 7 is sufficiently replaced with the carrier gas. The flow rate of the carrier gas was adjusted to 1.5 L/min. Note that nitrogen was used as the carrier gas.

4. Film formation Next, the ultrasonic vibrator 6 was vibrated at 2.6 MHz, and the vibration was propagated to the raw material solution 4a through the water 5a, whereby the raw material solution 4a was atomized to generate the mist 4b. The mist 4b is introduced into the film forming chamber 7 through the supply pipe 9 by the carrier gas, the substrate is impregnated with the mist 4b of the raw material solution, and the film is formed in the film forming chamber 7 at 40° C. under atmospheric pressure. The mist thermally reacted inside, and the dye was carried on the substrate 10. The film formation (impregnation) time was 2 minutes.

Evaluation 1. Comparison of Progress of Loading for Each Impregnation Time The progress of loading for each impregnation time in Examples and Comparative Examples was compared by observing the degree of coloring of the dye (red) on both front and back surfaces of the substrate. FIG. 4 shows appearance photographs of the front and back surfaces of the substrate for each impregnation time in Example 1 and Comparative Example 1 (normal dipping method). (A) shows the results of Comparative Example 1, and (b) shows the results of Example 1. As is apparent from FIG. 4, the case where the impregnation was performed for 5 minutes using the method of Example 1 and the case where the impregnation was performed for 30 minutes using the method of Comparative Example 1 showed the same coloring condition. I found out that From this result, according to the method for supporting a dye of the present invention, the coloring condition accompanying the mere progress of deposition is not shown in comparison with the ordinary impregnation method, and the dye is supported in the pores of the porous layer. As a result, a coloring degree equal to or more than the darkness due to the deposition is exhibited, and it is understood that not only the loading speed is remarkably improved, but also the substrate is more uniformly and satisfactorily loaded. Therefore, according to the method of the present invention, it is possible to support the dye and form the support layer in the porous layer without depending on the deposition of the dye.
Further, FIG. 5 shows appearance photographs of the front and back surfaces of the substrate for each impregnation time in Example 1 and Comparative Example 2 (mist CVD method). (A) shows the results of Comparative Example 2, and (b) shows the results of Example 1. As is clear from FIG. 5, the coloring condition when the impregnation is performed for 1 minute using the method of Example 1 is equal to or more than the coloring condition when the impregnation is performed for 2 minutes using the method of Comparative Example 2. I know there is. In Comparative Example 2, when the impregnation was performed for 1 minute, the color was not so much. From these results, according to the dye loading method of the present invention, the loading rate is not only significantly improved as compared with the conventional impregnation method using the mist CVD method, but also more uniform with respect to the substrate. Also, it is understood that they are well supported. Further, as is apparent from the photograph of the outer surface of the back surface of the substrate in FIG. 5, the dye loading method of the present invention has a sufficient loading amount and loading rate, unlike the case where the conventional mist CVD method is used. It can be seen that a good carrier layer is formed.

(Example 2 and Comparative Example 3)
In order to confirm reproducibility, each dye was carried in the same manner as in Example 1 and Comparative Example 1. As a result, the loading speed and uniformity in Example 2 and Comparative Example 3 were the same as those in Example 1 and Comparative Example 1, respectively.

(Example 3)
The substrate was made to carry the dye in the same manner as in Example 1 except that an iron organometallic complex was used as the dye. As a result, the carrying speed and the uniformity were the same as those in Example 1.

(Example 4)
A dye was carried on a substrate in the same manner as in Example 1 except that an organometallic complex of copper was used as the dye. As a result, the carrying speed and the uniformity were the same as those in Example 1.

(Example 5)
Example 1 except that SK-1 (dye) and chenodeoxycholic acid (CDCA) were dissolved in acetone at 0.5 mmol/L and 5 mmol/L, respectively, were used as the raw material solution. The dye was carried on the substrate in the same manner as in.

(Example 6)
A dye was carried on the substrate in the same manner as in Example 5 except that the impregnating apparatus shown in FIG. 2 was used as the impregnating apparatus, and the impregnation was performed according to the procedure described below.

(Procedure of impregnation in Example 6)
The raw material solution was placed in the impregnation chamber 12, and the substrate 14 was placed in the impregnation chamber 12. The vacuum pump 13a is connected to the impregnation chamber 12 via the vacuum valve 13b, the vacuum valve 13b is opened to operate the vacuum pump 13a, and the pressure in the impregnation chamber 12 is reduced to 100 Pa to 9000 Pa. The vacuum valve 13 was closed. Next, the solution injection valve 15b was opened, and the raw material solution 18 was injected into the impregnation chamber 12 from the solution tank 15a due to the pressure difference between the impregnation chamber 12 and the solution tank 15a, and the substrate 14 was impregnated with the raw material solution.

(Comparative Example 4)
Comparative Example 1 except that SK-1 (dye) and chenodeoxycholic acid (CDCA) were dissolved in acetone at 0.5 mmol/L and 5 mmol/L, respectively, as a raw material solution The dye was carried on the substrate in the same manner as in.

(Comparative example 5)
As a raw material solution, a solution prepared by dissolving SK-1 (dye) and chenodeoxycholic acid (CDCA) in a mixed solvent of 1-butanol and acetonitrile so that the concentrations are 0.2 mmol/L and 2 mmol/L, respectively. A dye was carried on a substrate in the same manner as in Comparative Example 1 except that the above was carried out.

Evaluation 2. Comparison of Progress of Loading for Each Impregnation Time The progress of loading for each impregnation time in Examples and Comparative Examples was compared by observing the degree of coloring of the dye (red) on both front and back surfaces of the substrate. FIG. 6 shows appearance photographs of the back surface of the substrate for each impregnation time in Examples 5 and 6 and Comparative Example 4 (normal dipping method). As is clear from FIG. 6, when the method of Example 5 was used for impregnation for 5 minutes, when the method of Example 6 was used for impregnation for 7 minutes, and when the method of Comparative Example 4 was used. It was found that the same degree of coloring was exhibited after 30 minutes. From this result, according to the method for supporting a dye of the present invention, the coloring condition accompanying the mere progress of deposition is not shown in comparison with the ordinary impregnation method, and the dye is supported in the pores of the porous layer. As a result, a coloring degree equal to or more than the darkness due to the deposition is exhibited, and it is understood that not only the loading speed is remarkably improved, but also the substrate is more uniformly and satisfactorily loaded. Therefore, according to the method of the present invention, it is possible to support the dye and form the support layer in the porous layer without depending on the deposition of the dye.

Evaluation 3. Measurement of open circuit voltage For the substrates after the impregnation treatment obtained in Example 5 (impregnation time 6 minutes) and Comparative Example 5 (impregnation time 40 minutes), the open circuit voltage was measured in order to evaluate the light conversion characteristics, The conversion efficiency was evaluated. An LED was used as the light source. The results are shown in Table 1. As is clear from Table 1, according to the method for supporting a dye of the present invention, even for a porous layer having a very small average pore size (100 nm or less), as compared with the case of using an ordinary impregnation method. It can be seen that the dye can be uniformly and satisfactorily supported, and a laminated structure having excellent light conversion characteristics can be obtained.

INDUSTRIAL APPLICABILITY The method for supporting a dye according to the present invention can be applied to various industries because the dye can be supported on various materials without limitation on the shape of the substrate. In particular, since a dye-supporting film can be suitably obtained, it is useful for photoelectric conversion elements (for example, dye-sensitized solar cells) and the like, and can be used in industrial fields such as solar cells and optical sensors.

1 Mist CVD Device 2 Carrier Gas Source 3 Flow Rate Control Valve 4 Mist Generation Source 4a Raw Material Solution 4b Mist 5 Container 5a Water 6 Ultrasonic Transducer 7 Film Forming Chamber 8 Hot Plate 9 Supply Pipe 10 Substrate 11 Impregnation Device 12 Impregnation Chamber 13a Vacuum Pump 13b Vacuum valve 14 Base (substrate)
15a Solution tank 15b Solution injection valve 16 Solution recovery valve 17 Leak valve 18 Raw material solution 21 Impregnation device

Claims (14)

A method of supporting the dye on the substrate by bringing the dye into contact with the substrate, wherein the substrate contains a porous layer having an average pore size of 100 nm or less on a part or all of the surface, and the dye has the average pore size. The method is characterized in that the contact is carried out by impregnating the substrate with a raw material solution containing the dye and a solvent under reduced pressure so that the dye is carried in the pores of the porous layer. The method according to claim 1, wherein the impregnation is performed by immersing the substrate in the raw material solution and then reducing the pressure. The method according to claim 1 or 2, wherein the dye is an organic dye or a metal complex dye. The method according to claim 1, wherein the dye is a metal complex dye. The method according to claim 1, wherein the dye is a metal complex dye containing a Group 8 metal of the periodic table. The method according to claim 1, wherein the solvent is an aprotic polar solvent. The method according to claim 1, wherein the boiling point of the solvent is 160° C. or lower. The method according to claim 1, wherein the porous layer is a porous semiconductor layer. The method according to claim 8, wherein the porous semiconductor layer is composed of semiconductor fine particles. The method according to claim 1, wherein the base body is a substrate. The method according to claim 1, wherein the impregnation is performed under a reduced pressure of 100 Pa to 90000 Pa. A method of manufacturing an electronic device or an electronic component, comprising the step of supporting a substrate, wherein the method according to any one of claims 1 to 11 is used in the step. A method for producing a dye-sensitized solar cell using at least a photoelectrode comprising a substrate carrying a dye, an electrolyte layer and a counter electrode, wherein the photoelectrode is the method according to any one of claims 1 to 11. A method for producing a dye, which is formed by supporting a dye on a substrate using. A method of adsorbing the dye on the substrate by bringing the dye into contact with the substrate, wherein the substrate contains a porous layer having an average pore size of 100 nm or less on a part or all of the surface, and the dye has the average pore size. The method is characterized in that the contact is carried out by impregnating the substrate with a raw material solution containing the dye and a solvent under a reduced pressure to adsorb the dye in the pores of the porous layer.