JP2020077719A - Method for supporting metal source and method of manufacturing electronic device or electronic component - Google Patents

Abstract

To provide a novel film forming method capable of allowing a substrate to uniformly and satisfactory support a metal source while greatly improving supporting speed.SOLUTION: There is provided a method for allowing a substrate to support a metal source by bringing the metal source into contact with the substrate. The substrate is allowed to support the metal source by performing the contact such that the substrate is impregnated under a reduced pressure (for example, 100-90,000 Pa) in a raw material solution containing the metal source and an aprotic polar solvent (for example, dimethylformamide).SELECTED DRAWING: None

Description

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

  Functional materials such as metal oxide thin films and metal-containing organic / inorganic compounds used in solar cells and liquid crystal display devices are generally formed by a sputtering method, a vapor deposition method, or a CVD (chemical vapor deposition) method using an organometallic compound. Method) etc. The metal-organic chemical vapor deposition method is difficult to handle because the metal-organic compounds that are the raw materials have explosiveness and toxicity, and it is difficult to increase the size, and additional equipment such as an exhaust gas treatment device is also required. A high level of safety design is required as a whole. Both of these requirements are major issues that hinder cost reduction.

  Under these 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 investigated to form a perovskite-type composite oxide having a perovskite structure by using mist CVD (Patent Document 2). Perovskite type complex oxides have various physical properties and are therefore used and studied in a wide range of fields. Such a perovskite-type composite oxide has physical properties such as anion conduction such as oxide ion conduction, cation conduction such as lithium ion conduction, proton conduction, electron conduction, ferroelectricity, ferromagnetism or high temperature superconductivity. Show. On the other hand, for example, when the perovskite-type composite oxide is formed on a porous body such as titanium oxide, it is difficult to sufficiently support the perovskite-type composite oxide on the substrate. According to the method, there is a problem that the shape of the substrate is restricted. The loading amount was still insufficient, the thickness of the loading layer was thin, and the loading rate was not satisfactory for industrial application.

Further, as another method, a dipping method and the like have been studied, but the metal source was not sufficiently supported, and a step of spraying after dipping was necessary. However, even if the metal source is supported in this way, there is a problem similar to the above mist CVD, and it is not satisfactory.
In addition, in the field of coating, for example, in Patent Document 3, a viscous coating liquid containing a scale-like metal flake of 5 to 50 μm and a binder is brought into contact with an object to be pressure-reduced, and the pressure is directly reduced. It is described that a coating film having two or more layers is formed by dipping treatment in. However, such a method has a problem that an undesired coating film (overcoat film) is formed on the intended coating film. Further, the method described in Patent Document 3 does not support a metal source in the pores of the porous substrate but improves the adhesion between the irregularities on the substrate surface and the coating film. There is a problem that the quality of the coat film is poor.

  As described above, the mist CVD method has been particularly attracting attention in recent years 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. Further, the coating method also does not try to support the metal source into the pores of the porous structure, and therefore, a method capable of easily and efficiently producing a highly functional material or a new material. Was long-awaited.

JP, 2013-251411, A International Publication No. 2017/1110953 Patent No. 5534780

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 method for supporting a metal source on a substrate, which is capable of industrially supporting the metal source.

As a result of earnest studies to achieve the above-mentioned object, the present inventors have proposed a method of supporting the metal source on the substrate by bringing the metal source into contact with the substrate, wherein the contact is performed under reduced pressure. When the above-mentioned substrate is impregnated with a raw material solution containing an aprotic polar solvent and aprotic polar solvent, surprisingly, compared with the case where the conventional mist CVD or the impregnation method is used, the loading speed is remarkably improved. In addition, it was found that even a substrate having a porous layer, for example, can support a metal source uniformly and satisfactorily without limitation on the shape of the substrate. It was found that the above problems can be solved 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 metal source on the substrate by bringing the metal source into contact with the substrate, wherein the contact is performed by applying a raw material solution containing the metal source and an aprotic polar solvent under reduced pressure to the substrate. The method is characterized by carrying out impregnation with.
[2] The method according to [1] above, wherein the impregnation is performed by impregnating the substrate with the raw material solution and then reducing the pressure.
[3] The substrate includes a porous layer on a part or all of the surface, the metal source is smaller than the average pore diameter of the porous layer, and the metal source is supported in the pores of the porous layer. The method according to [1] or [2].
[4] The method according to [3], wherein the average pore diameter is 100 nm or less.
[5] The method according to any one of [1] to [4], wherein the metal source is a metal compound.
[6] The method according to any one of [1] to [5] above, wherein the metal source is a metal halide.
[7] The method according to any one of [1] to [6] above, wherein the metal source contains at least one metal selected from Groups 8 to 14 of the periodic table.
[8] The method according to any one of [1] to [7] above, wherein the aprotic polar solvent contains a hetero atom-containing organic solvent.
[9] The method according to any one of [1] to [8], wherein the boiling point of the aprotic polar solvent is 160 ° C. or lower.
[10] The method according to any one of [1] to [9], wherein the raw material solution contains an additive containing halogen.
[11] The method according to the above [10], wherein the additive is an amine compound.
[12] The method according to any one of [1] to [11], wherein the base body is a substrate.
[13] The method according to any one of [1] to [12] above, wherein the impregnation is performed under a reduced pressure of 100 Pa to 90000 Pa.
[14] A method for manufacturing an electronic device or an electronic component, including the step of supporting a metal source on a substrate, characterized in that the method according to any one of [1] to [13] is used in the step. Manufacturing method.
[15] A method for producing a photoelectric conversion element using at least a photoelectric conversion layer and an electrode, wherein the photoelectric conversion layer is formed by using the method according to any one of [1] to [13] above. A method for manufacturing, comprising forming and using a metal source on a substrate.

  According to the method for supporting a metal source of the present invention, the metal source 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.

  The method for supporting a metal source of the present invention is a method for supporting the metal source on the substrate by bringing the metal source into contact with a substrate, wherein the contact is performed under reduced pressure with the metal source and an aprotic polar solvent. Is performed by impregnating the substrate with a raw material solution containing

(Raw material solution)
The raw material solution is in the form of a solution containing a metal source and an aprotic polar solvent, and is not particularly limited as long as it can support the metal source on the substrate, and may contain an inorganic material. , May contain an organic material. Further, the raw material solution may contain both an inorganic material and an organic material.

  The metal source is not particularly limited as long as it contains a metal. Examples of the metal source include simple metals or metal compounds containing at least one metal selected from Groups 1 to 15 of the periodic table. In the present invention, the metal source preferably contains at least one metal selected from Groups 8 to 14 of the Periodic Table, and Group 8 metals and Group 14 metals of the Periodic Table. More preferably, at least one metal selected from the above is included. Here, the "periodic table" means a periodic table defined by the International Union of Pure and Applied Chemistry (IUPAC). Examples of the metal of Group 8 of the periodic table include iron (Fe), ruthenium (Ru), osmium (Os) and the like. Examples of the Group 9 metal of the periodic table include cobalt (Co), rhodium (Rh), and iridium (Ir). Examples of the Group 10 metal of the periodic table include nickel (Ni), palladium (Pd), platinum (Pt), and the like. Examples of the Group 11 metal of the periodic table include copper (Cu), silver (Ag), gold (Au), and the like. Examples of the Group 12 metal of the periodic table include zinc (Zn), cadmium (Cd), and mercury (Hg). Examples of the Group 13 metal of the periodic table include aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and the like. The Group 14 metal of the periodic table includes, for example, silicon (Si), germanium (Ge), tin (Sn), lead (Pb), and the like. In the present invention, Pb is preferable.

  The metal source may be a simple substance of the metal or a metal compound of the metal, but in the present invention, a metal compound of the metal (organic compound or inorganic compound) is preferable. .. Examples of the organic metal compound include organic complexes and organic metal salts. Examples of the form of the organic complex include an acetylacetonate complex, a carbonyl complex, an ammine complex, a hydride complex, a phosphine complex, a pyridine complex, a terpyridine complex, a β-diketone complex, an azo metal complex, a bisphenyldiotylol metal complex, and a picinoline. Complex, quinolinol complex, benzoquinolinol complex, acridinol complex, phenanthdinol complex, hydroxyphenyloxazole complex, hydroxyphenylthiazole complex, hydroxydiaryloxadiazole complex, hydroxydiarylthiadiazole complex, hydroxyphenylpyridine complex, hydroxyphenylbenzimidazole complex , Hydroxybenzotriazole complex, hydroxyfulborane complex, phenanthroline complex, phthalocyanine complex and the like. Examples of the organic metal salt include salts of organic acids such as metal acetates, metal oxalates and metal citrates, alkoxides and dialkylamide salts. Examples of the inorganic compound include metal halides (eg, fluorides, chlorides, bromides, iodides, etc.) or metal inorganic acid salts (nitrates, hydrochlorides, sulfates, phosphates, etc.), and the like. Be done. In the present invention, when the metal source is a metal halide, the effects such as loading speed and loading uniformity can be better exerted, and by combination with a preferred solvent described later, It is preferable because the effect can be exhibited more satisfactorily. In the present invention, the metal source may further contain an ammonium compound.

  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, 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-based 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. The boiling point of the aprotic polar solvent is not particularly limited, but in the present invention, it is preferably 210 ° C or lower, more preferably 160 ° C or lower. 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 metal source 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. It may contain an inorganic solvent such as or an organic solvent such as an alcohol.

Further, the raw material solution may be mixed with additives such as hydrohalic acid, an oxidizing agent, and 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, and organic peroxides such as peracetic acid and nitrobenzene. Examples of the adsorbent include co-adsorbents 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 saturated fatty acid or 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. In the present invention, it is preferable that the raw material solution contains an additive containing halogen, because it is possible to further improve the loading rate of the metal source, and it is more preferable to contain an amine compound containing halogen. .. More specifically, examples of the amine compound include compounds represented by the following formula (I).
RNH ₃ X (I)
(In the formula, X is F, Cl, Br or I, and R is an alkyl group having 1 or more carbon atoms, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group or an aromatic heterocyclic group.)

(Base)
The substrate is not particularly limited as long as it can support the metal source to be carried. 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 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. , A spiral shape, a spherical shape, a ring shape, and the like, 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 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. .. The constituent metal of the metal film is, 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 having elements of Groups 3 to 5 and 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. Besides these resin films, an inorganic glass film may be used as the substrate. Moreover, as the flexible substrate, for example, nanofibers such as carbon nanofibers, cellulose nanofibers, and cyclodextrin nanofibers may be used.

  Further, in the present invention, it is also preferable that the substrate includes a porous layer on a part or all of the surface thereof, and such a substrate and the metal source having a smaller average pore diameter than the porous layer are used. Thereby, the metal source can be favorably supported in the pores of the porous layer. The average pore diameter of the porous layer is not particularly limited in the present invention, but is preferably 1 μm or less, more preferably 100 nm or less. In this case, the size of the metal source is not particularly limited, but is preferably 100 nm or less, more preferably 10 nm or less. According to the method for supporting a metal film of the present invention, the shape of the substrate is not limited, and even if the substrate includes a porous layer having such fine pores, the pores of the porous layer are uniformly and satisfactorily obtained. The metal source can be supported inside. The "average pore diameter" is a value obtained by doubling the average pore radius r obtained according to JIS K1150, which is obtained by the mercury intrusion method or the nitrogen adsorption isotherm. In the present invention, for example, for convenience, the average pore size may be calculated by measurement by SEM observation. The porosity of the porous layer is also not particularly limited, but in the present invention, it is preferably 20% to 90%, and more preferably 40% to 90%. 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. In the present invention, the porous layer preferably contains metal oxide particles. Examples of the metal oxide constituting the metal oxide particles include silicon oxide, titanium oxide, tin oxide, tungsten oxide, zinc oxide, indium oxide, niobium oxide, iron oxide, nickel oxide, cobalt oxide, strontium oxide, and oxide. Examples thereof include tantalum, antimony oxide, lanthanoid oxide, yttrium oxide, vanadium oxide and the like. The particle size of the metal oxide particles is also not particularly limited and is usually 5 nm to 1 μm, but in the present invention, it is preferably 5 nm to 100 nm. The thickness of the porous layer is not particularly limited in the present invention, and is usually 1 μm to 1000 μm, preferably 1 μm to 200 μm.

(Impregnation)
In the present invention, the raw material solution is impregnated with the substrate under reduced pressure to support the metal source on the substrate. The metal source may be supported on the substrate by impregnating the substrate 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 depressurizing 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 reduced pressure 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 means described above, or after the decompression treatment, the impregnation may be 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 for the impregnation is not particularly limited, but is preferably about 10 ° C to about 120 ° C. The treatment time of the impregnation 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 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. Although the temperature of the drying treatment is not particularly limited in the present invention, it 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 metal source on a substrate, using the above-mentioned method for supporting a metal source of the present invention in the step also provides more light conversion characteristics and the like Since it is possible to obtain an electronic device or electronic component having excellent electric characteristics, the manufacturing method is also included as one of the present inventions.

  INDUSTRIAL APPLICABILITY The present invention can be suitably applied to the production of a functional film containing a metal. For example, in the case of producing a perovskite film, the metal source (perovskite precursor) may be, for example, a lead halide or the like. By using a mixture of the metal halide of 1. and an ammonium compound such as methylammonium halide, it is possible to suitably obtain a high-quality perovskite film having excellent light conversion characteristics and the like, while significantly improving the loading rate. .. In the present invention, not only the perovskite film, but also functional materials containing various metals can be obtained. For example, semiconductor materials, charge transport materials, conductive materials, photoconductive materials, light emitting materials, coloring materials, insulating materials. A semi-insulating material or the like can be suitably obtained.

  The material obtained by the method of the present invention is suitable for use in electronic devices or electronic parts. Examples of the electronic device include solar cells such as perovskite solar cells, transistors, diodes, photoelectric conversion elements, and light receiving elements. 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 perovskite film is useful for photoelectric conversion elements and the like. In the present invention, for example, when the perovskite film is used for a photoelectric conversion element or the like, the perovskite film may be used for the photoelectric conversion element or the like after using a known means such as peeling from the substrate or the like, It may be used as it is for a photoelectric conversion element or the like.

  Hereinafter, a preferred example in which the perovskite film is used in a photoelectric conversion element will be described.

  When the perovskite film is used for a photoelectric conversion element, in the method for manufacturing the perovskite film, the base is preferably a transparent substrate, and more preferably a transparent conductive substrate having an electrode formed on the surface thereof. .. 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 (such as a glass substrate and an acrylic substrate) and a flexible substrate (such as 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.

  When the perovskite film is used for a photoelectric conversion element, a first electrode, an electron transport layer, a photoelectric conversion layer having a semiconductor and a perovskite structure, a hole transport layer, and a second electrode are provided on the transparent substrate. Thus, a photoelectric conversion element can be manufactured. Further, in such a method for producing a photoelectric conversion element using at least a photoelectric conversion layer (including a perovskite film) and an electrode, the photoelectric conversion layer is formed by using the above-described metal source supporting method of the present invention. It is also preferable to use by forming a metal source on a substrate so that a photoelectric conversion element having excellent light conversion characteristics can be industrially advantageously obtained.

  The first electrode is usually disposed between the transparent substrate and the photoelectric conversion layer, and is provided on one surface opposite to the light incident direction of the transparent substrate, but is not particularly limited in the present invention. Not done. The first electrode preferably has a light transmittance of 60% or more, more preferably 80% or more, most preferably 90% to 100%. The light transmittance is the same as that described in the description of the transparent substrate.

The material forming the first electrode is not particularly limited and may be a known material. For example, metals such as platinum, gold, silver, copper, magnesium, aluminum, rhodium and indium or alloys thereof, SnO ₂ , CdO, ZnO, CTO series (CdSnO ₃ , Cd ₂ SnO ₄ , CdSnO ₄ ), In ₂ O. ₃ , metal oxides such as CdIn ₂ O _{4, and the} like. Among these, the metal is preferably gold, silver or magnesium or an alloy thereof, and a grid-patterned film having openings or fine particles or nanowires dispersed and applied to have light transmittance. The film is preferably used. Further, as the metal oxide, preferably, a composite (doped) material obtained by adding one or more selected from Sn, Sb, F and Al to the metal oxides exemplified above is used. More preferred are conductive metal oxides such as Sn-doped In ₂ O ₃ (ITO), Sb-doped SnO ₂ and F-doped SnO ₂ (FTO), and among them, from the viewpoint of heat resistance. FTO is most preferred. The amount of the material forming the first electrode applied to the substrate is not particularly limited, but is preferably about 1 to 100 g per 1 m ^{2 of} the substrate.

  The means for forming the first electrode is not particularly limited as long as it does not impair the object of the present invention, and known means may be used. Means for forming the first electrode include, for example, 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, dropping, doctor blade, inkjet, spin coating, brush coating, spray coating, roll coater, air knife coating, curtain coating, wire bar coating, gravure coating, inkjet coating, etc.) and the like.

  The first electrode is preferably a transparent conductive substrate provided on the transparent substrate. The average thickness of the transparent conductive substrate is not particularly limited, but is preferably in the range of about 0.1 mm to 5 mm. The surface resistance of the transparent conductive substrate is preferably 50Ω / □ or less, more preferably 20Ω / □ or less, and most preferably 10Ω / □ or less. Since the lower limit of the surface resistance of the transparent conductive substrate is preferably as low as possible, it is not necessary to specify it, but 0.01 Ω / □ or more is sufficient. The preferable range of the light transmittance of the transparent conductive substrate is the same as the preferable range of the light transmittance of the transparent substrate.

The electron transport layer usually has a film shape (layer shape) as a short circuit prevention means, a sealing means, and a rectifying function, and is arranged between the first electrode and the photoelectric conversion layer (semiconductor layer). The electron transport layer preferably comprises a porous structure. When the porosity of the electron transport layer is C [%] and the porosity of the semiconductor layer is D [%], D / C is preferably about 1.1 or more, and about 5 or less. More preferably, it is more than about 10 and most preferably about 10 or more. The upper limit of D / C is preferably as large as possible and is not particularly limited, but is usually about 1000 or less. Thereby, the electron transport layer and the semiconductor layer can exhibit their respective functions more suitably. The electron transport layer is usually formed on the first electrode.
More specifically, the porosity C of the electron transport layer is preferably a dense layer, and more specifically, for example, preferably about 20% or less, and about 5% or less. More preferably, it is most preferably about 2% or less. As a result, effects such as short circuit prevention and rectification can be further improved. Here, since the lower limit of the porosity of the electron transport layer is preferably as small as possible, it is not particularly limited, but is usually about 0.05% or more.

  The average thickness (film thickness) of the electron transport layer is, for example, preferably about 0.001 to 10 μm, more preferably about 0.005 to 0.5 μm. Thereby, the effect can be further improved.

The constituent material of the electron transport layer is not particularly limited, but an n-type semiconductor can be used. For example, in the case of inorganic substances, zinc, niobium, tin, titanium, vanadium, indium, tungsten, tantalum, zirconium, molybdenum, manganese, iron, copper, nickel, iridium, rhodium, chromium, ruthenium or their oxides, α-type oxidation Gallium, β-type gallium oxide, oxide semiconductors such as IGZO, nitride semiconductors such as GaN, silicon-containing semiconductors such as SiC, strontium titanate, calcium titanate, barium titanate, magnesium titanate, and strontium niobate. Such a perovskite, or a complex oxide or oxide mixture thereof, one kind or a combination of two or more kinds of various metal compounds such as CdS, CdSe, TiC, Si ₃ N ₄ , SiC and BN should be used. You can In the case of organic substances, fullerene or its derivative (for example, phenyl-C61-butyric acid methyl ester ([60] PCBM), phenyl-C61-butyric acid n-butyl ester ([60] PCBnB), phenyl-C61-butyric acid isobutyl ester). ([60] PCBiB), phenyl-C61-butyric acid n-hexyl ester ([60] PCBH), phenyl-C61-butyric acid n-octyl ester ([60] PCBO), diphenyl-C62-bis (butyric acid methyl ester) ( Bis [60] PCBM), phenyl-C71-butyric acid methyl ester ([70] PCBM), phenyl-C85-butyric acid methyl ester ([84] PCBM), thienyl-C61-butyric acid methyl ester ([60] ThCBM), C60. Pyrrolidine tris acid, C60 pyrrolidine tris acid ethyl ester, N-methyl fulleropyrrolidine (MP-C60), (1,2-methanofullerene C60) -61-carboxylic acid, (1,2-methanofullerene C60) -61- Carboxylic acid t-butyl ester), octaazaporphyrin, and the like, perfluoro compounds (for example, perfluoropentacene and perfluorophthalocyanine) in which hydrogen atoms of a p-type organic semiconductor compound are replaced by fluorine atoms, naphthalene tetracarboxylic acid anhydride, naphthalene Examples thereof include aromatic carboxylic acid anhydrides such as tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized compound as a skeleton.

  Note that, for example, when the hole transport layer is a p-type semiconductor and a metal is used for the electron transport layer, the work function value is smaller than that of the hole transport layer, and Schottky contact is performed. It is preferable to use one that does. Further, for example, when a metal oxide is used for the electron transport layer, it is possible to use one that is in ohmic contact with the transparent conductive layer and has an energy level in the conduction band lower than that of the porous semiconductor layer. preferable. At this time, by selecting an oxide as a constituent material of the electron transport layer, the electron transfer efficiency from the porous semiconductor layer (photoelectric conversion layer) to the electron transport layer can be improved. Above all, a titanium oxide layer containing titanium oxide as a main component and having an electric conductivity equivalent to that of the semiconductor layer (photoelectric conversion layer) is preferable as the electron transport layer. In this case, the titanium oxide layer may be either anatase type titanium oxide or rutile type titanium oxide having a relatively high dielectric constant.

  The means for forming the electron transport layer is not particularly limited and may be a known means as long as the object of the present invention is not impaired. Examples of the means for forming the electron transport layer 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. The method (for example, dipping, dropping, 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 used.

  The photoelectric conversion layer usually includes a semiconductor and a perovskite structure. Here, the perovskite structure includes the above-mentioned perovskite film. In the present invention, it is preferable that the perovskite thin film comprises a semiconductor layer containing the semiconductor formed on a part or all of the surface.

The semiconductor is not particularly limited and may be a known one. Examples of the semiconductor include elemental elements such as silicon and germanium, compounds having elements of Groups 3 to 5 and Groups 13 to 15 of the periodic table, metal oxides, metal sulfides, and metal selenium. Compounds, metal nitrides, and the like. Preferred semiconductors include, for example, gallium oxide, titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide. Oxide, indium, cerium, yttrium, lanthanum, vanadium, niobium oxide, or tantalum oxide, cadmium sulfide, zinc sulfide, lead sulfide, silver sulfide, antimony or bismuth sulfide, Examples thereof include selenide of cadmium or lead, telluride of cadmium, and the like. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium, gallium-arsenic or copper-indium selenides, copper-indium sulfides, and titanium nitrides. More specifically, specific examples of the _{semiconductor, Ga 2 O 3, TiO 2} , SnO 2, Fe 2 O 3, WO 3, ZnO, Nb 2 O 5, CdS, ZnS, PbS, Bi 2 S 3 , CdSe, CdTe, GaP, InP, GaAs, CuInS ₂ , CuInSe ₂ , Ti ₃ N _{4 and the} like. The above semiconductors may be used alone, or a plurality of semiconductors may be used in combination. For example, several kinds of the above-mentioned metal oxides or metal sulfides may be used together, or several kinds may be mixed and used. At this time, when a component other than the metal oxide or metal sulfide is added as a semiconductor, the mass ratio of the additional component to the metal oxide or metal sulfide semiconductor is preferably 30% or less.

  Examples of the shape of the semiconductor include a filler shape, a particle shape, a conical shape, a columnar shape, a tubular shape, and a flat plate shape, and are not particularly limited. Further, as the semiconductor layer, a film-like one formed by aggregating these semiconductors having a filler shape, a particle shape, a conical shape, a columnar shape, a tubular shape or the like may be used. In this case, a semiconductor whose surface is previously coated with a perovskite film may be used, or the perovskite film may be coated after forming a layer made of the semiconductor. When the semiconductor has a particulate shape, it is preferably a primary particle and has an average particle size of about 1 to 5000 nm, more preferably about 2 to 100 nm. The “average particle size” of the semiconductor is the average particle size (primary average particle size) of the primary particle diameter when 100 or more samples are observed with an electron microscope.

  The method for forming the semiconductor is not particularly limited as long as it does not impair the object of the present invention, and known means can be used. Examples of the semiconductor forming means include a mist CVD method, a sputtering method, a CVD method (vapor phase growth method), an SPD method (spray pyrolysis deposition method), a vapor deposition method, and an ALD (atomic layer deposition) method. ..

  The semiconductor may be surface-treated with an organic base. Examples of the organic base include diarylamine, triarylamine, pyridine, 4-t-butylpyridine, polyvinylpyridine, quinoline, piperidine, amidine and the like, and among them, pyridine, 4-t-butylpyridine and polyvinylpyridine are preferable. .. The surface treatment method is not particularly limited, and known means may be used. For example, when the organic base is a liquid, a solution (organic base solution) dissolved in an organic solvent is prepared as it is when it is a solid, and the semiconductor is added to the liquid or organic base solution at about 0 to 80 ° C. for about 1 minute. The surface treatment of the semiconductor can be carried out by immersing the semiconductor for about 24 hours.

  The means for coating the perovskite film is as described above. In the present invention, a substrate on which a semiconductor, an electron transport layer and a first electrode are formed may be used for forming the perovskite film.

  The hole transport layer usually contains a polymer (preferably a conductive polymer). The hole transport layer usually has a function of supplying electrons to the perovskite film oxidized by photoexcitation to reduce the electrons, and transport holes generated at the interface with the photoelectric conversion layer to the second electrode. The hole transport layer is preferably filled not only in the layered portion formed on the porous semiconductor layer, but also in the voids of the porous semiconductor layer.

Examples of the constituent material of the hole transport layer include selenium, iodide such as copper iodide (CuI), cobalt complex such as layered cobalt oxide, CuSCN, MoO ₃ , NiO, and organic hole transport material. .. Examples of the iodide include copper iodide (CuI). Examples of the layered cobalt oxide include A _x CoO ₂ (A = Li, Na, K, Ca, Sr, Ba; 0 ≦ X ≦ 1). Examples of the organic hole transport material include poly-3-hexylthiophene (P3HT), polythiophene derivatives such as polyethylenedioxythiophene (PEDOT), 2,2 ′, 7,7′-tetrakis- (N, N- Di-p-methoxyphenylamine) -9,9'-spirobifluorene (spiro-MeO-TAD) and other fluorene derivatives, polyvinylcarbazole and other carbazole derivatives, triphenylamine derivatives, diphenylamine derivatives, polysilane derivatives, polyaniline derivatives, etc. Is mentioned.

  The method for forming the hole transport layer is not particularly limited as long as the object of the present invention is not impaired, and known means can be used. Examples of the means for forming the hole transport layer 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, Examples thereof include coating methods (for example, dipping, dropping, doctor blade, inkjet, spin coating, brush coating, spray coating, roll coater, air knife coating, curtain coating, wire bar coating, gravure coating, inkjet coating, etc.).

  The second electrode is not particularly limited as long as it has conductivity and functions as an electrode. For example, even if it is an insulating material, if the conductive material layer is provided on the side facing the hole transport layer and can be used as an electrode, this can be used as the second electrode. In the present invention, the second electrode preferably has good contact with the hole transport layer. It is also preferable that the second electrode has a small work function difference from the hole transport layer and is chemically stable. Such materials are not particularly limited, but metal thin films such as gold, silver, copper, aluminum, platinum, rhodium, magnesium and indium, carbon, carbon black, conductive polymers, conductive metal oxides (indium). -Tin composite oxides, tin oxide doped with fluorine, etc.) and other organic conductors. The average thickness of the second electrode is also not particularly limited, but is preferably about 10 to 1000 nm. The surface resistance of the second electrode is not particularly limited, but is preferably low, and specifically, the range of the surface resistance of the second electrode is preferably 80Ω / □ or less, more preferably 20Ω / □. It is below. The lower limit of the surface resistance of the second electrode is preferably as low as possible and is not particularly limited, but may be 0.1Ω / □ or more.

  The method for forming the second electrode is not particularly limited as long as it does not impair the object of the present invention, and known means can be used. Examples of the means for forming the second electrode include a mist CVD method, a sputtering method, a CVD method (vapor phase growth method), an SPD method (spray pyrolysis deposition method), and a vapor deposition method.

  The photoelectric conversion element 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 element 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.

(Example 1)
1. Impregnation Apparatus The impregnation apparatus 11 used in this example will be described with reference to FIG. The impregnation device 11 includes an impregnation chamber (decompression container) 12, a vacuum pump 13a and a vacuum valve 13b for decompressing the impregnation chamber, a substrate 14 installed in the impregnation chamber 12, and an atmosphere for opening the impregnation chamber 12 to the atmosphere. A leak valve 17 is provided.

2. Preparation of raw material solution In 50 mL of dimethylformamide (DMF), 11.52252 g of lead iodide and 3.9743 g of methylammonium iodide were dissolved to obtain a raw material solution.

3. Preparation for impregnation 2. The raw material solution obtained in step 1 and the substrate 14 were placed in the impregnation chamber 12. 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.

4. Impregnation treatment Next, the vacuum pump 13a was operated to impregnate (immerse) the interior of the impregnation chamber 12 while reducing the pressure inside the substrate, and the metal source was carried on the substrate. The impregnation time was 5 minutes, and depressurization was continued until the impregnation was completed. After the impregnation, the leak valve 17 was opened to open the impregnation chamber 12 to the atmosphere, and the substrate 14 was taken out. Further, the obtained substrate with a carrier was dried at 70 ° C. for 1 hour.

(Comparative Example 1)
The metal source was loaded on the PEN substrate having the porous layer on the surface in the same manner as in Example 1 except that the pressure was not reduced during the impregnation and the impregnation time was 60 minutes.

(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 vibrator 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 In 50 mL of dimethylformamide (DMF), 11.52252 g of lead iodide and 3.9743 g of methylammonium iodide were dissolved to obtain 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 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 was opened, the carrier gas was supplied from the carrier gas supply means 2a and 2b, which are carrier gas sources, into the film forming chamber 7, and the atmosphere in the film forming chamber 7 was sufficiently replaced with the carrier gas. After that, 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. This 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 forming chamber 7 is heated at 40 ° C. under atmospheric pressure. The mist thermally reacted inside, and a perovskite film was formed 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 perovskite support (brown) 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). As is clear from FIG. 4, the case where impregnation was performed for 5 minutes using the method of Example 1 and the case where impregnation was performed for 60 minutes using the method of Comparative Example 1 showed the same coloring condition. I found out that From these results, according to the method for supporting the metal source of the present invention, compared with the usual impregnation method, the degree of coloring accompanying mere progress of deposition is not shown, and the metal source is supported in the pores of the porous layer. By doing so, it is possible to reach a coloring degree equal to or more than the darkness due to the deposition, and not only the loading speed is remarkably improved, but also it is found that the substrate is more uniformly and satisfactorily loaded. Therefore, according to the method of the present invention, it is possible to support the metal and form the supporting layer in the porous layer without depending on the deposition of the metal source.
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). As is apparent 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 addition, in Comparative Example 2, when the impregnation was carried out for 1 minute, the color was not so colored. From these results, according to the metal source supporting method of the present invention, not only the supporting speed is remarkably improved as compared with the conventional impregnation method using the mist CVD method, but also more excellent for the substrate. It can be seen that the particles are uniformly and satisfactorily supported. Further, as is apparent from the photograph of the appearance of the back surface of the substrate in FIG. 5, the metal source supporting method of the present invention has a sufficient supporting amount and supporting rate, unlike the case where the conventional mist CVD method is used. It can be seen that a good supporting layer is formed.

(Example 2 and Comparative Example 3)
In order to confirm reproducibility, supporting treatment was performed 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.

Evaluation 2. Measurement of open circuit voltage With respect to the substrates after the impregnation treatment obtained in Examples 1 and 2 and Comparative Examples 1 and 3, the open circuit voltage was measured in order to evaluate the light conversion characteristics. A fluorescent lamp and an LED were 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 metal source of the present invention, a porous layer having a very fine average pore diameter (100 nm or less) is used as compared with the case of using a normal impregnation method. It can be seen that the metal source can be uniformly and satisfactorily supported, and a laminated structure having excellent light conversion characteristics can be obtained.

(Example 3)
A metal source was supported on the substrate in the same manner as in Example 1 except that an organometallic complex of iron was used as the metal source. As a result, the carrying speed and the uniformity were equivalent to those in the case of Example 1, and the obtained substrate with the carrier was excellent in light conversion characteristics as in the case of Example 1. ..

(Example 4)
A metal source was supported on the substrate in the same manner as in Example 1 except that an organometallic complex of copper was used as the metal source. As a result, the carrying speed and the uniformity were equivalent to those in the case of Example 1, and the obtained substrate with the carrier was excellent in light conversion characteristics as in the case of Example 1. ..

(Example 5)
1. Impregnation Device The impregnation device 21 used in this example will be described with reference to FIG. The impregnation device 21 includes a decompression chamber 12 as an impregnation chamber, a vacuum pump 13a and a vacuum valve 13b for decompressing the impregnation chamber 12, a substrate 14 installed in the impregnation chamber 12, and a solution tank for containing a raw material solution. 15a and a solution injection valve 15b for connecting the solution tank to the impregnation chamber 12, a solution recovery valve 16 for recovering an unreacted solution, and a leak valve 17 for opening the impregnation chamber 12 to the atmosphere.

2. Impregnation Treatment A metal source was supported on the substrate in the same manner as in Example 1 except that the impregnation apparatus shown in FIG. 2 was used as the impregnation apparatus and the impregnation was performed according to the procedure described below. As a result, the carrying speed was equivalent to that in Example 1.

(Impregnation procedure in Example 5)
The raw material solution was stored in the solution tank 15a. Further, the substrate 14 is installed in the impregnation chamber 12, the vacuum valve 13b is opened and the vacuum pump 13a is operated to reduce the pressure in the impregnation chamber 12 to fall within the range of 100 Pa to 9000 Pa. I closed it. Then, 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 by the pressure difference between the impregnation chamber 12 and the solution tank 15a, and the substrate 14 was impregnated with the raw material solution.

(Example 6)
A metal source was supported on the substrate in the same manner as in Example 1 except that the impregnation apparatus shown in FIG. 2 was used and the impregnation was performed according to the procedure described below. As a result, the uniformity was equivalent to that in the case of Example 1.

(Impregnation procedure in Example 6)
The raw material solution was stored in the solution tank 15a. Further, the substrate 14 is installed in the impregnation chamber 12, the vacuum valve 13b is opened and the vacuum pump 13a is operated to reduce the pressure in the impregnation chamber 12 to fall within the range of 100 Pa to 9000 Pa. While kept open, the solution injection valve 15b was opened, and the raw material solution 18 was injected from the solution tank 15a into the impregnation chamber 12 due to the pressure difference between the impregnation chamber 12 and the solution tank 15a to impregnate the substrate 14 with the raw material solution.

  INDUSTRIAL APPLICABILITY The metal source supporting method of the present invention can be used in various industries because the metal source can be supported on various materials without limitation on the shape of the substrate. In particular, since a perovskite film can be preferably obtained, the perovskite film is useful for photoelectric conversion elements and the like, and can be used for industrial fields such as solar cells and optical sensors.

1 Mist CVD Device 2 Carrier Gas Source 3 Flow 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 (15)

  A method of supporting the metal source on the substrate by bringing the metal source into contact with the substrate, wherein the contact is performed by impregnating the substrate with a raw material solution containing the metal source and an aprotic polar solvent under reduced pressure. A method characterized by being performed.   The method according to claim 1, wherein the impregnation is performed by impregnating the substrate with the raw material solution and then reducing the pressure.   The said base | substrate contains a porous layer in a part or all of the surface, the said metal source is smaller than the average pore diameter of the said porous layer, and the said metal source is made to carry in the hole of the said porous layer. The method described in 2.   The method according to claim 3, wherein the average pore size is 100 nm or less.   The method according to claim 1, wherein the metal source is a metal compound.   The method according to claim 1, wherein the metal source is a metal halide.   7. The method according to claim 1, wherein the metal source contains at least one metal selected from Groups 8 to 14 of the periodic table.   The method according to claim 1, wherein the aprotic polar solvent comprises a heteroatom-containing organic solvent.   The boiling point of the said aprotic polar solvent is 160 degrees C or less, The method in any one of Claims 1-8.   The method according to claim 1, wherein the raw material solution contains an additive containing halogen.   The method according to claim 10, wherein the additive is an amine compound.   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 metal source on a substrate, wherein the method according to any one of claims 1 to 13 is used in the step. A method for manufacturing a photoelectric conversion element using at least a photoelectric conversion layer and an electrode, wherein the photoelectric conversion layer is supported on a substrate by a metal source by using the method according to any one of claims 1 to 13. A manufacturing method characterized by being formed and used.