JP5493289B2 - Inorganic oxide film containing arrayed metal fine particles and method for producing the same - Google Patents

Description

  The present invention relates to a method for arranging metal fine particles in an orderly manner, and more particularly, to a method for arranging metal fine particles in a layer in a direction parallel to the film in an inorganic oxide film.

Optical thin films are widely used in various products such as display devices such as liquid crystal display elements, optical components for optical communication, optical discs, window glass for construction, and windshields for automobiles. Such a thin film is formed of a single layer or a multilayer, but the multilayer film has a higher degree of freedom in optical design depending on the wavelength characteristics than a single layer film, and an optical multilayer film is used as an optical filter. Widely used.

Conventionally, in such an optical multilayer film, an extremely large number of layers (for example, about 100 layers) of a transparent thin film having a high refractive index and a transparent thin film having a low refractive index, or a transparent thin film having an intermediate refractive index between them are laminated. By combining these, the optical interference effect is utilized and the desired optical characteristics are expressed. Specific materials having a high refractive index include TiO ₂ , Ta ₂ O ₅ , SnO ₂ , ZnO, Nb ₂ O ₅ , ZrO ₂ , and HfO ₂ , and low refractive index materials include MgF ₂ , SiO ₂ , As an intermediate refractive index material such as Al ₂ O ₃ , inorganic materials such as Si ₃ N ₄ , WO ₃ , and MgO are widely used (see, for example, Patent Documents 1 to 4).

  As a film forming method for forming an optical multilayer film made of an inorganic material, a vacuum vapor deposition method and a sputtering method are well known. These methods are easy to control the thickness of the thin film, but require a vacuum environment. Further, since the deposition source is exchanged every time the thin film is formed, there are problems such as a complicated manufacturing process and an increase in the size of the apparatus.

On the other hand, the present inventors have ordered the metal fine particles in the polymer by utilizing the light interference phenomenon for the purpose of providing a method for producing a metal fine particle array polymer film by a general and simple method. Research has been conducted on a method for arranging the target (for example, Non-Patent Document 5). However, an inorganic material film containing arranged metal fine particles has not been known yet.
JP-A-7-27907 JP 2006-171645 A JP 2006-99049 A JP 2007-47530 A Optical Interference Coatings (OIC) Topical Meeting and Tabletop Exhibit (2007) Proceedings No. MC3 “A Facial, Novel Methodology for Preparation of Multilayer Metal / Polymer Composite Films”

  An object of the present invention is to provide a method for producing a novel alignment film in which metal fine particles are arranged in layers in an inorganic oxide film by a simple method. Another object of the present invention is to provide an inorganic oxide film in which novel metal fine particles are arranged.

  The present invention relates to the following matters.

1. A step (A) of forming a thin film containing an inorganic oxide sol-gel component and a metal component on a reflective substrate;
And (B) irradiating the thin film on the reflective substrate with light having a specific wavelength. A method for producing an inorganic oxide film containing arranged metal fine particles.

  2. 2. The manufacturing method according to 1 above, wherein the structure of the inorganic oxide film containing the arranged metal fine particles is a structure in which a layer in which metal fine particles are densely present periodically as a multilayer in the film thickness direction of the inorganic oxide film.

  3. The step (A) includes (1) a sub-step of preparing an inorganic oxide sol from an inorganic alkoxide, (2) a sub-step of preparing a coating solution containing the sol and a metal component, and (3) reflecting the coating solution. 3. The manufacturing method according to 1 or 2 above, comprising: a sub-step of coating on a substrate and forming a coating film; and (4) a sub-step of drying the coating film.

  4). The inorganic alkoxide is Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, In. 4. The production method according to 3 above, comprising at least one element selected from the group of elements described above.

  5. 5. The production method according to 4 above, wherein the inorganic alkoxide is represented by the following general formula (I).

^{_{MR 1 x (OR 2) m}} -x ··· (I)
(Wherein M represents an element selected from the group consisting of Si, Ti, Al, Zr, B, Ta, P, Li, Na, Ga, Ge, Sb and V, and R ¹ has a substituent. Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group or an acyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, m represents a valence of the element M, and x represents 0 to (m -1) represents an integer, provided that when two or more of R ¹ and R ² are present in the formula, they may be the same or different from each other.
6). 6. The method according to 5 above, wherein the inorganic alkoxide contains at least one selected from tetraethoxysilane and methyltriethoxysilane.

  7). Any one of the above items 3 to 6, wherein in the sub-step of preparing the inorganic oxide sol from the inorganic alkoxide, the inorganic alkoxide is hydrolyzed and polymerized in an aqueous solution containing a catalyst. The manufacturing method as described.

  8). 8. The production method according to any one of 1 to 7, wherein the metal component includes a metal compound that is reduced by light having the specific wavelength to generate metal fine particles.

  9. 9. The manufacturing method according to any one of 1 to 8, wherein the metal component includes metal fine particles.

  10. 9. The production method according to 8 above, wherein the metal compound is chloroauric acid.

  11. The manufacturing method according to any one of the above items 1 to 10, further comprising a baking step after the step (B).

  12 12. The manufacturing method according to any one of 1 to 11 above, wherein in the step (B), the repetition distance of the metal fine particle layer in the inorganic oxide film is adjusted by changing the wavelength of the irradiated light. .

  13. In the step (B), the repetition distance of the metal fine particle layer in the inorganic oxide film is adjusted by changing the angle of light applied to the reflective substrate. The manufacturing method as described.

  14 An inorganic oxide film in which metal fine particles having a structure in which a layer in which metal fine particles are densely present as a multilayer in the film thickness direction are periodically arranged in the inorganic oxide film.

  15. 15. The inorganic oxide film as described in 14 above, wherein the film thickness is from 100 nm to 10 μm.

  According to the present invention, a novel metal fine particle arrayed inorganic oxide film having a structure in which metal fine particle layers are periodically multilayered can be produced by a very simple method. The obtained metal fine particle arrayed inorganic oxide film can be widely applied to various optical elements, optical components and the like, as in the case of the conventional optical multilayer film.

  The inventors of the present invention have intensively studied to apply a method of regularly arranging metal fine particles in a polymer using an interference phenomenon of light to an inorganic material. In general, high-temperature conditions are required to cure and mold inorganic materials. Therefore, even if a regular structure can be formed inside the inorganic material before curing and molding, diffusion and convection that occur inside the film by the heating operation. It is considered extremely difficult to maintain the regular structure under the influence of the phenomenon. On the other hand, it is conceivable to perform an alignment operation on the structure after curing / molding, but the cured / molded body after heating generally forms a very dense crystal structure. It was extremely limited and it was considered difficult to form a regular structure.

  On the other hand, the sol-gel method is known as a method capable of synthesizing an inorganic oxide thin film at a low temperature, but also in the sol-gel method, hydrolysis of inorganic alkoxide to form a three-dimensional network of inorganic element-oxygen is performed. A heating operation for the purpose of densification of the reaction and the film is necessary, and disorder of the regular structure once constructed was expected in such a process. However, according to the present invention, it has been surprisingly found that an inorganic oxide film containing metal fine particles having a regular arrangement structure can be obtained by a simple method.

  In the production method of the present invention, after a thin film containing an inorganic oxide sol-gel component and a metal component is formed on a reflective substrate, light having a specific wavelength λ is irradiated. Thereafter, the thin film on the obtained reflective substrate is cured as necessary. Hereinafter, the present invention will be described in detail.

  In this application, the term “inorganic oxide” refers to a sol in which the inorganic (atom) -oxygen network is incomplete and fluid in addition to the oxide in which the inorganic (atom) -oxygen three-dimensional network is completely formed. It is used to mean a gel with a more advanced network structure, and all of these intermediate states. Therefore, it may have not only a complete “oxide” but also a partial OH group, alkoxy group or the like. The specific state is clear according to the stage of the manufacturing process. The term “inorganic oxide sol-gel component” means an inorganic oxide component in all states from sol to gel. The term “inorganic oxide sol” means that the inorganic oxide is in a colloidal particulate sol state, itself dispersed in a liquid or dispersion solvent, as well as concentrated and dry sols. including. The term “inorganic oxide gel” means that an inorganic (atom) -oxygen network is at least partially constructed and the inorganic oxide is in a non-flowable gel state, and includes wet gel and dry gel. .

<Preparation of inorganic oxide sol>
For the “inorganic oxide sol-gel component”, an “inorganic oxide sol” is first prepared. This can be synthesized using a known sol-gel method. The sol-gel method is generally known as a method for producing glass or inorganic oxide. In this method, first, an inorganic alkoxide is hydrolyzed and then polymerized to prepare an “inorganic oxide sol”. The inorganic oxide sol is gelled by further proceeding with this reaction, and the resulting porous gel is heated to produce glass or an inorganic oxide [Reference: For example, Sakuo Sakuo “Sol-Gel Science of Law "Agne Jofusha (published) (1988)]. One of the features of this sol-gel method is that low-temperature synthesis is possible. In particular, low-temperature synthesis of silica glass using an alkoxide of Si has been widely put into practical use as a hard coat film on the surface of plastic or the like. .

  The “inorganic oxide sol” is preferably one that can be synthesized by hydrolysis and polycondensation of an inorganic alkoxide using a sol-gel method, and is at least solidified (gelled) before being applied on a reflective substrate. It is not in the state.

  Inorganic alkoxides include Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In. What contains at least 1 type of element chosen from an element group is preferable, and 2 or more types of elements may be included. Furthermore, the inorganic alkoxide used may be used alone or in combination of two or more. Among these, since alkoxides having various substituents are known and are commercially available and easily available, the elements include Si, Ti, Al, Zr, B, Ta, P, Li, Na, Ga. , Ge, Sb, and V, various inorganic alkoxides are preferably used.

  Various inorganic alkoxides including Si, Ti, Al, Zr, B, Ta, P, Li, Na, Ga, Ge, Sb, and V as the element are not particularly limited, but A compound represented by formula (I) is desirable.

^{_{MR 1 x (OR 2) m}} -x ··· (I)
In the formula, M represents an element selected from the group consisting of Si, Ti, Al, Zr, B, Ta, P, Li, Na, Ga, Ge, Sb and V, and R ¹ may have a substituent. A good alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or acyl group; R ² represents an alkyl group having 1 to 6 carbon atoms; m is a valence of element M; x is 0 to (m- The integer of 1) is shown. However, when two or more of R ¹ and R ² are present in the formula, they may be the same as or different from each other.

  M is preferably Si, Ti, Al, Zr, B, or Ta.

In the general formula (I), R ¹ is a non-hydrolyzable group which may have a substituent. As an alkyl group, a C1-C20 alkyl group is preferable, and an alkenyl group and an alkynyl group have a C2-C20 thing. As the aryl group, those having 6 to 20 carbon atoms and the aralkyl group having 7 to 20 carbon atoms are preferable. Furthermore, as an acyl group, a C2-C20 aliphatic acyl group and a C7-C20 aromatic acyl group (aroyl group) can be mentioned preferably.

  Examples of the substituent include halogens such as fluorine, chlorine and bromine, 3,4-epoxycyclohexyl group, glycidyloxy group, (meth) acryloyloxy group, amino group, aminoalkyl group, mercapto group, anilino group and ureido group. It is done.

On the other hand, OR ² is a hydrolyzable group. The alkyl group having 1 to 6 carbon atoms represented by R ² may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples include n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, vinyl group and the like.

In the formula (I), at least one OR ² group is present, preferably two or more. Therefore, x is an integer of 0 to (m−1), and preferably 0 to (m−2) on condition that it is not negative.

Two or more inorganic alkoxides of the formula (I) may be used in combination. At that time, inorganic alkoxides having different Ms may be combined, alkoxides having different R ¹ and / or R ² and / or x may be combined, or both of them may be combined.

  In the general formula (I), specific silica alkoxide in which M = Si is not particularly limited, but includes trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, Trimethylethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, cyclohexylmethyldimethoxysilane, hexyltrimethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, dodecyltriethoxysilane, vinyltrimethoxysilane, vinyltri (β-methoxyethoxy) silane , Divinyloxydimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropylmethyldichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, β- (3 4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltriethoxysilane, glycidyl Xylpropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, glycidyloxypropylmethyldimethoxysilane, γ-acryloyloxy-n-propyltri-n-propoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltri Ethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxy-n-propyl-n-propoxysilane, di (γ-acryloyloxy) -N-propyl) di-n-propoxysilane, acryloyloxydimethoxyethylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxy Silane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropylethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltri Ethoxysilane, γ-bromopropyltrimethoxysilane, γ-bromopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-urei It may be mentioned propyl triethoxysilane, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific titanium alkoxide in which M = Ti is not particularly limited, but titanium n-butoxide, titanium methoxide, titanium ethoxide, titanium n-propoxy , Titanium isopropoxide, titanium t-butoxide, titanium n-nonyl oxide, titanium i-butoxide, titanium methoxypropoxide, titanium di-n-butoxide (bis-2,4-pentadionate), titanium diisopropoxide ( Bis-2,4-pentadionate), titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethyl acetoacetate), titanium 2-ethylhexoxide, titanium oxide bis (penta Diate), titanium oxybis (tetramethylhepta) Diate), tetrakis (trimethylsiloxy) titanium, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium methacrylate triisopropoxide, (2-methacryloxyethoxy) triisopropoxy titanate, titanium Examples thereof include methacryloxyethyl acetoacetate triisoproxide and titanium methylphenoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific aluminum alkoxide in which M = Al is not particularly limited, but aluminum (III) n-butoxide, aluminum (III) s-butoxide, aluminum (III) t-butoxide, aluminum (III) ethoxide, aluminum (III) isopropoxide, aluminum (III) s-butoxide bis (ethyl acetoacetate), aluminum (III) di-s-butoxide ethyl acetoacetate, aluminum ( III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropentadionate, aluminum (III) 3-hydroxy-2-methyl-4-pyronate, a Minium (III) 9-octadecenyl acetoacetate diisopropoxide, aluminum (III) 2,4-pentandionate, aluminum (III) phenoxide, aluminum (III) 2,2,6,6-tetramethyl- Mention may be made of 3,5-heptanedionate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific zirconium alkoxide in which M = Zr is not particularly limited, but zirconium ethoxide, zirconium isopropoxide, zirconium n-propoxide, zirconium n -Butoxide, zirconium t-butoxide, zirconium 2-ethylhexyl oxide, zirconium 2-methyl-2-butoxide, tetrakis (trimethylsiloxy) zirconium, zirconium di-n-butoxide (bis-2,4-pentandionate), zirconium diiso Propoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate, zirconium dimethacrylate dibutoxide, zirconium hexafluoropentanedionate, zirconium methacryloxye Mention may be made of acetoacetate tri n-propoxide, zirconium 2,4-pentanedionate, zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, zirconium trifluoropentanedionate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific boron alkoxide in which M = B is not particularly limited, but boron methoxide, boron ethoxide, boron isopropoxide, boron n-butoxide, boron Examples thereof include t-butoxide and boron allyl oxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific tantalum alkoxide in which M = Ta is not particularly limited, but includes tantalum (IV) methoxide, tantalum (IV) ethoxide, tantalum (IV) isoform. Propoxide, Tantalum (IV) n-propoxide, Tantalum (IV) n-butoxide, Tantalum (IV) t-butoxide, Tantalum sodium methoxide, Tantalum (V) trifluoroethoxide, Tantalum (V) tetraethoxide pentane Dionate can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific phosphorus alkoxides with M = P are not particularly limited, and examples thereof include trimethoxyline and triethoxyline. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific lithium alkoxide in which M = Li is not particularly limited, but lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium t-butoxide. , Lithium 2,4-pentanedionate, and lithium tetramethylheptanedionate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific sodium alkoxide in which M = Na is not particularly limited, but sodium methoxide and sodium ethoxide can be exemplified. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific gallium alkoxide in which M = Ga is not particularly limited, but includes gallium triethoxide, gallium (III) 2,4-pentanedionate, Mention may be made of gallium (III) 2,2,6,6-tetramethylheptanedionate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific germanium alkoxides in which M = Ge is not particularly limited, but germanium methoxide, germanium ethoxide, germanium isopropoxide, germanium n-butoxide. And germanium t-butoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific antimony alkoxides in which M = Sb are not particularly limited, but include antimony trimethoxide, antimony triethoxide, antimony tri-n-butoxide, antimony. Mention may be made of tri-t-butoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the general formula (I), specific vanadium alkoxides in which M = V are not particularly limited, but include vanadium triisopropoxide oxide, vanadium triisobutoxide oxide, vanadium (III ) 2,4-pentanedionate, vanadium (IV) oxide bis (2,4-pentanedionate), vanadium (IV) oxybis (benzoylacetonate). These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these inorganic alkoxides, the combined use of tetraethoxysilane and methyltriethoxysilane is particularly preferably used because the resulting thin film can be thickened.

An inorganic oxide sol can be obtained by subjecting the above inorganic alkoxide to hydrolysis / condensation reaction. For example, taking tetraalkoxysilane as an example,
The hydrolysis reaction is, for example, Si (OR) ₄ + H ₂ O → Si (OR) ₃ (OH) + ROH
Si (OR) ₃ (OH) + H ₂ O → Si (OR) ₂ (OH) ₂ + ROH
The polycondensation reaction proceeds by, for example, 2Si (OR) ₃ (OH) → (OR) ₃ Si—O—Si (OR) ₃ + H ₂ O
Si (OR) ₃ (OH) + Si (OR) ₄ → (OR) ₃ Si—O—Si (OR) ₃ + ROH
It progresses by the reaction. When the condensation reaction proceeds to a high degree and a three-dimensional network of Si—O—Si is formed, it gels and solidifies. The inorganic oxide sol before being applied to the reflective substrate is in a state of fluidity and colloidal particles before gelation.

  The hydrolysis / condensation reaction of the inorganic alkoxide can be performed without a solvent or in a solvent. In the case where the reaction proceeds without any problem, the production cost is reduced, so that no solvent is preferably selected. On the other hand, when an organic solvent is used to uniformly mix the components, for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The solvent is preferably a solvent that dissolves the inorganic alkoxide and the catalyst. Moreover, it is preferable on a process to use a solvent as a coating liquid or a part of coating liquid. Although it is possible to add some alkoxides to the coating solution without hydrolysis, they generally have adverse effects on the coating state, such as cissing and uneven stripes when applied, and the hydrolysis proceeds. It is preferable to use in the state.

  Examples of alcohols that can be used as the solvent include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monomethyl ether, ethylene glycol monobutyl ether, and acetic acid ethylene glycol monoethyl ether.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.

  These organic solvents can be used alone or in combination of two or more. The ratio of the solvent in the reaction is not particularly limited, but is usually in the range of 10% by mass to 99% by mass of the total mass, and preferably in the range of 30% by mass to 80% by mass.

  The hydrolysis and condensation reaction of the inorganic alkoxide is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, And organic bases such as pyridine. Here, the metal alkoxide is selected to be more basic than the reaction raw material inorganic alkoxide. From the viewpoint of the production stability of the sol solution and the storage stability of the sol solution, acid catalysts (inorganic acids and organic acids) are preferred. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferable because they are inexpensive and easily available, and hydrochloric acid is particularly preferable.

  The hydrolysis and condensation reaction is usually performed by adding 0.3 to 2 mol, preferably 0.5 to 1 mol of water with respect to 1 mol of the hydrolyzable group of the inorganic alkoxide, and in the presence or absence of the solvent. Under stirring and preferably in the presence of a catalyst at 25-100 ° C. The water required for hydrolysis may be sufficient in the solvent or in the air. When alcohol is used as the solvent or when the catalyst is added as an aqueous solution, substantially no water is added. It is also suitable.

  When the catalyst is an inorganic acid, the amount of the catalyst used is usually 0.0005 to 10 mol%, preferably 0.001 to 1 mol%, based on the hydrolyzable group. If too much catalyst is added, the reaction proceeds rapidly and gels, which may make it difficult to form a uniform coating film in the subsequent process, and if it is too small, the reaction is slow and complete hydrolysis occurs. Absent.

  The reaction is usually carried out by stirring at 25 to 100 ° C., but is preferably adjusted as appropriate depending on the reactivity of the inorganic alkoxide.

  The inorganic oxide sol thus obtained is itself liquid or obtained as a dispersion liquid dispersed in a solvent (hereinafter, these may be collectively referred to as a sol solution), and in the next step Metal components are mixed.

<Reflective substrate>
The “reflective substrate” that can be used in the present invention is not particularly limited as long as the surface of the substrate can reflect light having a specific wavelength λ. For example, a reflecting mirror (mirror) in which a single layer film or a multilayer film is formed on the surface of the substrate using a material selected from various metals such as aluminum and silver and metal oxides. Among these, a film obtained by sequentially forming aluminum and silica on a glass substrate is preferable. This is because aluminum can form a film having a high reflectance stably in the ultraviolet to visible region. The silica layer is effective in preventing aluminum from being oxidized.

  The thickness (film thickness) of aluminum in the reflective substrate is, for example, about 100 to 2000 nm, preferably about 150 to 1000 nm, and more preferably about 200 to 800 nm. Further, the thickness (film thickness) of silica is better because it does not deteriorate the reflective properties of aluminum, and is, for example, about 5 to 100 nm, preferably about 10 to 50 nm, and more preferably about 10 to 30 nm.

<Metal component>
There may be one kind of metal element constituting the “metal component” or two or more kinds. The metal component preferably contains at least one of a metal compound (including a complex and a salt; the same applies hereinafter) and metal fine particles. In general, a method of applying a sol solution containing a metal compound and / or metal fine particles to a reflective substrate is preferable, and a method of applying a sol solution in which a metal compound is dissolved to the reflective substrate is particularly preferable.

  The metal compound used in the present invention generates metal fine particles by irradiation with a specific wavelength λ. As such a material, a compound that absorbs light energy and generates metal fine particles (or a metal constituting the metal fine particles) by reduction (that is, a metal compound having a positive oxidation number of metal atoms) is known. Usually, it is often a metal salt.

Examples of such metal compounds include metal oxides, metal hydroxides, metal halides (metal chlorides, etc.), metal acid salts [metal inorganic acid salts (sulfates, nitrates, phosphates, perchloric acid). Salt, oxo acid salt such as hydrochloride), metal organic acid salt (such as acetate) and the like. The form of the metal salt may be a single salt, a double salt, or a complex salt (electrolyte complex or non-electrolyte complex, usually an electrolyte complex), or a multimer (for example, a dimer). The metal compound (metal salt) includes, for example, an acid component [hydrogen chloride (HCl) and the like], a base component (ammonia and the like), water (H ₂ O) and the like (for example, a halogenated hydrogen compound, It may be a hydrate or hydrate). The metal compounds may be used alone or in combination of two or more.

  Moreover, the metal element which comprises a metal compound is not specifically limited. As the metal element constituting the metal compound, Group 8-11 metals of the periodic table (that is, iron, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, etc.) are preferable, and specific implementation In the form, noble metals (silver, gold, platinum, rhodium, etc.) are particularly preferable. The metal compound may contain one or more of these metal elements.

Specific examples of the metal compound include Group 8-11 metal compounds (including metal salts) of the periodic table. For example, as Group 8-11 metal salts of the periodic table, inorganic acid salts [for example, noble metal inorganic acid salts such as silver perchlorate (AgClO ₄ ), silver nitrate (AgNO ₃ )], and organic acid salts [for example, acetic acid Palladium (Pd (CH ₃ CO ₂ ) _{2 and the} like), rhodium acetate (noble metal organic acid salts such as noble metal acetates such as [Rh (CH ₃ CO ₂ ) ₂ ] ₂ ) and the like. Further, as a periodic group 8-11 metal halide, noble metal halide [eg, silver chloride (AgCl), gold chloride (AuCl ₃ ), platinum chloride (PtCl ₂ , PtCl ₄ etc.), palladium chloride (PdCl ₂ etc.) Noble metal chlorides such as], acid component-containing metal halides [for example, hydrogen chloride-containing noble metal halides such as chlorinated noble metal acids such as chloroauric acid (HAuCl ₄ etc.), chloroplatinic acid (H ₂ PtCl ₆ etc.)] And hydrates thereof.

  Below, typical metal compounds are illustrated about gold | metal | money, silver, copper, platinum, palladium, and rhodium among periodic table 11 group metals.

Examples of the gold compound include gold halides (AuCl, AuCl ₃ , AuBr ₃ , AuI, AuI ₃ , AuCl (PPh ₃ ), AuCl (SC ₄ H ₈ ), halogenated gold acid or a salt thereof (HAuCl ₄ , HAuCl). _{4 · 4H 2 O, NaAuCl 4} · 4H 2 O, KAuCl 4 · 4H 2 O , etc.), gold hydroxide (AuOH), gold cyanide (AuCN), such as gold oxide _(Au 2 _{O 3),} gold sulfide (Au ₂ S, Au ₂ S ₃ (III), etc.), or trimethyl gold (III) (Au ₂ (CH ₃ ) ₆ ), methyl (triphenylphosphine) gold (I) (Au ₂ CH ₃ ( PPh _3)), 4-ethylbenzene-thio Ratn gold _{(I) (Au {S (} C 6 H 4) C 2 H 5}), {μ-1,8- bis (diphenylphosphino) 3,6 Dioxaoctane} bis {chloroauric _{(I)} ((AuCl)} 2 (μ- {Ph 2 P (CH 2) 2 O (CH 2) 2 O (CH 2) 2 PPh 2}), ( pentafluorophenyl ) (Tetrahydrothiophene) gold (I) ([Au (C ₆ F ₅ ) (SC ₄ H ₈ )]), tris (pentafluorophenyl) (tetrahydrothiophene) gold (III) ([Au (C ₆ F ₅ ) ₃ (SC ₄ H ₈ )]) and the like.

Silver compounds include inorganic salts [for example, silver halides such as AgF, AgCl, AgI, AgBr, silver oxides such as Ag ₂ O, Ag ₂ SO ₄ , AgS, AgCN, AgClO ₄ , Ag ₃ PO ₄ , AgSCN, _{AgNO 3, Ag 2 SO 3,} Ag 2 CO 3, Ag 2 CrO 4, Ag 2 Se, AgReO 4, AgBF 4, AgW 4 O 16, Ag 3 AsO 4, AgSbF 6, AgPF 6, AgHF 2, AgIO 3, Inorganic acid salts such as AgBrO ₃ , AgOCN, AgMnO ₄ , AgVO _3, etc.], organic salts (or complexes) [eg, C ₆ H ₅ CO ₂ Ag, C ₆ H ₁₁ (CH ₂ ) ₃ CO ₂ Ag, CH ₃ CH (OH) CO ₂ Ag, silver trifluoroacetate (CF ₃ CO ₂ Ag), C ₂ F ₅ CO ₂ Ag, C ₃ F ₇ CO _{2 Ag,} carboxylates such as _{AgO 2 CCH 2 C (OH)} (CO 2 Ag) CH 2 CO 2 Ag, p- toluenesulfonate, silver silver trifluoromethanesulfonate _(CF 3 _SO 3 Ag), etc. (CH ₃ C (O) CHC (O) CH ₃ ) Ag, (C ₂ H ₅ ) ₂ NCS ₂ Ag, phenyl silver (I), tetramesityl tetrasilver (I), butyl acetylide silver (I ), Chloro (isocyanocyclohexane) silver, (cyclopentadienyl) triphenylphosphine silver (I), bispyridine silver (I) perchlorate, (η ⁴ -1,5-cyclooctadiene) (1,1, 1,5,5,5-hexafluoro-2,4-pentanedionato) silver (I), bromo (tri-n-butylphosphine) silver (I), bisimidazole silver (I) nitrate, Bis (1,10-phenanthroline) silver (I) perchlorate and nitrate, 1,4,8,11-tetraazacyclotetradecane silver (II) perchlorate, (1,1,1,5,5 , 5-hexafluoro-2,4-pentanedionato) (N, N, N′-trimethylethylenediamine) silver (I)] and the like.

Examples of the copper compound include inorganic salts [eg, Cu ₂ O, CuO, Cu (OH) ₂ , CuF ₂ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI and other copper halides, CuCO ₃ , CuCN, Cu (NO _{3) 2, Cu (ClO 4} ) 2, Cu 2 P 2 O 7, Cu 2 Se, CuSe, CuSeO 3, CuSO 4, Cu 2 S, CuS, Cu (BF 4) 2, Cu 2 HgI 4, CuSCN, Inorganic acid salts such as (CF ₃ CO ₂ ) ₂ Cu, (CF ₃ SO ₃ ) ₂ Cu, CuWO ₄ , Cu ₂ (OH) PO ₄ ], organic salts (or complexes) [eg, copper (I) acetate , copper acetate _{(II), [C 6 H} 11 (CH 2) 3 CO 2] 2 Cu, [CH 3 (CH 2) 3 CH (C 2 H 5) CO 2] 2 Cu, (HCO 2) 2 _{u, [HOCH 2 [CH (} OH)] 4 CO 2] carboxylate such as _{2 Cu, (CH 3 C (} O) CHC (O) CH 3) 2 Cu, CH 3 (CH 2) 3 SCu, ( CH ₃ O) ₂ Cu] and the like.

Platinum compounds include inorganic salts [for example, platinum halides such as PtO ₂ , PtCl ₂ , PtCl ₄ , PtBr ₂ , PtBr ₄ , PtI ₂ , PtI ₅ , haloplatinic acids such as HPtCl ₆ · 2H ₂ O, PtS ₂ , Pt (CN) _2, etc.], organic salt (or complex) [eg (CH ₃ C (O) CHC (O) CH ₃ ) ₂ Pt, (C ₆ H ₅ CN) ₂ PtCl ₂ , (CH ₃ CN) ₂ PtCl ₂ ] and the like.

Examples of the palladium compound include inorganic salts [eg, palladium halides such as PdO, PdCl ₂ , PdBr ₂ , PdI ₂ , PdCN ₂ , Pd (NO ₃ ) ₂ , PdS, PdSO ₄ , K ₂ Pd (S ₂ O ₃ ) ₂ · H ₂ O, chloropalladic acid, etc.], organic salts (or complexes) [for example, carboxylates such as Pd (CH ₃ CO ₂ ), palladium (II) propionate, (CF ₃ CO ₂ ) ₂ Pd , (CH ₃ C (O) CHC (O) CH ₃ ) ₂ Pd, (C ₆ H ₅ CN) ₂ PdCl ₂ , (CH ₃ CN) ₂ PdCl ₂ ], and the like.

Examples of rhodium compounds include inorganic salts [eg, rhodium halides such as Rh ₂ O ₃ , RhO ₃ , RhCl ₃ , RhBr ₃ , RhI ₃ , RhPO ₄ , Rh ₂ SO _4, etc.], organic salts (or complexes) [eg, , [Rh (CH ₃ CO ₂ ) ₂ ] ₂ , (CF ₃ CO ₂ ) ₂ Rh, {[CH ₃ (CH ₂ ) ₆ CO ₂ ] ₂ Rh} ₂ , [(CF ₃ CF ₂ CF ₂ CO ₂ ) ₂ Rh] ₂ , carboxylates such as {[(CH ₃ ) ₃ CCO ₂ ] ₂ Rh} ₂ , (CH ₃ C (O) CHC (O) CH ₃ ) ₃ Rh] and the like.

  Of these metal compounds, chloroauric acid, which is a metal compound that is easily reduced by light, is particularly preferably used.

  In addition, as a metal fine particle (here, means a metal fine particle contained in a thin film at the time of forming a thin film containing an inorganic oxide sol-gel component and a metal component on a reflective substrate), a specific wavelength is used. Those which can move in the film by irradiation with λ are preferred, and metal particles such as colloidal particles of about 10 nm or less, particularly preferably 2 nm or less are preferred. For example, the thing which metal fine particles precipitated from said metal compound is mentioned. For example, silver or gold fine particles are preferable. Further, it may be a mixture of a metal compound and metal fine particles.

<Film Formation of Inorganic Oxide Sol-Gel Component and Metal Component>
In order to form a thin film containing an inorganic oxide sol-gel component and a metal component on a reflective substrate, an inorganic oxide sol (sol solution) prepared as described above and a coating solution containing the metal component are prepared. Prepare.

  The metal component or a solution containing the metal component is dissolved or uniformly mixed and dispersed in the sol solution described above to prepare a coating solution. The ratio of the metal component to be contained in the sol solution is, for example, 0.2 to 500 parts by weight, preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the inorganic alkoxide as a starting material, although it depends on the kind of sol. The amount is about 400 parts by weight, more preferably about 1 to 200 parts by weight.

  The method for forming the coating solution on the reflective substrate is not particularly limited as long as the film can be formed. Conventional coating methods such as spin coating method (rotary coating method), roll coating method, curtain coating method, dip coating are applicable. Law, cast method, etc. can be used. As the coating device, a device corresponding to the above coating method, for example, a spin coater, a slit coater, a roll coater, a bar coater or the like can be used.

  Next, the formed coating film is dried. In this drying step, the solvent, water, alcohol desorbed from the alkoxide, the solvent in the metal component solution, and the like contained in the sol solution are evaporated. The drying method is not particularly limited, and examples thereof include a conventional solvent distillation method, for example, evaporation by heating and vacuum drying by various evaporators. After drying, a solid film of an inorganic oxide sol-gel component containing a metal component is obtained. Note that “drying” means removing at least a part of the evaporation component, and the solid film may contain a solvent, water, and alkoxide.

  During the drying process from application of the coating solution, under normal conditions, the solution is solidified by gelation to form an “inorganic oxide gel”. Further, a sol may be contained in a gel composed of a part of an inorganic (atom) -oxygen network (in the present invention, this state is also included in the “inorganic oxide gel”). In the present invention, it is considered preferable to be an inorganic oxide gel after the drying step, but if possible, it may be present as an inorganic oxide sol (concentrated sol, dry sol).

  The thickness of the thin film containing the metal component formed on the reflective substrate is not particularly limited and can be appropriately set according to the use, but the inorganic oxide in which the metal fine particles produced in the present invention are arranged In order to obtain a film, it is necessary that the film thickness is at least larger than the arrangement interval of the metal fine particles. In addition, if a film having a thickness of submicron or more is produced by a single film forming operation using the sol-gel method, a crack is generated in the film due to stress generated in the film surface direction during the firing process. It is widely known as a problem of the sol-gel method. In order to realize a thick film, it is possible to perform a plurality of film forming operations, but since an interface occurs and adversely affects the uniform transmission of light in the film during the light irradiation operation described later, In the present invention, one film forming operation is preferable. For this reason, the thickness of the thin film containing the metal component formed on the reflective substrate is, for example, about 50 nm to 100 μm, preferably 70 nm to 50 μm, and more preferably about 100 nm to 10 μm.

<Light irradiation>
In the production method of the present invention, the inorganic oxide sol-gel component film containing the metal component formed on the reflective substrate is then irradiated with light having a specific wavelength λ. A desired wavelength can be selected as the wavelength λ, but when the above-described metal component receives light of this wavelength, generation of metal fine particles, movement of metal, and growth of metal particles may occur. Set from various wavelength ranges. Usually, it is selected from a wavelength region having sufficient energy to excite a metal compound and reduce it to metal fine particles, and an ultraviolet to visible light region is preferable. Specifically, it is preferable that one wavelength is selected from a wavelength region of 200 to 600 nm, preferably 300 to 500 nm, more preferably 350 to 500 nm. In such a wavelength range, various metal compounds can be efficiently photoreduced into metal fine particles.

  Examples of light sources to be irradiated include halogen lamps, mercury lamps (low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, etc.), deuterium lamps, UV lamps, lasers (eg, helium-cadmium lasers, excimer lasers, etc.), etc. Can be used. In one embodiment, an ultra high pressure mercury lamp is suitable. Further, it is preferable to irradiate one wavelength with a narrow half width as much as possible. The full width at half maximum of the irradiation wavelength is preferably 50 nm, more preferably 30 nm or less, particularly preferably 20 nm or less, and most preferably 10 nm or less. In order to reduce the half-value width, it is preferable to combine a commercially available narrow band-pass filter.

Although the light irradiation time largely depends on the ability (irradiation intensity) of the irradiation light source, it is preferable to determine the size of the generated metal particles in consideration of the reaction rate and the movement of the metal component. For example, when a 500 W high-pressure mercury lamp (irradiation intensity: 165 W / cm ² or more) is used, the irradiation time is 20 minutes to 24 hours, preferably 3 hours to 15 hours, and particularly preferably 5 hours. -10 hours.

<Inorganic oxide film containing arranged metal fine particles>
By the light irradiation step, metal fine particles are generated from the metal compound in the thin film containing the metal component, or the metal fine particles move and densely form a layer parallel to the film surface. A multilayer structure. That is, when viewed in the cross-sectional direction of the film, it has a multi-layer structure in which metal fine particle layers densely packed with metal and layers of only metal oxides are alternately laminated.

  It is presumed that the incident light and reflected light interfere to generate a standing wave with a distribution with periodic light intensity, and the metal compound moves, resulting in the formation of a multilayer structure. The On the other hand, it is presumed that a standing electric field intensity distribution also occurs in the thin film containing metal fine particles, and the metal fine particles move and a multilayer structure is formed by the same mechanism.

  Moreover, in the manufacturing method of this invention, the repetition distance (pitch) of a metal fine particle layer can be adjusted arbitrarily. According to the above theory, by adjusting the period of the light intensity generated in the thickness direction of the inorganic oxide film, the repetition distance (pitch) of the metal fine particle layer is changed. Typically, it can be adjusted by changing the wavelength λ of the irradiation light. For example, the repetition distance of the metal fine particle layer can be increased by setting the wavelength of the irradiation light to a long wavelength. Furthermore, the repetition distance (pitch) of the metal fine particle layer can also be adjusted by changing the angle of the irradiation light. For example, the repetition distance of the metal fine particle layer can be increased by increasing the incident angle of the irradiation light. The change in the incident angle is a very simple method because it can be realized simply by tilting the substrate or making the irradiation light incident at a certain angle. Furthermore, in this method, the repetition distance of the metal fine particle layer can be adjusted independently from the wavelength of the irradiation light. Therefore, at the time of manufacture, light having a wavelength suitable for obtaining a desired repetition distance (pitch). Can be selected. Therefore, it is easy to produce a film that selectively reflects light having a wavelength different from the wavelength of irradiation light. In the inorganic oxide film in which the metal fine particles are arranged according to the present invention, the arrangement of the metal fine particle layers can be determined by arbitrary control in this way. Note that the film thickness may shrink or increase due to the treatment after the light irradiation, and in this case, the repetition distance (pitch) of the metal fine particle layer may also change.

  The metal fine particles in the metal fine particle layer are extremely small at the time of generation, but the particle diameter becomes large due to the aggregation and consolidation normally observed in the metal fine particles, and the metal fine particles are substantially reduced. It may take the form that can be considered. On the other hand, even in a thin film containing metal fine particles, by increasing the light intensity, the difference between the portion where the electric field strength generated as a standing wave is high and the portion where the electric field strength is small becomes large. growing.

  Thus, although it depends on conditions, it is usually 2 to 100 nm. In a particular embodiment, the majority (eg 80% or more) of the fine particles have a nano-level particle size of 50 nm or less.

  The inorganic oxide film on which the metal fine particles are arranged on the reflective substrate thus obtained may be used as it is, or may be used after being peeled and attached to a suitable substrate. For example, when a transparent or opaque film or sheet, particularly a resin (polymer) film or sheet, is used as a substrate, and an inorganic oxide film in which metal fine particles are arranged is pasted or laminated, the metal fine particles of the present invention are arranged. The inorganic oxide film can be provided with mechanical flexibility and light weight, and can be used for various applications because the handleability is improved.

<Baking of inorganic oxide film>
After the light irradiation, the inorganic oxide film may be heated or baked together with the reflective substrate or after being peeled from the reflective substrate. By heating and baking, a polycondensation reaction or the like further proceeds, whereby the film can be cured and densified. Depending on conditions, it can be vitrified. As a curing method, various methods can be selected depending on conditions, but a method such as heating or heating in a state irradiated with ultraviolet light is preferably used. In particular, heating using a baking furnace is preferable because it is simple. The heating temperature at this time largely depends on the type of the inorganic matrix, but is, for example, about 100 ° C. or higher and 1000 ° C. or lower, preferably 300 ° C. or higher and 900 ° C. or lower, more preferably 400 ° C. or higher and 800 ° C. or lower. .

  The inorganic oxide film in which the metal fine particles are produced according to the present invention can be used in place of a conventional optical multilayer film made of an inorganic substance or an inorganic oxide. Therefore, it can be widely applied to optical parts as an optical material.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

(Reference Example 1)
A 200 nm aluminum film was formed on soda lime glass by a direct current sputtering method, and further a 10 nm silica film was formed by a 13.56 MHz alternating current sputtering method to produce a reflective substrate.

Example 1
To a mixed solution of 3.05 g of tetraethoxysilane and 4.20 g of methyltriethoxysilane was added 1.14 g of 0.1M hydrochloric acid aqueous solution, and the mixture was heated and stirred at 40 ° C. for 4 hours. The resulting solution was allowed to stand for 30 minutes, and then 1.03 g of a 17 wt% dilute hydrochloric acid solution was added dropwise and stirred for 1 hour. The obtained solution was spin-coated (1000 rpm, 10 seconds) on the reflective substrate prepared in Reference Example 1, and then vacuum-dried at room temperature. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 8 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (“Multi Light” manufactured by USHIO INC.) And a narrow band-pass filter. did. Thereafter, the thin film on the reflective substrate was heated and baked at 500 ° C. for 30 minutes using a baking furnace.

  A transmission electron microscope (TEM) photograph of the cross section of the thin film on the obtained reflective substrate is shown in FIG. It was confirmed that gold fine particles were arranged in a layered manner in the direction parallel to the substrate at intervals of about 100 nm (geometric distance) in silica. It was also observed that many of the gold particles have a particle size of 10 nm or less.

  Further, a transmission electron microscope (TEM) photograph of the cross-section of the thin film on the obtained reflective substrate is processed with image analysis software (NIH Image (ImageJ)), and the distance from the A surface in FIG. A graph showing the relationship with the number of metal particles up to the B-plane (distance from the A-plane; 1000 nm) is shown in FIG. The graph showed a maximum value at a constant period, and it was confirmed that gold fine particles were arranged in layers in a direction parallel to the substrate in silica.

(Comparative Example 1)
To a mixed solution of 3.02 g of tetraethoxysilane and 4.23 g of methyltriethoxysilane was added 1.07 g of 0.1M hydrochloric acid aqueous solution, and the mixture was heated and stirred at 40 ° C. for 4 hours. The resulting solution was allowed to stand for 30 minutes, and then 1.09 g of a 17 wt% chloroauric acid dilute hydrochloric acid solution was added dropwise and stirred for 1 hour. The obtained solution was spin-coated (1000 rpm, 10 seconds) on a glass substrate without a reflective metal layer, and then vacuum-dried at room temperature. After that, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 8 hours to the thin film on the glass substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did. Thereafter, the thin film on the glass substrate was baked at 500 ° C. for 30 minutes using a baking furnace.

  The transmission electron microscope (TEM) photograph of the thin film cross section on the obtained glass substrate is shown in FIG. Compared with the structure produced in Example 1, there was no regularity in the distribution of the gold fine particles in the silica, and it was observed that the gold fine particles were almost uniformly dispersed in the silica film.

  Further, a transmission electron microscope (TEM) photograph of the cross-section of the thin film on the obtained reflective substrate is processed with image analysis software (NIH Image (ImageJ)), and exists at the position and the distance from the A surface in FIG. FIG. 4 shows a graph representing the relationship with the number of metal particles up to the B-plane (distance from the A-plane; 1000 nm). The graph does not show clear regularity as compared with that analyzed in Example 1, and it was confirmed that the gold fine particles were dispersed almost uniformly in the silica.

2 is a TEM photograph of a metal fine particle arrayed inorganic oxide film produced in Example 1. FIG. It is the graph which analyzed the TEM photograph of Example 1 and analyzed the relationship between the distance from the A plane and the number of metal particles existing at that position until the B plane (distance from the A plane; 100 nm). . 4 is a TEM photograph of a metal fine particle arrayed inorganic oxide film produced in Comparative Example 1. It is the graph which image-analyzed the TEM photograph of the comparative example 1, and represented the relationship between the distance from A surface and the number of the metal particle which exists in the position until it reached B surface (distance from A surface; 100 nm). .

Claims (13)

A step (A) of forming a thin film containing an inorganic oxide sol-gel component and a metal component on a reflective substrate;
And (B) irradiating the thin film on the reflective substrate with light having a specific wavelength. A method for producing an inorganic oxide film containing arranged metal fine particles.   The manufacturing method according to claim 1, wherein the structure of the inorganic oxide film containing the arranged metal fine particles is a structure in which a layer in which metal fine particles are densely present periodically as a multilayer in the film thickness direction of the inorganic oxide film.   The step (A) includes (1) a sub-step of preparing an inorganic oxide sol from an inorganic alkoxide, (2) a sub-step of preparing a coating solution containing the sol and a metal component, and (3) reflecting the coating solution. 3. The manufacturing method according to claim 1, further comprising: a sub-process for coating on a substrate to form a coating film; and (4) a sub-process for drying the coating film.   The inorganic alkoxide is Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, In. The production method according to claim 3, comprising at least one element selected from the group of elements. The said inorganic alkoxide is represented by the following general formula (I), The manufacturing method of Claim 4 characterized by the above-mentioned.
^{_{MR 1 x (OR 2) m}} -x ··· (I)
(Wherein M represents an element selected from the group consisting of Si, Ti, Al, Zr, B, Ta, P, Li, Na, Ga, Ge, Sb and V, and R ¹ has a substituent. Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group or an acyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, m represents a valence of the element M, and x represents 0 to (m -1) represents an integer, provided that when two or more of R ¹ and R ² are present in the formula, they may be the same or different from each other.   6. The method according to claim 5, wherein the inorganic alkoxide contains at least one selected from tetraethoxysilane and methyltriethoxysilane.   7. The inorganic oxide sol is prepared by hydrolyzing the inorganic alkoxide in an aqueous solution containing a catalyst in the sub-step of preparing the inorganic oxide sol from the inorganic alkoxide. The manufacturing method as described in.   The manufacturing method according to claim 1, wherein the metal component includes a metal compound that is reduced by light having the specific wavelength to generate metal fine particles.   The manufacturing method according to claim 1, wherein the metal component includes fine metal particles.   The method according to claim 8, wherein the metal compound is chloroauric acid.   The method according to any one of claims 1 to 10, further comprising a baking step after the step (B). The said process (B) WHEREIN: The repetition distance of the metal fine particle layer in the said inorganic oxide film is adjusted by selecting the wavelength of the light to irradiate, The Claim 1 characterized by the above-mentioned. Production method. The said process (B) WHEREIN: The repetition distance of the metal fine particle layer in the said inorganic oxide film is adjusted by selecting the angle of the light irradiated with respect to the said reflective substrate, The any one of Claims 1-11 characterized by the above-mentioned. The manufacturing method of crab.