JP2803602B2 - Inorganic polymer thin film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sol-gel reaction-based inorganic polymer thin film.

[0002]

2. Description of the Related Art Conventionally, a method of forming an oxide thin film has been disclosed in Journal of Vacuum Science Technology A, Vol. 1, No. 3, (1983), No. 136.
Page 2 to 1366 (J. Vac. Sci. Technol. A, Vol. No. 3)
(1983), pp. 1362 to 1366), a journal is applied to a sputtering method which is a physical film forming method.
Of Electrochemical Society, 120 volumes,
(1973), pp. 927- (J. Electrochem. Soc., 12
0 , (1973), pp927-), a chemical vapor deposition method (Chemical Vapor D method).
eposition method: CVD method) is known.

In the sputtering method, a high frequency sputtering method using an oxide as a target or a metal using a target is used.
After forming the metal thin film, there is a method of performing thermal oxidation, or a method of forming an oxide thin film by a reactive sputtering method (using Ar + O ₂ or the like as a sputtering gas).

On the other hand, as a CVD method, a thermal CVD method using a metal chloride as a raw material or, recently, Japanese Patent Application Laid-Open No. 61-190074, which aims at film formation at a lower temperature, has been proposed. There is an optical CVD method and the like.

The chemical film formation method is described in Material Research Society Symposium Proceeding, 73 (1986), pp. 725-730 (Ma
t.Res.Symp.Proc., 73 , (1986), pp. 725-73
The sol-gel method, which is a kind of liquid phase method as shown in (0), has recently attracted attention as a low-temperature film forming method. other,
JP-A-62-97151 and JP-A-53-149281 are known.

Further, a photo-activated catalyst such as α-hydroxyketone is added to various silane compounds and reacted to form a network structure having three-dimensional cross-linking. How to (XIV International Congress on Glass, (1986) pp. 429-436 (XIVIntl.
Congr.on Glass, (1986) pp. 429-436).

Although different from film formation, there is known a technique of irradiating an ultraviolet curable resin with light to produce a three-dimensional model of an organic substance (Nikkei New Materials, June 5, 1989).
JP, pp. 45-51).

Further, an organic acid salt of a alkoxide of a rare earth metal or an alkaline earth metal with copper and a β-diketone complex are mixed, coated and dried, and then irradiated with ultraviolet rays and infrared rays to decompose and oxidize to form a composite metal. There is a method for producing an oxide (Japanese Patent Application Laid-Open No. 64-87780).

There is also a method of producing a surface protective film by irradiating a reactive silane and a metal ester with ultraviolet rays (US Patent, 4,073, 967).

[0010]

SUMMARY OF THE INVENTION Among the above prior arts,
The sputtering method is a film formation method under a high vacuum, and a film having many oxygen defects is generated, and a film having a stoichiometric composition cannot be obtained. Also,
Argon gas or the like used as a sputtering gas easily remains in the film, and there is a defect that the oxygen-deficient portion and the residual gas adversely affect the characteristics of the oxide thin film.

In the thermal CVD method, in order to obtain a metal oxide film by hydrolyzing a metal halide as a raw material, 6
A high temperature of 00 ° C. or higher is required.

In the photo-CVD method, light energy is used for a decomposition reaction of a raw material, and a thin film is formed at a lower temperature. However, the decomposition energy of the raw material and the reaction energy with oxygen after the decomposition are all consumed. It cannot be given by light energy, requires heat application, and requires heating of the substrate. Further, although the growth rate of the oxide thin film is increased by this method, the film quality is the same as that when no light is irradiated.

Further, a method of performing thermal oxidation after sputtering,
In the method D, since a step of applying heat is indispensable, it has been difficult to form a thin film on a substrate having a low heat resistance, for example, an organic substrate or a substrate having a large difference in thermal expansion coefficient. Also, sputtering method,
The CVD method also requires a large-scale apparatus, and has a problem that the apparatus is expensive and it is difficult to form a large-area film.

The sol-gel method, which is one of the liquid phase methods, is based on a chemical reaction in a solution, and synthesizes an inorganic polymer which is a ceramic at ordinary temperature or a temperature close to ordinary temperature. However, since a metal alkoxide, which is a kind of organic substance, is used as a raw material, carbon tends to remain in a product. In addition, there is a problem that a long time is required for the reaction. Furthermore, a method of performing heat treatment after film formation is known,
Since heat is applied, the method of irradiating ultraviolet rays after film formation also has a problem that carbon remains. In a method in which the reaction solution does not contain moisture and does not irradiate light, carbon tends to remain in the thin film after film formation, and it is difficult to remove carbon even by irradiating ultraviolet rays thereafter. In addition, the sol
Most of the films produced by the gel method are single-layer films, and there is no known method for obtaining a multilayer film or a composite film at a low temperature. Further, formation of a composite film or a multilayer film having a predetermined shape has not been considered.

The method of adding a photoactivation catalyst to various silanes and irradiating light is intended to increase the three-dimensional crosslinking, and no consideration has been given to removing organic substances from the film. The same applies to the case where a reactive silane and a metal ester are used. Further, when a material utilizing both characteristics is obtained by dispersing a metal oxide in an organic compound, since it is a mere mixture, uniformity is not sufficient and there is a problem in the obtained characteristics.

An object of the present invention is to solve the problems of the CVD method as the physical film forming method and the chemical film forming method and the conventional sol-gel method. That is, an object is to obtain a high-quality polymer metal oxide thin film having a stoichiometric composition in a short time without requiring high-temperature heat treatment, and to enable a large-area film to be formed by a simple apparatus. Another object is to obtain a multilayer film and a composite film by the above-described means. It is still another object of the present invention to provide a method for forming an inorganic or inorganic / organic composite having a predetermined shape or an inorganic or inorganic / organic composite having a multilayer structure at a low temperature, which has not been achieved by the conventional method.

Another object of the present invention is to obtain a high-quality oxide thin film which does not require a heat treatment and which is applied to an electronic device to obtain a high-performance thin film capacitor, an electroluminescent element and its display device, Semiconductor device,
The object is to obtain an optical disk. It is a further object of the present invention to provide a corrosion-resistant metal member having an environment-resistant protective film formed by forming an amorphous or polymer metal oxide thin film on the surface of the metal member.

[0018]

The above object is achieved by the following means of the present invention.

According to the present invention, there is provided a method for forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water, the method comprising: bonding a metal atom of the organometallic compound to an organic group to the solution. Irradiating an electromagnetic wave containing a component having a specific wavelength required to destroy the, a step of promoting the hydrolysis or thiolysis of the organometallic compound to form a metal oxide or metal sulfide prepolymer in the solution, and An object of the present invention is to provide a method for forming an inorganic polymer thin film, comprising a step of applying the prepolymer solution on the substrate and drying the solution.

The present invention also relates to a method for forming an inorganic polymer thin film on a substrate from a solution containing a low-molecular-weight organometallic compound and water, wherein the metalloxane between the metal atoms of the organometallic compound is added to the solution. Irradiating an electromagnetic wave containing a component of a specific wavelength necessary for generation of a bond, and forming a prepolymer of a metal oxide or a metal sulfide by hydrolysis or thiolysis of the organometallic compound in the solution;
And a method for forming an inorganic polymer thin film, comprising a step of applying a solution of the prepolymer to the substrate and drying the solution.

Further, the present invention provides a method for forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water, wherein the solution has a specific wavelength required for polycondensation of the organometallic compound. Irradiating light energy containing light to promote hydrolysis or thiolysis to form a prepolymer of metal oxide or metal sulfide in the solution, and apply and dry the solution of the prepolymer on the substrate There is provided a method for forming an inorganic polymer thin film including a step.

A preferred embodiment of the present invention is a method for forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water. Irradiating light energy including light having a specific wavelength necessary to break the bond between the metal atom and the organic group of the organometallic compound and promote hydrolysis of the organometallic compound while in the state, The present invention relates to a method for forming an inorganic polymer thin film including a step of forming a metal oxide prepolymer therein and a step of exposing the coating film to an atmosphere containing ozone to oxidize organic substances in the film to reduce the organic substances.

According to another preferred embodiment, in a method of forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water, a step of applying the solution on a substrate, While the solution is in a wet state, the organic metal compound is irradiated with light energy including light of a specific wavelength necessary to break the bond between a metal atom and an organic group and promote thiolysis of the organic metal compound, The present invention relates to a method for forming an inorganic polymer thin film, comprising: a step of forming a metal sulfide prepolymer in a coating film; and a step of exposing the coating film to an atmosphere containing hydrogen sulfide to reduce an organic substance by sulfided an organic substance in the film.

Another aspect of the present invention is a method of forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water, the method comprising: applying the solution to a substrate; Disposing a pattern mask having a desired pattern on the substrate, while breaking the bond between a metal atom and an organic group of the organometallic compound while the solution is in a wet state to promote hydrolysis or thiolysis of the organometallic compound. Irradiating light energy including light of a specific wavelength necessary for the light through the pattern mask to form a metal oxide or sulfide prepolymer on a selected portion of the coating film;
Removing a non-selected portion of the coating film from the substrate, exposing the pattern film remaining on the substrate to an atmosphere containing ozone or hydrogen sulfide, and oxidizing or sulfurizing the organic material in the film to reduce the organic material. This is a method for forming an oxide thin film.

As the low molecular weight organometallic compound, one or more substances selected from the group consisting of metal alkoxides, metal β-ketoester complexes, metal β-diketone complexes and metal thioesters are used.

The solution can contain an organic acid and an alcohol.

The electromagnetic wave is light energy such as ultraviolet light or laser light.

According to still another aspect of the present invention, in a method of forming a metal oxide multilayer film on a substrate from a solution containing a metal alkoxide and water, the solution contains at least two kinds of metal alkoxides, Light energy including light of a specific wavelength required to break the bond between a metal atom and an organic group is sequentially irradiated to the solution so as to correspond to each metal alkoxide, and a metal oxide prepolymer is contained in the solution. Forming, a step of applying the prepolymer solution to the substrate, and irradiating light energy of a specific wavelength necessary for generating ozone to the coating film to oxidize and remove organic substances in the coating film. A method for forming a metal oxide multilayer film including a step is provided.

The present invention further comprises a step of coating a solution containing a metal alkoxide and water on a substrate, wherein a specific wavelength required to break the bond between a metal atom and an alkoxy group while the coating solution is in a wet state. Irradiating light energy to hydrolyze the alkoxide to form a precursor of the inorganic polymer; relatively moving the position of the substrate and the irradiation source to irradiate a selected portion of the coating solution to form the precursor; Forming a predetermined pattern of the body on the substrate and exposing the pattern to an atmosphere containing ozone to oxidize and remove organic substances in the precursor and convert the precursor to an inorganic polymer substantially consisting of a metal oxide; It is intended to provide a method for forming an inorganic polymer thin film including steps.

The metal polymer obtained by the present invention is an amorphous inorganic polymer having a carbon content of 0.01 to 4 atomic%, containing a small amount of C—H bonds, and substantially consisting of a metal oxide. According to the present invention, a metal polymer thin film formed on a substrate having a decomposition initiation temperature of 300 ° C. or less, particularly 200 ° C. or less, has a carbon content of 0.01 to 4 atomic% and a small amount of carbon.
An inorganic polymer thin film containing an -H bond and being an amorphous noble metal polymer substantially consisting of a metal oxide is obtained.

According to the present invention, in a composite comprising a substrate and an inorganic thin film formed thereon, the difference in thermal expansion coefficient between the substrate and the thin film is at least 5 × 10 ⁻⁶ K ⁻¹ , Is an inorganic polymer composed of a stoichiometric composition of 86 atomic% or more of oxygen, 0.01 to 4 atomic% of carbon, a small amount of C—H bonds, and substantially composed of a metal oxide. An object thin film is obtained.

Utilizing the present invention, it has a particle size of 0.05 μm or less, contains 85 atomic% or more of stoichiometric oxygen,
In addition, a composite structure is obtained in which an inorganic polymer having a carbon content of 0.01 to 4 atomic% and containing a small amount of C—H bonds and substantially consisting of a metal oxide is dispersed in an organic polymer.

In practicing the present invention, when a solution containing a metal alkoxide as an active ingredient is added, a container, a specific wavelength necessary for breaking the bond between the metal and the alkoxy group, and the metal-to-metal A light irradiation device for irradiating light energy of a specific wavelength required for the production of metalloxane or a specific wavelength required for the condensation polymerization of the metal alkoxide,
A metal alkoxide solution processing apparatus including a monochromator that converts light generated from the light irradiation apparatus into light mainly having the specific wavelength can be used.

According to the present invention, from a solution having alcohol, water and a metal oxide prepolymer, a composition for forming a metal oxide thin film in which the residual carbon content of the prepolymer in the solution is 8 atomic% or less can be obtained.

As a specific application example of the present invention, in an electroluminescence device having a light emitting layer on a substrate,
A withstand voltage between the substrate and the light emitting layer is 2.8 MV / cm.
The above polymer metal oxide insulating thin film is formed, and the thin film contains 85 atomic% or more of oxygen in a stoichiometric composition,
In addition, there is an electroluminescent element comprising 0.01 to 4 atomic% of carbon and containing a small amount of C—H bonds and substantially consisting of an inorganic polymer composed of a metal oxide.

In addition, the thin film capacitor formed on the substrate is composed of a polymer amorphous metal oxide thin film, has a stoichiometric oxygen content of 85 atomic% or more, and / or has a residual carbon content of the thin film. Having a oxygen content of at least 85 atomic% in stoichiometric composition and / or 0.01 to 4 atomic%. % Transparent carbon, a first insulating layer, a light emitting layer, a second insulating layer, and an upper electrode are sequentially formed on a metal member or a substrate, the light emitting layer being formed on a lattice. In the display device, the transparent electrode, the first insulating layer and the second insulating layer are polymer metal oxide thin films, the thin films contain oxygen of 85 atomic% or more in stoichiometric composition, and 0.01 to 4 atoms In substantially consist of inorganic polymer comprising a metal oxide containing a small amount of C-H bonds, 200
The present invention can be applied to a display device which is driven by a voltage of volt or less.

Further, in an optical disk provided with a recording medium made of a polymer metal oxide on a transparent substrate, the metal oxide is a thin film, and the oxygen content of the thin film has a stoichiometric composition of the metal oxide. There is an application to an optical disc in which 85 atomic% or more and / or the residual carbon content is 0.01 to 4 atomic%.

According to the present invention, a solution containing a metal alkoxide as an active ingredient is irradiated with light having a wavelength corresponding to the binding energy between a metal and an alkoxy group, in order to achieve the object of obtaining a structure having a predetermined shape. The irradiation position is moved to form a predetermined shape, and if necessary,
It irradiates light for generating ozone in an oxygen-containing atmosphere.

The solution containing a metal alkoxide as an active ingredient may be a plurality of solutions composed of a single component, a solution containing a plurality of components, or a resin or the like which undergoes polymerization by light irradiation. Further, when an organic / inorganic composite having a multilayer structure is formed, a resin or the like which undergoes polymerization by light irradiation is contained as a solution for forming an organic layer.

The light irradiation is performed by controlling the movement of the formed body, the movement of the light source, or controlling both the formed body and the light source.

This method utilizes a feature that a predetermined shape can be formed at a low temperature by light energy.
An oxide film is formed on a substrate having a heat resistance temperature of 300 ° C. or less or a large difference in thermal expansion coefficient.

Since the amount of carbon can be reduced by the first-stage light irradiation, the second-stage light irradiation can be performed in an atmosphere having a low oxygen concentration. For this reason, the generated ozone concentration can be kept low, and the damage to the organic substrate and the metal substrate can be suppressed.

The metal oxide having a predetermined shape formed according to the present invention has an oxygen content of 85 atomic% or more in stoichiometric composition, or a residual carbon amount of 4 atomic% or less. Further, C—H having a carbon content of 0.01 to 4 atomic%.
It has bonding and is amorphous.

In the apparatus used in the present invention, a monochromator is installed in the light irradiation section so that light having a wavelength that accelerates the reaction of various kinds of metal alkoxides and organic resins can be irradiated.

The formed body obtained by the above method is
It can be applied to various electronic devices, antireflection films, wires and the like.

Further, the above method can be used for the following applications.

The electroluminescent device including the base and the light emitting layer can be used as a polymer metal oxide thin film having a withstand voltage between the base and the light emitting layer of 2.8 MV / cm or more.

It can be used as a dielectric film of a thin film capacitor on a metal substrate, a printed substrate or in a substrate.

It can be used as a polymer metal oxide thin film on the surface of a highly corrosion-resistant metal member.

The protective film of the integrated circuit device having a protective film on the surface of the integrated circuit can be used as a polymer metal oxide thin film.

A transparent electrode, a first insulating layer, a light emitting layer,
A second insulating layer and an upper electrode are sequentially formed, the light emitting layer is formed on a grid, and the transparent electrode, the first insulating layer, and the second insulating layer of the display device driven at a voltage of 200 volts or less include: It can be used as a polymer metal oxide thin film.

It can be used as a polymer metal oxide thin film of an optical disk having a recording medium made of a polymer metal oxide on a transparent substrate.

By forming the polymer metal oxide multilayer film of the present invention on an organic substrate having no heat resistance or a substrate having a small difference in thermal expansion coefficient from a film, an antireflection film and a heat ray reflection film are produced. be able to.

It can be used as a polymer metal oxide thin film for an environment-resistant protective film of a plastic optical fiber bar.

A semiconductor element can be manufactured by protecting a Si chip with the inorganic film of the present invention and sealing it with a resin.

[0056]

The present invention will be described by taking a metal alkoxide as an example. Metal alkoxides have the general formula M (OR) _n (M: metal,
R: alkyl group, n: integer).
The metal alkoxide absorbs the energy of the reaction in the presence of water and causes a hydrolysis reaction to produce a compound having a structure in which a part of an alkoxy group represented by (RO) _n-1 MOH is substituted with a hydroxyl group. The intermediate formed by partial hydrolysis in this way further reacts with another metal alkoxide molecule,

[0057]

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A condensed product grows. The sol-gel method synthesizes an inorganic polymer, that is, an oxide, based on the above chemical reaction, that is, a hydrolysis reaction and a condensation reaction. In this sol-gel reaction, the rate-determining step of the reaction is said to be cleavage of a metal-alkoxy group bond during a hydrolysis reaction.

The present invention selectively cleaves a metal-alkoxy group bond by irradiating a solution containing a metal alkoxide as an active ingredient with an electromagnetic wave, particularly light energy, having a specific wavelength required to break the metal-alkoxy group bond. In this method, the hydrolysis reaction, which is the rate-determining step of the sol-gel reaction, is promoted to increase the degree of polymerization, thereby completing the sol-gel reaction in an ideal stoichiometric composition as a metal oxide. Various lasers are suitable as light energy in addition to ultraviolet light. For example, a He-Cd laser is 325 nm.
The Kr-F laser generates light having a wavelength of 249 nm, and the Ar-F laser generates light having a wavelength of 193 nm. In addition, irradiation of light having a wavelength for generating ozone on a thin film formed on a substrate using the above-described reaction solution is performed by oxidizing organic substances remaining in the film in a small amount with ozone to further reduce organic substances in the film. To reduce the oxygen content in the metal oxide of the film to 85% or more of the stoichiometric composition, or to reduce the residual carbon content to 0.01%.
To 4 at%. In particular, it is preferable in terms of characteristics that the oxygen content be 95% or less of the stoichiometric composition and the residual carbon content be 0.2 atomic% or more. Further, such a film can be obtained in a short time.

By adding the light irradiation step to the solution in the sol-gel reaction, an oxide thin film having a uniform stoichiometric composition at a low temperature can be obtained. This eliminates the need for a heat treatment for improving the film quality after the film is formed, and makes it possible to form an oxide thin film on a substrate such as a resin or paper having a heat-resistant temperature of 300 ° C. or less or a substrate having a large difference in thermal expansion coefficient. Become. The oxide thin film thus obtained has a carbon content of 0.01 to 4 atomic%. In addition, the composition MOx of the oxide
In this case, a thin film having an oxygen content of 85 atomic% or more of the stoichiometric composition can be obtained, and a film having excellent electric characteristics can be obtained.

In the present invention, when the metal thioester M (SR) _n is used as a starting material, thiolysis occurs in the presence of hydrogen sulfide.

[0062]

M (SR) _n + X · H ₂ S → M (SH) _x (SR) _nx + RSH (Formula 2) When hydrogen sulfide is further acted on this, a polymer of metal sulfide is formed.

If a deesterification condensation reaction is used instead of the hydrolysis reaction and the polymerization reaction in the sol-gel reaction, a sol-gel reaction in a non-aqueous solvent system becomes possible.
The deesterification reaction utilizes a co-condensation reaction using an organic acid shown below.

[0064]

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In the above reaction, since the reaction proceeds in all directions in a three-dimensional manner, an inorganic polymer is generated.

Further, by irradiating light energy having a specific wavelength necessary for breaking the metal-alkoxy group bond, the metal-alkoxy group bond is selectively cleaved, and the reaction is accelerated to cause high polymerization. Thus, a metal oxide having a stoichiometric composition can be obtained. The solution irradiated with light energy does not contain water, and the reaction can be performed in a non-aqueous solvent system.

Accordingly, since the obtained metal oxide does not contain moisture, the application of this method to an electronic device or the like in which moisture is a problem is effective.

Similarly, of the techniques using light, the photo CVD
In the method, the reaction rate is improved, but heat application is indispensable for the decomposition reaction of the raw material, and substrate heating is required. Therefore, it is difficult to form a film on a substrate having a low heat-resistant temperature or a substrate having a large difference in thermal expansion coefficient.

In the method of adding a photoactivation catalyst to various silanes to increase three-dimensional crosslinking by light irradiation, an organic chain compound is generated in the crosslinking portion, and the organic substance in the film is removed. It does not meet the purpose of the invention.

The apparatus for forming a metal oxide thin film according to the present invention is capable of promoting a chemical reaction by irradiating light in a solution state to make a polymer higher and to form a film using the solution and to form a film of the solution. Furthermore, by irradiating light of a specific wavelength necessary for generating ozone to oxidize and remove organic substances in the film, the resulting polymer metal oxide thin film has a high purity with few impurities and a high stoichiometry. A composition close to the composition is obtained. The formation of a metal oxide prepolymer having a higher molecular weight at the stage of a solution containing a metal alkoxide can provide excellent properties as a final metal oxide thin film.

The light irradiated into the solution has a specific wavelength necessary for breaking the bond between the metal and the alkoxy group, a specific wavelength required for forming a metalloxane bond between the metal and the metal, or a metal alkoxide. It is necessary to use light of a specific wavelength required for polycondensation. Therefore, it is possible to obtain a polymer having a higher purity by irradiating only light having a specific wavelength. Irradiation with light having another wavelength may cause the light other than the wavelength to obtain a polymer other than the polymer of the target molecule, and a high-purity polymer cannot be obtained.

In the present invention, it is possible to irradiate a light-irradiated solution on a substrate by forming a film on the substrate without performing a special drying step, thereby improving the effect of removing impurities in the film. Can be. To irradiate this specific wavelength light, a monochromator is provided in the light irradiating section so that only the specific wavelength light can be irradiated. Therefore, irradiation of light having a specific wavelength corresponding to the metal-alkoxide bond of various various metal alkoxides becomes possible. Thereby, more effective light irradiation can be performed for the sol-gel reaction using various metal alkoxides.

According to the present invention, it is possible to obtain a metal oxide thin film having a low stoichiometric ratio and a low organic matter content at a low temperature.
Since this metal oxide thin film shows good performance as a dielectric and an insulator, a high-capacity thin film capacitor, a low-voltage driven electroluminescent element, a coating protective film with good environmental resistance, and a protective film for a semiconductor element Recording media for optical disks, protective films for plastic optical fibers, protective films for plastic lenses, capacitors formed on printed circuit boards, polarizing plates for STN liquid crystals, semiconductor mounting with metal oxide films on Cu or Cu-based alloys It is suitable as a substrate. For example, when this method is used for producing a liquid crystal,
It can be applied to the production of the transparent electrode 141, the phase compensator 146, and the like shown in FIG. 26 and can be formed at a low temperature, so that a high-quality product can be obtained without heat treatment.

If a laser having strong directivity is used for light irradiation, a fine pattern of an oxide thin film can be formed on a substrate.

The sol-gel reaction solution to be irradiated with light in the present method may contain a catalyst such as an acid or an alkali. In addition, by keeping the reaction solution at a low temperature, the reaction solution can be kept stable, and by irradiating light during film formation,
A sol solution suitable for film formation can be obtained.

According to the present invention, since a solution containing a metal alkoxide is irradiated with light having a specific wavelength, the degree of polymerization of the metal alkoxide at the stage of the solution can be measured. Forming a film is the most significant feature of obtaining a high-purity metal oxide thin film. Another feature is that the degree of polymerization of the metal oxide can be monitored by examining the solution using the absorption spectrum or the light scattering method, and a product of stable quality can be obtained.

The present invention is effective for metal alkoxides, metal β-ketoester complexes, metal β-diketone complexes or metal thioesters.

Specific compounds for the β-ketoester complex and β-diketone complex are as follows.

[0079]

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Here, a proton is displaced by one and a resonance phenomenon occurs, and the entire β-diketone is negatively charged and coordinates to the metal with oxygen. The number of β-diketones coordinated to the metal depends on the type of metal,
It changes depending on the valence. In particular,

[0081]

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[0082]

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[0083]

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The following can be mentioned.

On the other hand, a β-ketoester complex is a β-ketoester

[0086]

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[0087]

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R ⁰ is represented by a methyl group, but the same applies to other alkyl groups. The properties are the same as those of the β-diketone complex. In particular

[0089]

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The following are examples:

It is necessary to irradiate these reaction solutions with light having the above-mentioned required wavelength. This wavelength is appropriately selected depending on the substance. It is preferable that the following Ti alkoxide is mainly irradiated with light having a wavelength of 248 nm.

LiOCH ₃ , NaOCH ₃ , Ca (OC
H ₃ ) ₂ , Ba (OC ₂ H ₅ ) ₂ , Zn (OC ₂ H ₅ ) ₂ , B (OC
_{H 3) 3, Al (i} -OC 3 H 7) 3, Ga (OC 2 H 5) 3, Ya
(OC ₄ H ₉ ) ₃ , Si (OC ₂ H ₅ ) ₄ , Ge (OC ₂ H ₅ ) ₄ , Pb
(OC ₄ H ₉ ) ₄ , P (OCH ₃ ) ₃ , Sb (OC ₂ H ₅ ) ₃ , VO
(OC ₂ H ₅ ) ₃ , Ta (OC ₃ H ₇ ) ₅ , W (OC ₂ H ₅ ) ₆ , Nd
(OC ₂ H ₅ ) ₃ , Ti (iso-OC ₃ H ₇ ) ₄ , Zr (OC
_{2 H 5) 4, La [} Al (iso-OC 3 H 7) 4] 3, Mg [Al (i
so-OC ₃ H ₇ ) ₄ ] ₂ , Mg [Al (iso-OC ₄ H ₉ ) ₄ ] ₂ , N
_{i [Al (iso-OC 3} H 7) 4] 3, (C 3 H 7 O) 2 Zr [Al
(OC ₃ H ₇ ) ₄ ] ₂ , Ba [Zr ₂ (OC ₂ H ₅ ) ₉ ] ₂ .

By moving the position where the light energy is irradiated, it is possible to form not only a thin film but also a component having a predetermined shape. At that time, when the wavelength of the light to be irradiated is changed by a device equipped with a monochromator,
The formed article can have various functions. For example,
In the process of or after the formation of the component having a predetermined shape, the component remains in the component by irradiating light energy having a wavelength necessary for generating ozone in addition to light energy having a wavelength for promoting a reaction. Organic matter can be reduced.

In addition, not only the position of the light source but also the formed object may be moved, or even if both are moved, the formed object may have a two-dimensional or three-dimensional predetermined shape.

In the present invention, the reaction is promoted or the function is increased by light irradiation. However, since the reaction can be completed at a low temperature, an organic-inorganic composite or a laminated structure which cannot be achieved by the conventional method requiring heat treatment is required. Can be formed.

Examples of the solution for forming a predetermined shape include a solution mainly composed of a plurality of metal alkoxides, a solution mainly composed of an organic polymer, a solution mainly composed of an organic polymer, and a metal alkoxide in addition to the above-mentioned solution mainly composed of a metal alkoxide. There are a solution mainly containing a mixture with an organic polymer and a solution mainly containing an organic metal compound other than the metal alkoxide. By using these solutions alone or in combination, it is possible to obtain a formed product having a predetermined shape having various functions.
Even when various fillers are contained in the solution, they can be effectively used as the present invention.

When the technique of the present invention is applied to a solution mainly containing a mixture of a metal alkoxide and an organic polymer, the resulting structure is obtained because the metal alkoxide is uniformly dispersed in the organic polymer in the molecular order. Are highly reliable and superior to those of the prior art. The metal oxide, which is a derivative of the dispersed metal alkoxide, is not aggregated unlike the one obtained by adding a powder or the like in the conventional method, and is uniformly dispersed at a maximum of 0.05 μm.

As described above, a structure in which a metal oxide is uniformly dispersed in an organic polymer by applying the present invention has a higher dielectric constant than, for example, an organic polymer alone, and is suitable for applications such as high-performance film capacitors. Can be expected.

[0099]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

Embodiment 1 FIG. 1 is a structural view showing an example of a film forming apparatus for carrying out the present invention.

Box 1 in which atmosphere such as pure air can be replaced
A light irradiation device such as an ultraviolet lamp, a monochromator capable of selectively extracting light of a specific wavelength, a support 7 for fixing the monochromator, and a substrate 9 for immersing the substrate 9 in the reaction solution in the beaker 6. An immersion device 4 is provided.
The light emitted from the light irradiation device 2 is selected in wavelength by the monochromator 3, reflected by the mirror 8, and irradiated to the reaction solution contained in the beaker 6. The reaction solution is set on the stirrer 5 and is stirred by the rotation of the stirrer 10. After the sol-gel reaction has sufficiently progressed by light irradiation for a certain period of time, the mirror 8 is pulled up to the upper part of the monochromator 3. Next, the substrate 9 is immersed in the reaction solution by the immersion device 4 to form a film. The substrate 9 is stopped at the position where the light after passing through the mono-micrometer is most frequently irradiated, and the light is irradiated for a certain time. At this time, ozone is generated in the air, and the formed thin film is oxidized with ozone.

Using this apparatus, a Ta ₂ O ₅ thin film was formed according to the flow shown in FIG.

A 0.5 mol / l ethanol (C ₂ H ₅ OH) solution of tantalum ethoxide Ta (OR) ₅ was prepared. 8 ml of a 0.5 mol / l ethanol solution of water (H ₂ O) and 2.5 ml of a 0.1 mol / l hydrochloric acid ethanol solution are added to ₂ ml of this solution.
A solution obtained by adding 2 ml of ethanol to a mixed solution of
The solution was dropped at a speed of 1 minute to obtain a transparent and uniform mixed solution. Using a film forming apparatus shown in FIG. 1, a 254 nm mercury lamp corresponding to the absorption position of the tantalum-ethoxy group was added to this mixed solution.
For 30 minutes and 1 hour.

By this light irradiation, Ta is produced by the following reaction.
It is believed that polymerization of the oxide occurs and a high degree of polymerization prepolymer is formed in the solution.

Ta (OR) ₅ + H ₂ O → (RO) ₄ TaOH + ROH (RO) ₄ TaOH + Ta (OR) ₅ → (RO) ₄ Ta—O—Ta (OR) ₄ + ROH If the structure of the prepolymer is shown, It is as follows.

[0106]

Embedded image

Thereafter, the reaction solution having the prepolymer having a high degree of polymerization was subjected to SiO 2 deposition using an immersion apparatus attached to the film forming apparatus.
Films were formed on _two substrates, and irradiated with light (ultraviolet light) having a wavelength of 184 nm for about 10 minutes to generate ozone in the air. The temperature of the film during light irradiation is about 50-60 ° C. Thus, an amorphous polymer of a tantalum pentoxide film having the following molecular structure is formed on the substrate.

[0108]

Embedded image

FIG. 3 is an absorption spectrum diagram of a reaction solution when a tantalum ethoxide ethanol solution is irradiated with light from a mercury lamp having a wavelength of 254 nm. As shown in the figure,
Compared to the light before the solid light irradiation, the spectral line shifts to the short wavelength side by the light irradiation of the dotted line from 0.5 hour to the dotted line for 1 hour, and is formed in the reaction solution by monitoring this absorption spectrum. The polymerization of the tantalum pentoxide polymeric prepolymer can be monitored.

FIG. 4 shows the light irradiation time for the reaction solution and FIG.
FIG. 4 is a diagram showing the relationship between the light irradiation time and the wavelength at the peak value of the absorbance for each light irradiation time.

The peak value of each wavelength was 250 n without light irradiation.
m, 30 minutes irradiation at 224 nm, 60 minutes irradiation at 208 nm
The peak value is considered to be almost complete in about 100 minutes. About 50% prepolymerization occurs in 30 minutes and about 80% in 60 minutes. Therefore, the irradiation of the reaction liquid with light is preferably as high as the degree of prepolymerization, but is particularly preferably at least 50%, more preferably at least 80%, as the degree of prepolymerization.

The infrared absorption spectrum of the Ta ₂ O ₅ thin film produced by the above-mentioned production method, the amount of residual organic matter in the film, and the stoichiometric composition ratio were measured by comparing with a film formed by other methods using ESCA. .

FIG. 5 is an infrared absorption spectrum diagram of the obtained film. In the figure, (a) shows the case where the reaction solution and after the film formation were not irradiated with light, (b) the case where the light irradiation of the present invention was carried out, and (c) the film was formed without light irradiation on the above-mentioned reaction solution. Thereafter, heat treatment was performed at 400 ° C. in the air. As shown in the figure, which is lower compared to that of (a) and intensity of the absorption spectral line in the vicinity of and around 1600 cm ^-1 wavenumber 3300 cm ^-1 is that of (b) is (c), which is water This is because there is. Further, in (a), C based on organic matter is used.
H vibration is required. In addition, the polymer film of Ta oxide has the same absorption spectrum.

[0114] Figures 6-9 are each various relative dielectric constant of the Ta oxide film obtained by preparation of (epsilon), the withstand voltage (MV / cm), in the film
It is a figure which shows C content and TaOx composition . What the heat treatment the sol-gel film was heat-treated at 400 ° C. After depositing the reaction solution without light irradiation described above, the light-assisted sol-gel film is a film obtained by the process of FIG. 2 of the present invention, O ₂ after deposition in an oxygen The light-irradiated film, the sol-gel film had a reaction time of 6 hours without light irradiation, the photo-CVD film was formed at 200 to 300 ° C., and the thermal CVD was formed at 350 ° C.

Each sol-gel film is repeated four times and has a thickness of about 2000 °.

As shown in FIG. 6, the film of the present invention has a high relative dielectric constant of ε25 or more equivalent to the heat-treated film, but the CVD film and the sol-gel film have lower relative dielectric constants.

As shown in FIG. 7, the film of the present invention was 2.7 M
A withstand voltage of not less than V / cm is obtained.

As shown in FIG. 8, the C content in this film is particularly low at 4 atomic% in the photo- assisted sol-gel film in O ₂ , and a film having a low C content equivalent to that of the heat-treated film can be obtained.

As shown in FIG. 9, the light assist sol in oxygen
It can be seen that the TaOx composition of the gel film is 2.2, which has 88% oxygen with respect to the theoretical oxygen amount of 2.5, and a film having a stoichiometric ratio higher than 80% of 2.0 of the heat-treated film can be obtained.

The resistivity of the photo-assisted sol-gel film in oxygen has a high value of 10 ¹¹ Ωcm.

As is clear from the above results, the film of the present invention irradiated with light has a CH bond, has a residual organic content of 4.0 atomic% in terms of C, and has a TaOx composition ratio (O / Ta).
2.2.

The film irradiated with ultraviolet light at an irradiation intensity of 40 mW / cm ² for 3 hours was analyzed, and as a result, the C content was 0.01.
atm%.

On the other hand, the film not irradiated with light had a CH bond, had a residual organic matter content of 11.0 at% in terms of C amount, and had a TaOx composition ratio (O / Ta) of 1.6. The light-irradiated film shows a value of 1 / 2.8 in the amount of residual organic substances and a value of 1.4 times in the TaOx composition ratio (O / Ta), as compared with the film not irradiated with light. A film close to the theoretical ratio was obtained. Organic matter remaining amount similar to the film irradiated with light, Ta
In order to obtain a thin film having an Ox composition ratio, a heat treatment at 400 ° C. or higher was required for a film not irradiated with light.

Also, using the same method, the heat resistant temperature is 30
Organic substrate such as polyester film, mylar sheet, acrylic resin or the like at 0 ° C. or less, or stainless steel having a difference of thermal expansion coefficient of 5 × 10 ⁻⁶ K ⁻¹ or more.
7.3 × 10 ^-6 K ^-1 ), aluminum (coefficient of thermal expansion 23.6 × 1
A thin film was also formed on a metal substrate such as 0 ^-6 K ^-1 ). The organic residue and the TaOx composition ratio (O / Ta) of these films are as follows:
The values were similar to those of the film formed on the SiO ₂ substrate.

Example 2 A vapor-deposited transparent conductive film on a glass substrate with a transparent conductive film (34 mm × 34 mm) was subjected to photoetching to obtain a glass plate with a transparent conductive film having a width of 2 mm.

By using this glass substrate, FIG.
Electroluminescent element (EL element) shown in (b)
Was prepared.

A tantalum pentoxide film was similarly formed on the glass substrate 13 provided with the transparent conductive film 14 using the method of Example 1 in which the reaction solution was irradiated with light for 60 minutes. The steps of the method described in Example 1 were repeated four times, and an amorphous polymer Ta ₂ O ₅ film serving as the first insulating layer 15 of the EL element was formed on the transparent conductive film to a thickness of 2000 °. Next, as the light emitting layer 16, ZnS containing 0.5 wt% of Mn was vapor-deposited by 5000 ° electron beam, and then 2.6 × 10 ⁻⁴ Pa and 1 ° C. at 300 ° C.
Vacuum heat treatment was performed for hours. Further, BaTa ₂ O ₆ was formed as the second insulating layer 17 by a 2000 ° sputtering method. Aluminum was deposited as the upper electrode 18 by heating at a resistance of 2000 °, and then an electrode terminal was attached to obtain an EL element.

In the plan view of the EL element shown in FIG. 10B, the intersection of the transparent conductive film 14 and the upper electrode 18 corresponds to a pixel and emits light.

In the conventional EL element, since the Y ₂ O ₃ film having a dielectric constant of 12 and a withstand voltage of about ₃ to 5 MV / cm is used for the first insulating layer and the second insulating layer, the driving voltage of the EL element is reduced. Is about
A high voltage of 200 V was required. In this device, the characteristics of the Ta ₂ O ₅ film used for the first insulating layer were a dielectric constant of 28 and a withstand voltage of 2.8 MV / cm 2, and low voltage driving at 170 V was possible. On the other hand, in an EL device using a Ta ₂ O ₅ film that is not irradiated with light as the first insulating layer, the characteristics of the Ta ₂ O ₅ film as the first insulating layer can be maintained at a dielectric constant of 14 ° C. even after heat treatment at 300 ° C. after the light emitting layer is deposited. ,
Since the withstand voltage was as low as 2.3 MV / cm, a driving voltage of 210 V was required.

As the light emitting layer, Eu-containing CaS (red),
In addition to Ca-containing CaS (green) and Ce-containing SrS (blue-green), ZnS has Sm ³ + (red), Tb ³ + (green), and Tm ³ +.
(Blue) or the like.

As the insulating layer, a polymer film of SiO ₂ or Y ₂ O ₃ can be used. As described above, these compositions have a high oxygen content of 85% or more of the stoichiometric composition by the sol-gel method. An amorphous film can be obtained.

As the transparent conductive film 14, a tin alkoxide Sn (OC ₂ H ₅ ) ₄ and an indium alkoxide In (OCH ₃ ) ₃ solution were used.
A light having a wavelength of 0 nm is irradiated for 60 minutes to form a prepolymer solution of tin oxide and indium oxide, and a glass substrate 13 is immersed in this solution to form a film.
The step of irradiating 84 nm ultraviolet rays was repeated to form a transparent conductive film 14 having a predetermined film. Thereafter, it was formed in the same manner as the first insulating layer as described above. The subsequent light-emitting layer,
The second insulating layer and the upper electrode are formed similarly.

The EL element has a large number of pixels formed on a substrate and is driven by a high frequency power supply. The EL element is further provided with a protective film of SiO _{2 on} the entire surface, and is made of a polymer amorphous film formed by the method of the present invention as described above.

As described above, in the EL device manufactured according to the present embodiment, except for the light emitting layer and the upper electrode, the transparent conductive film and the insulating film can be formed by the polymer amorphous film by the sol-gel method which does not require heat treatment, so that the thermal expansion. There is an effect that the thermal effect due to the difference can be reduced and manufacturing can be performed.

Example 3 As shown in FIG. 11, Si [(P-type surface index
(100), specific resistance of 1.2 to 1.8 Ω · cm)], and a Ta ₂ O ₅ film was formed on this substrate by the method described in Example 1. Of the methods described in Example 1, 60
4 the steps used after irradiation minutes light times repeated, Ta ₂
An O ₅ film 20 was formed on a 2000 ° Si substrate. Further, after the Al electrode 21 was vacuum-deposited at a thickness of 1000 ° on the insulating film, the Al electrode 21 was similarly deposited on the back side of the substrate,
A thin film capacitor was manufactured.

The dielectric constant of the insulating layer is about 5 times larger than that of SiO ₂ at 28, and the withstand voltage is 2.8 MV / cm, which is larger than that of the conventional Ta ₂ O ₅ . By using the insulating film according to the present invention, a thin film capacitor having a large capacitance per unit area and a good withstand voltage characteristic could be obtained.

A similar thin-film capacitor could be formed directly on or in a printed circuit board. The printed circuit board in this case is effective for countermeasures against noise in the high-frequency circuit.

Example 4 SUS304 stainless steel beaker 22 (inner diameter 50 mm, depth 60
The process was repeated four times in the same manner as described in Example 3 on the inner surface of (mm), and a Ta ₂ O ₅ film 23 of about 2000 ° was coated. 3N hydrochloric acid 20 in this stainless beaker
ml, the entrance was sealed with parafilm and left for one month. After that, the hydrochloric acid was discarded and the inside of the beaker was observed.
No corrosion of the stainless steel surface was observed. The corrosion resistance was improved by coating the Ta ₂ O ₅ film by the present method.

In the case where no light was irradiated, the durability of the film on the stainless steel was poor, and the same experiment was carried out. After 7 days, the film was peeled off and corrosion occurred. In addition, when heat treatment was performed at 200 ° C. to increase the adhesion of the film, film peeling occurred, which was considered to be caused by a difference in thermal expansion coefficient between stainless steel and the thin film.

In addition to SUS304 stainless steel, it is also effective as protection against carbon steel against atmospheric oxidation and corrosion, and similar protection against oxidation and corrosion against metals and alloys such as Al and Cu. In this embodiment, an example of the Ta ₂ O ₅ film is shown, but the above-mentioned film material can be selected depending on the type of the material for other oxide films.

Example 5 A 0.5 mol / l ethanol solution of silicon tetraethoxide was prepared. 0.5 mol / l of water is added to 20 ml of this solution.
A mixed solution of 80 ml of ethanol solution and 10 ml of ethanol solution of 0.1 mol / l hydrochloric acid was dropped at a rate of 3 ml / min to obtain a transparent homogeneous solution. The mixed solution was irradiated with light of 210 nm corresponding to the absorption position of the silicon-ethoxy group using the film forming apparatus shown in FIG. 1 for 60 minutes. Next, a semiconductor element having a thin film integrated circuit formed on a silicon substrate 24 shown in FIG.
After being immersed in the solution to form the thin film 27 on the integrated circuit, light of 184 nm required for generating ozone was irradiated in the air for 10 minutes. In FIG. 12, 24 is a Si substrate,
25 is SiO ₂ , 26 is an Al electrode, and 27 is a polymer film of the SiO ₂ film produced by the method of the present invention. 27
In SiO ₂ polymer film, a protective film to protect the thin film integrated circuits from disturbance element (passivation). This film has a very pure composition close to the stoichiometric ratio and is more polymerized, so that a highly protective film can be obtained. Further, since the heat treatment is not performed after the film formation as in the conventional method, there is no generation of stress or diffusion of impurities such as Na + in the heat treatment step, and there is no adverse effect on the semiconductor element. For this reason, reduction of the soft error of the element having 75 or less fit is achieved. SiO
_{The two} films 25 are formed by thermal oxidation, and the Al electrodes 26 are formed by vapor deposition, sputtering, or the like.

Incidentally, as 27, Ta was used instead of SiO _2.
A high dielectric constant film such as ₂ O ₅ or PZT may be provided.

Example 6 A 1 mol / l isopropyl alcohol solution of tripropoxyantimony was prepared. Add 1mo of water to 30ml of this solution
15 ml of l / l isopropyl alcohol solution and 0.1 ml of hydrochloric acid.
A mixed solution of 5 ml of 1 mol / l isopropyl alcohol was dropped at a rate of 3 ml / min to obtain a transparent homogeneous solution. The mixed solution was irradiated with light of 250 nm corresponding to the absorption wavelength of antimony-isopropoxy group for 30 minutes using the film forming apparatus shown in FIG. Subsequently, a polymethyl methacrylate resin (PMMA) substrate 28 (having a diameter of 13) shown in FIG.
(0 cm, 1 mm thick), using a dipping device attached to the film forming device, dipping in a solution to form a thin film 29 on the PMMA substrate.
Irradiated with 4 nm light for 10 minutes. Thus, a recording medium layer having a thickness of 1000 ° was formed on the PMMA substrate. Similarly, a thin film was formed on another PMMA substrate. The two substrates are bonded via a spacer 30,
An optical disk having the configuration shown in FIG. 13 was manufactured.

This optical disc is not subjected to a heat treatment step, and has a long-term reliability because an antimony oxide thin film having a stoichiometric composition and good adhesion to a substrate is formed.

In the same manner, a metal alkoxide is used as a memory material, and mainly Te oxide, Ga, G
An oxide of at least one kind of e and As and at least 10% by weight of at least one kind of In, Sn and Sb can be obtained.

In some cases, a protective film is provided on the recording medium.
As this protective film, Si was formed in the same manner as in this embodiment.
An O ₂ polymer film can be formed. The SiO ₂ film can be obtained in the same manner as in the fifth embodiment. In addition, a protective film can be formed on the entire disk by this method.

As the substrate, other materials such as polycarbonate and epoxy resin can be used.

Example 7 0.5 mol / l ethanol solution of silicon ethoxide 2
20 ml of a 0.5 mol / l ethanol solution of titanium ethoxide was mixed with 0 ml. A mixed solution obtained by adding 1 ml of a 0.1 mol / l ethanol solution of hydrochloric acid to 20 ml of a 0.5 mol / l ethanol solution of water to this solution was added at 0.2 ml / min.
Add slowly at speed. A polyethylene substrate (50 × 20 × 2 (thickness) mm) was placed at a position 5 mm below the liquid level in the uniform mixed solution thus prepared. Next, a wavelength 210 corresponding to the absorption wavelength of silicon ethoxide was measured from above the liquid surface.
After irradiating with light of 10 nm for 10 minutes, the substrate was pulled out of the liquid and irradiated with light of 184 nm required for ozone oxidation on the substrate for 10 minutes. This substrate is placed again at a position 5 mm below the liquid level,
This time, 260 nm corresponding to the absorption wavelength of titanium ethoxide
For 10 minutes. Then, the substrate was pulled up and irradiated with light of 184 nm necessary for ozone oxidation. Such 2
The steps of irradiating light of 10 nm, 184 nm, 260 nm, and 184 nm were alternately repeated five times. FIG. 14 shows the structure of the multilayer film thus manufactured. In the figure, a polyethylene substrate 31, a layer containing a large amount of SiO ₂ (containing TiO ₂ ) 32, a layer containing a large amount of TiO ₂ (containing SiO ₂ )
33. Thus, the multilayer film produced on the polyethylene substrate showed good performance as a lightweight, high-strength antireflection film. In addition, as a result of fixing the chemical species of SnO ₂ and TiO ₂ by ESCA, SnIV and TiIV
Was observed.

Example 8 0.5 mol / l ethanol solution of indium ethoxide 2
20 ml of a 0.5 mol / l ethanol solution of 0 ml tin (tin) ethoxide was mixed. A mixed solution obtained by adding 30 ml of a 0.5 mol / l ethanol solution of water and 2 ml of a 0.1 mol / l ethanol solution of hydrochloric acid to this solution was added at 0.2 ml / min.
Was slowly added. A polyethylene substrate (50 × 50 × 2) was placed in the homogeneous mixed solution thus prepared.
(Thickness) mm) was placed at a position 5 mm below the liquid level. Then, after irradiating 270 nm light corresponding to the absorption wavelength of indium ethoxide from the upper part of the liquid for 10 minutes, the substrate is pulled out of the liquid and 184 nm light required for ozone oxidation is irradiated on the substrate.
Irradiated for minutes. The substrate was placed again at a position 5 mm below the liquid level, and then irradiated with light of 230 nm corresponding to the absorption wavelength of tin (tin) ethoxide for 10 minutes. Then, the substrate was lifted and irradiated with light of 184 nm required for ozone oxidation for 10 minutes. Such steps of light irradiation in the solution and light irradiation in the air were repeated five times. FIG. 15 shows the structure of the multilayer film thus manufactured. (Containing SnO ₂₎ containing a large amount of film polyethylene substrate 34, an In ₂ O in FIG. 35, (containing an In ₂ O) film containing SnO ₂ in a large amount is 36.

The multilayer film formed on the polyethylene substrate shows good performance as a lightweight, high-strength infrared reflection film.

Embodiment 9 FIG. 16 is a block diagram showing an example of an apparatus for implementing the present invention.

An irradiation position for forming a predetermined shape,
A light source 61 having a system for controlling a scanning speed, a beam diameter wavelength, etc., a substrate 62 for forming a shape body,
The substrate 62 is held, can be immersed and pulled up in the sample solutions 64 and 65, and can form a predetermined shape in conjunction with the light source 61. A substrate support device 63 provided with a vertical movement mechanism, a stirrer 66 for keeping a sample solution homogeneous, and a stirrer 67 are provided in a box 68. The box is provided with an atmosphere control section 69 that can be kept in an inactive state or the like.

The light generated from the light source 61 is immersed in each sample solution, and the substrate 6 on which it is coated is coated.
2 is irradiated. The irradiation position moves automatically under the set conditions.

Example 10 0.5 mol / l ethanol solution of indium ethoxide 2
20 ml of a 0.5 mol / l ethanol solution of tin (tin) ethoxide was mixed with 0 ml. 0.5 mol of water /
l, a solution obtained by adding 30 ml of an ethanol solution, 0.1 mol / l of hydrochloric acid and 2 ml of an ethanol solution were slowly added at a rate of 0.2 ml / min. Thus, a homogeneous mixed solution A was prepared. Next, epoxy acrylate resin (specific gravity
1.14, viscosity 200cps (20 degreeC), B were prepared.

Using the above A and B as sample solutions, a transparent conductive layer built-in material was formed using the predetermined shape forming apparatus shown in FIG.

The above A was put in 64 in FIG. 16, and B was put in 65 in FIG. An acrylic resin was used as the substrate 62. First, after the substrate 62 is immersed in 64, it is pulled up and the scanning speed 10
He-Cd laser (output 30 mW) was irradiated at 0 mm / sec. This was followed by scanning with 184 nm light at a speed of 10 mm / sec. This operation was repeated five times to form an indium-tin oxide (ITO) layer on the acrylic resin plate. The ITO layer formed on the acrylic resin plate has a thickness of 0.5
It has a pattern shown in FIG. 17A with a width of 30 μm and a width of 30 μm.

After the ITO layer was formed in this manner, the substrate was immersed in 55, and the whole surface of the substrate was irradiated with He-Cd laser light. This was repeated twice to form an epoxy acrylate resin coating layer having a thickness of 0.1 mm. Formed. The product formed in this example has the shape shown in FIGS. 17A and 17B, and by applying a current from both ends of the ITO, prevention of fogging of the substrate can be achieved.

Example 11 To a solution of polyvinyl butyral dissolved in 1% aqueous ethanol was added an ethyl seal solution of tantalum ethoxide [Ta (OC ₂ H ₅ ) ₅ ], and the mixture was sufficiently stirred to obtain a mixed solution.
The viscosity of this solution was adjusted during vacuum defoaming operation to about 5000 cps, and then formed into a sheet on a polyester sheet by a doctor blade method which is a well-known method.
At this time, the irradiation of Kr-F laser beam on the surface of the sheet-like formed body at a scan rate of 100 mm / sec at the outlet from the blade shines,
Then, light of 184 nm was irradiated by a UV lamp at a scanning speed of 10 mm / sec. After allowing the chemical reaction to proceed in this manner, it is dried to a thickness of about 30 μm, a length of 1000 mm,
A sheet having a width of 10 mm was obtained. The dielectric constant of this sheet is 6.1
Thus, it was larger than 3.6 of polyvinyl butyral alone.

Aluminum was vapor-deposited on one side of the formed sheet, and two sheets prepared in the same manner were overlapped and wound, and then heated to about 80 ° C. and pressurized at a pressure of 20 kg / cm ² , thereby forming a sheet between the wound sheets. After improving the adhesion, aluminum external electrodes were formed on both ends by metallikon, and lead wires were soldered to form capacitors.

In the capacitor thus formed, since the inorganic substance is uniformly compounded with the organic substance, the dielectric constant of the dielectric substance itself is higher than that of a capacitor using a film made of only an organic substance. High capacity of the capacitor was achieved.

Example 12 Using the mixed solution A and the resin B prepared in Example 10 as materials, a touch panel was manufactured by the following method.

First, the mixed solution A was coated on a polyester sheet by a doctor blade method. At this time, at the exit from the blade, Kr-
F laser light was irradiated at a scanning speed of 100 mm / sec, and then 184 nm light was irradiated at a scanning speed of 10 mm / sec by an ultraviolet lamp. This operation was repeated four times to form a transparent conductive film (ITO) having a thickness of 0.5 μm on the polyester sheet.
Was formed. Subsequently, a resin B is coated on the ITO film, and an irradiation light diameter of 0.3 m is applied on the coated surface at intervals of 5 mm.
Irradiated with a He-Cd laser of m m to form a structure having a cross-sectional shape as shown in FIG.

[0163] The spacer 75 formed of the resin B serves as a touch panel spacer.

A member in which an ITO film was formed on a polyester sheet was further manufactured in the same manner as described above, and after forming electrodes, both were combined to form a touch panel. The touch panel formed by this method satisfies applications in terms of responsiveness, transparency, and other characteristics.

Example 13 A 0.5 mol / l ethanol solution of silicon ethoxide 2
20 ml of a 0.5 mol / l water solution of ethanol and 0.1 mol / l of hydrochloric acid and 1 ml of an ethanol solution are added to 0 ml,
Mixed.

After the aluminum conductor wire was immersed in the homogeneous mixed solution thus prepared, the wire was irradiated with an Ar-F laser at the interface of the solution when the wire was pulled out of the solution. The wire lifting speed was 60 mm / sec. afterwards,
Irradiation with ultraviolet light of 184 nm was performed, and this operation was repeated five times to form an SiO ₂ insulating film on the surface of the electric wire. It was recognized that the insulating film formed in this way could secure insulation even when used in an environment of 600 ° C., and that it could be used in a vacuum without generating hydrocarbons or carbon dioxide gas. .

Further, it was confirmed that the coating layer can be continuously formed at a low temperature on the wire by the method of this embodiment, and that the present invention is industrially useful.

Example 14 A 0.5 mol / l ethanol solution of silicon ethoxide was added to a 0.5 mol / l ethanol solution of water and 0.1 ml of a hydrochloric acid solution.
A solution (I) was prepared by adding a mol / l ethanol solution. Further, a 0.5 mol / l ethanol solution of water and a 0.1 mol / l ethanol solution of hydrochloric acid were added to a 0.5 mol / l ethanol solution of titanium ethoxide to prepare a solution (II).

First, a polyester substrate was placed at a position 5 mm below the liquid level of the solution (I), and 210 nm light corresponding to the absorption wavelength of silicon ethoxide was irradiated from above the liquid level for 10 minutes, and then the substrate was moved from the liquid. And 18 needed for ozone oxidation
Irradiated with 4 nm light for 10 minutes. Thereafter, the substrate was placed at a position 5 mm below the liquid level of the solution (II), and irradiated with light of 260 nm corresponding to the absorption wavelength of titanium ethoxide for 10 minutes. Next, the substrate was moved from the liquid and irradiated with light of 184 nm required for ozone oxidation for 10 minutes. Light irradiation of 210 nm in the solution (I) → substrate movement → light irradiation of 184 nm → light irradiation of 260 nm in the solution (II) → substrate movement →
The step of irradiating 184 nm light was alternately repeated 5 times. Thereby, a SiO ₂ layer / TiO _{2 is formed} on the polyester substrate.
It was possible to form a multilayer film of layers. This multilayer film showed good properties as an antireflection film. Example 15 An environment-resistant protective film was formed on a plastic optical fiber. FIG. 19 is a cross-sectional view of the plastic optical fiber with a protective film manufactured this time. 81 is a protective film, 82 is an organic resin part, 83 is a gladd part, and 84 is a core part. The method for forming the protective film is described below.

A 0.5 mol / l ethanol solution of silicon ethoxide was prepared. 0.5 mol of water is added to 20 ml of this solution.
A mixed solution of 80 ml of a 1 / l ethanol solution and 10 ml of an ethanol solution of 0.1 mol / l hydrochloric acid was dropped at a rate of 3 ml / min to obtain a transparent homogeneous solution. The mixed solution was irradiated with light of 210 nm for 60 minutes using the film forming apparatus shown in FIG. In this solution, a plastic optical fiber (thickness: 2)
mmφ), soak the SiO ₂ protective film 8 on the fiber surface.
1 was formed. Then, the fiber was irradiated with 184 nm light required for generating ozone in the air for 10 minutes. The plastic optical fiber thus obtained was subjected to an environmental resistance test at 100 ° C. in engine oil. FIG. 20 shows the result. The vertical axis indicates the light amount holding ratio (%), and the horizontal axis indicates the elapsed time (hr). In the case of a fiber without a protective film, the light quantity holding ratio decreased to about 40% after 1000 hours due to diffusion of oil into the fiber. As described above, it was found that extremely excellent oil resistance was exhibited. Therefore, it is suitable, for example, as a plastic fiber for controlling an automobile engine.
Further, since the film formation method of this time is excellent as a low temperature process, it has become possible to form an inorganic film on a plastic fiber having no heat resistance.

Example 16 According to a normal plastic mold type semiconductor device manufacturing process, an Au wire was wire-bonded from a lead frame through a chip and a pellet as shown in FIG. An inorganic film was undercoated on this device by the following method.

0.5 mol / l of silicon tetraethoxide
An ethanol solution was prepared. 80 ml of a 0.5 mol / l ethanol solution of glacial acetic acid as an organic acid was slowly added to 20 ml of this solution. This mixed solution was irradiated with 210 nm light corresponding to the absorption position of the silicon-ethoxy group for 30 minutes. The element was immersed in this solution to form an inorganic protective film 95. Then, the device was irradiated with 184 nm light in air for 10 minutes. The device was immersed again in the solution to form a film, and then irradiated with 184 nm light in air for 10 minutes. This process was repeated 10 times to undercoat. The device manufactured in this manner was sealed with an epoxy resin to complete a semiconductor device. FIG. 21 shows the structure. In this figure, 91 is a lead frame,
92 denotes an Au wire, 93 denotes an Au-Si alloy, 94 denotes a chip, 95 denotes an inorganic protective film, and 96 denotes an epoxy resin.

Since the device manufactured by this method does not include a heat treatment step and does not contain water in the solution for forming the inorganic protective film, a very good semiconductor device can be obtained. That is, there is no generation of stress in the heat treatment step, and the wettability between the Au wire and the inorganic protective film is good, so that a protective film having high adhesion can be manufactured. Also,
No moisture is contained in this protective film. Therefore, reduction of the soft error of the element is achieved.

Example 17 A high frequency Ta ₂ O ₅ thin film capacitor was manufactured by using the method of the present invention. The fabrication method is as follows.

A 0.5 mol / l ethanol solution of tantalum ethoxide was prepared. 0.5 ml of glacial acetic acid was added to 20 ml of this solution.
80 ml of an ol / l ethanol solution were added. The mixed solution was irradiated with light of 254 nm for 60 minutes. As shown in FIG. 22, a backside masked Fe-42% Ni
The plate (10 × 10 × 0.5 t) 101 was immersed to form a film.
The surface on which the film was formed was irradiated with light of 184 nm in air for 10 minutes. Then, the plate was immersed again in the solution, and then irradiated with 184 nm light in the air for 10 minutes. This step is
This was repeated to produce a 1 μm Ta ₂ O ₅ film 102. T
The a ₂ O ₅ film with Fe-42% Ni Al103 on the plate to produce a thin film capacitor was vacuum-deposited. This thin-film capacitor shows almost no change in capacitance even at 1 GHz.
For this reason, when high-speed devices and circuits are mounted and operated with high density using this thin film capacitor, noise countermeasures, which are the largest cause of malfunctions, can be taken.

Example 18 A protective film was formed on a plastic lens. FIG.
FIG. 2 is a sectional view of a plastic lens with a protective film manufactured this time. 111 is a plastic lens, and 112 is a protective film. Hereinafter, a method for forming the protective film on the lens will be described.

A 0.5 mol / l ethanol solution of silicon ethoxide was prepared. 0.5 mol of water is added to 20 ml of this solution.
A mixed solution of 80 ml of a 1 / l ethanol solution and 10 ml of a 0.1 mol / l hydrochloric acid ethanol solution was dropped at a rate of 3 ml / min to obtain a transparent homogeneous solution. This mixed solution was irradiated with 210 nm light for 60 minutes using the film forming apparatus shown in FIG. A plastic lens (100 mmφ, maximum convex portion 5 mm), in which the concave portion was protected with a tape and the solution did not adhere, was immersed in this solution, and a SiO ₂ protective film 112 was formed on the convex lens surface of the plastic lens 111. . Then, this lens is used in air to generate the necessary
Light of 84 nm was irradiated for 10 minutes. Since the plastic lens obtained in this way is provided with a dense and hard protective film, there is no flaw on the lens in normal use, and the service life can be greatly extended. According to this method, a uniform film can be formed even on a convex portion or the like.

Example 19 Using the method of the present invention, Ta ₂ O ₅ was printed on a printed circuit board.
A thin film capacitor was manufactured. The fabrication method is as follows.

A 0.5 mol / l ethanol solution of tantalum ethoxide was prepared. 0.5 ml of glacial acetic acid was added to 20 ml of this solution.
80 ml of an ol / l ethanol solution were added. The mixed solution was irradiated with light of 254 nm for 60 minutes. A printed wiring board was masked at the position where the ground electrode of the silicon chip was grounded on the entire back surface and the front surface in this solution, and a Ta ₂ O ₅ film was formed on the surface of the printed wiring board.
The surface on which the film was formed was irradiated with light of 184 nm in air for 10 minutes. Then, the substrate was immersed again in the solution to form a film, and then irradiated with 184 nm light in air for 10 minutes. This process was repeated 10 times to produce a 0.5 μm Ta ₂ O ₅ film. Then, after removing the mask material, Al was vacuum-deposited on the upper portion of Ta ₂ O _{5 and on} the portion where the mask was removed to produce an electrode. A silicon chip was mounted on this upper part. FIG.
It is sectional drawing of the silicon chip on the printed wiring board produced in this way. In the figure, 121 is a printed circuit board, 12
2 is an electrode, 123 is a Ta ₂ O ₅ film as a dielectric layer, 124
Is a silicon chip. The Ta ₂ O ₅ film acts as a thin film capacitor, and almost no change in capacitance is observed even at 1 GHz. For this reason, the semiconductor element manufactured by the above-described method was able to take measures against noise, which is the largest cause of malfunction when high-speed devices and circuits are mounted and operated at high density.

Example 20 By using the method of the present invention, a semiconductor mounting substrate in which an insulating layer of a metal oxide film was provided on a copper plate was manufactured.

A 0.5 mol / l ethanol solution of silicon ethoxide was prepared. 80 ml of a 0.5 mol / l ethanol solution of glacial acetic acid as an organic acid was slowly added to 20 ml of this solution. This mixed solution was irradiated with 210 nm light for 30 minutes. A copper plate of a predetermined size is immersed in this solution,
An O ₂ film was formed. Then, 184n in air
m of light for 10 minutes. The steps of immersion film formation and light irradiation in the air were repeated 20 times to produce a SiO ₂ film of about 10 μm on a copper plate. This substrate is suitable as a substrate for mounting a semiconductor because an insulating layer is formed on copper having good heat conductivity. FIG. 25 shows a semiconductor element manufactured using this substrate. In this figure, 131 is a silicon chip, 132 is a bonding wire, 133 is a lead, 1
34 is a SiO ₂ film, 135 is a copper substrate, 136 is sealing glass, 137 is a metal layer, 138 is a cap, 139 is a cooling fin, and 140 is an adhesive layer. According to the present invention, a substrate provided with a sealing glass 136 made of an insulating layer SiO ₂ film on a copper 135 having good thermal conductivity can be used as a semiconductor mounting substrate. Therefore, heat generated during operation of the semiconductor element can be efficiently removed.

The following table summarizes the intensity and time of light irradiation in the examples.

[0183]

[Table 1]

In the table, a represents the wavelength, irradiation time, and light intensity of light used for the metal alkoxide prepolymer, and b represents the wavelength, irradiation time, and light intensity of light for oxidizing and decarburizing the prepolymer. .

[0185]

According to the present invention, a polymer metal polymer thin film having a small amount of residual organic substances and a uniform stoichiometric ratio can be obtained by a method in which heat treatment is not performed at a low temperature. Further, the polymer metal oxide thin film obtained by the present method exhibits good properties as a dielectric film and an insulating film. Therefore, it is used for a recording medium of an EL element, a thin film capacitor, a protective film optical disk of a semiconductor element, and the like. Higher performance of various electronic devices becomes possible.

Further, an oxide multilayer film having a uniform stoichiometric ratio at a low temperature can be obtained very easily and can be formed on an organic substrate, so that a light-weight, high-strength antireflection film and a heat ray reflection film can be formed.

Further, according to the present invention, since a predetermined shape can be formed at a low temperature by utilizing light energy, it is possible to form an organic / inorganic composite or a laminated structure which has been difficult to produce by the conventional method. Therefore, it is possible to ensure performance such as flexibility utilizing characteristics of both organic and inorganic substances. Also,
Since a coating layer or the like having a predetermined shape and a predetermined function can be continuously formed at a low temperature, it is efficient, economical, and industrially useful.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a film forming apparatus used in an embodiment of the present invention.

FIG. 2 is a process flow chart showing a method for forming a polymer metal oxide of the present invention.

FIG. 3 is a diagram showing wavelength and absorbance.

FIG. 4 is a diagram showing the relationship between wavelength and light irradiation time.

FIG. 5 is a diagram showing a relationship between a wave number and an absorbance.

FIG. 6 is a diagram showing the relative dielectric constant, withstand voltage, and TaOx composition of C content of a metal oxide film formed by various methods.

FIG. 7 is a diagram of a TaOx composition of relative permittivity, withstand voltage, and C content of a metal oxide film formed by various methods.

FIG. 8 is a diagram of TaOx composition of relative permittivity, withstand voltage, and C content of a metal oxide film formed by various methods.

FIG. 9 is a diagram of TaOx composition of relative permittivity, withstand voltage, and C content of a metal oxide film formed by various methods.

FIGS. 10A and 10B are a cross-sectional view and a plan view of an electroluminescence element.

FIG. 11 is a sectional view of a thin film capacitor.

FIG. 12 is a cross-sectional view of an integrated circuit device.

FIG. 13 is a sectional view of an optical disk.

FIG. 14: SiO ₂ -T prepared on a polyethylene substrate
sectional view of iO ₂ anti-reflection film.

FIG. 15: In ₂ O—S fabricated on a polyethylene substrate
FIG. 3 is a cross-sectional view of the nO ₂ heat ray reflective film.

FIG. 16 is a configuration diagram of an apparatus for forming a predetermined shape used in the present invention.

FIG. 17 is a configuration diagram of a dew condensation preventing plate manufactured by the method of the present invention.

FIG. 18 is a schematic cross-sectional view of a touch panel component manufactured according to the present invention.

FIG. 19 is a sectional view of a plastic optical fiber with a protective film.

FIG. 20 is a view showing test results of oil resistance.

FIG. 21 is a process chart of resin prevention of a semiconductor element.

FIG. 22 is a structural view of a high frequency Ta ₂ O ₅ thin film capacitor.

FIG. 23 is a sectional view of a plastic lens provided with a protective film.

FIG. 24 is a sectional view of a silicon chip on a printed board.

FIG. 25 is a cross-sectional view of a semiconductor element.

FIG. 26 is a cross-sectional view of a liquid crystal display device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Box, 2 ... Light irradiation device, 3 ... Monochromator,
4: immersion device, 4, 67: stirrer, 6: beaker, 7
... Support, 8 ... Mirror, 9,62 ... Substrate, 10,66 ...
Stirrer, 11, 20, 23 ... tantalum pentoxide (Ta
₂ O ₅ ) film, 12: SiO ₂ substrate, 13: glass substrate, 1
4: transparent conductive film, 15: first insulating layer, 16: light emitting layer, 1
7 ... second insulating layer, 18 ... upper electrode, 19, 24 ... Si substrate, 21,26,103 ... Al electrode, 22 ... stainless steel _{beaker, 25 ... SiO 2, 27,32,134 ...} Si
O ₂ film, 28: PMMA substrate, 29: recording medium, 30:
Spacer, 31, 34 ... polyethylene substrate, 33 ... T
iO ₂ film, 35 ... In ₂ O film, 36 ... SnO ₂ film, 61
... Light source, 63 ... Substrate support device, 64, 65 ... Sample solution,
68 box, 69 atmosphere control part, 70 acrylic resin, 71 indium-tin oxide layer (ITO layer), 7
2: Polyacrylate layer, 73: Polyester sheet,
74: ITO film, 75: Epoxy acrylate spacer, 81: Protective film, 82: Organic resin part, 83: Glad part, 84: Core part, 91: Lead frame, 92: Au
Wire, 93: Au-Si alloy, 94: Tip, 95:
Inorganic protective film, 96 epoxy resin, 101 Fe-42
% Ni plate, 102: Ta ₂ O ₅ , 111: plastic lens, 112: protective film, 121: printed circuit board, 122
... electrodes, 123 ... dielectric layers, 124, 131 ... silicon chips, 132 ... bonding wires, 133 ... leads,
135: copper substrate, 136: sealing glass, 137: metal layer, 138: cap, 139: cooling fin, 140
... Adhesive layer, 141 ... Transparent electrode, 142 ... Color filter, 143 ... Glass substrate, 144 ... Polarizer, 145 ... Color liquid crystal panel, 146 ... Phase compensator, 147 ... Reflector.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C01B 33/12 C01G 15/00 B C01G 15/00 19/02 C 19/02 23/04 C 23/04 G11B 7/24 511 G11B 7/24 511 538K 538 H01L 21/314 Z H01G 4/33 B41M 5/26 X H01L 21/314 H01G 4/06 102 (72) Inventor Shigeru Tanaka 4023 Kujimachi, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Hitachi, Ltd. Within the laboratory (72) Inventor Tadahiko Miyoshi 4023 Kuji-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Within the Hitachi Research Laboratory (58) Fields investigated (Int.Cl. ⁶ , DB name) C01B 13/32

Claims (5)

(57) [Claims] An inorganic polymer thin film formed on a substrate having a decomposition initiation temperature of 300 ° C. or lower has a carbon content of 0.01 to 4%.
An inorganic polymer thin film comprising at least atomic%, a small amount of C—H bonds, and an amorphous inorganic polymer substantially composed of a metal oxide. 2. An inorganic polymer thin film formed on a substrate having a decomposition onset temperature of 200 ° C. or lower contains oxygen in a stoichiometric composition of 86 atomic% or more and has a carbon content of 0.01 to 4%.
A metal oxide thin film comprising a C-H bond at atomic%. 3. A composite comprising a substrate and an inorganic thin film formed thereon, wherein the difference in thermal expansion coefficient between the substrate and the thin film is 5 × 10 ⁻⁶ K ⁻¹ or more, and the thin film is stoichiometric. 85 by composition
A metal oxide thin film containing at least atomic% of oxygen and having a small amount of carbon having a carbon content of 0.01 to 4 atomic% and substantially consisting of a metal oxide. . 4. A particle having a particle size of 0.05 μm or less, containing at least 85 atomic% of oxygen in a stoichiometric composition, and having a carbon content of 0.0.
A composite structure, wherein an inorganic polymer substantially containing a metal oxide and having a small amount of 1 to 4 atomic% and comprising a CH bond is dispersed in an organic polymer. 5. A container containing a solution containing a metal alkoxide as an active ingredient, a specific wavelength required for breaking the bond between a metal and an alkoxy group, and a solution necessary for producing a metalloxane between a metal and a metal. A light irradiation device for irradiating light energy of a predetermined wavelength or a specific wavelength necessary for polycondensation of the metal alkoxide, and a monochromator for converting light generated from the light irradiation device to light mainly having the specific wavelength are provided. A metal alkoxide solution processing apparatus, comprising: