JP3435262B2 - Anti-reflective coating - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film using a thin film of polymer metal oxide by a novel sol-gel reaction.

[0002]

2. Description of the Related Art Conventionally, regarding the method of forming an oxide thin film, Journal of Vacuum Science Technology A, Vol. 1, No. 3, (1983), No. 136.
Pages 2 to 1366 (J.Vac.Sci.Technol.A, Vol.No.3)
(1983), pp1362-1366), a method of sputtering is a physical film forming method.
Of Electrochemical Society, Volume 120,
(1973), pp. 927- (J. Electrochem. Soc., 12
0 , (1973), pp927-), a chemical vapor deposition method (Chemical Vapor D).
The eposition method: CVD method) is known.

In the sputtering method, a high-frequency sputtering method using an oxide as a target and a metal as a target are used.
There is a method of forming a metal thin film and then thermally oxidizing it, 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 the CVD method, a thermal CVD method using a metal chloride as a raw material, or recently, as disclosed in Japanese Patent Laid-Open No. 19-190074, which is aimed at film formation at a lower temperature. There is a photo CVD method.

Further, as the chemical film forming method, Material Research Society Symposium Proceeding, Volume 73 (1986), pages 725 to 730 (Ma
t.Res.Symp.Proc., 73 , (1986), pp725-73.
The sol-gel method, which is a type 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-activating catalyst such as α-hydroxyketone is added to various silane compounds to react with each other to form a network structure having three-dimensional cross-linking, and the cross-linking is further increased by irradiation with light to cure the film. Is the way to do it. (The XIV International Congress on Glass, (1986) pp429-436 (XIVIntl.
Congr. On Glass, (1986) pp429-436).

Further, 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).
Japanese issue, pp 45-51).

Further, after mixing, coating and drying an organic acid salt of a rare earth metal or an alkaline earth metal alkoxide and copper, a β-diketone complex, ultraviolet rays and infrared rays are irradiated to decompose and oxidize the composite metal. There is a method for producing an oxide (Japanese Patent Laid-Open No. 64-87780).

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

[0010]

Of the above-mentioned conventional techniques,
The sputtering method is a film forming method under a high vacuum, a film with many oxygen defects is formed, and a film having a stoichiometric composition cannot be obtained. Also,
Argon gas, which is used as a sputtering gas, is likely to remain in the film, and the oxygen defect 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 which is a raw material, 6
A high temperature of 00 ° C or higher is required.

The photo-CVD method uses light energy for the decomposition reaction of the raw material to form a thin film 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, heat must be applied, and the substrate must be heated. Further, although the growth rate of the oxide thin film is increased by this method, the quality of the film is the same as that when light is not irradiated.

Further, a method of thermal oxidation after sputtering or CV
In the D method, since the step of applying heat is indispensable, it is difficult to form a thin film on a substrate having a low heat resistance temperature, for example, on an organic substrate or a substrate having a large difference in thermal expansion coefficient. In addition, the sputtering method,
Both the CVD method and the CVD method require a large-scale apparatus, and there is a problem that the apparatus is expensive and it is difficult to form a large-area film.

The sol-gel method, which is a type of liquid phase method, is based on a chemical reaction in a solution and synthesizes an inorganic polymer which is a ceramic at room temperature or a temperature close to room temperature. However, since a metal alkoxide, which is a type of organic substance, is used as the raw material, carbon easily remains in the product. In addition, there is a problem that the reaction takes a long time. Furthermore, a method of heat treatment after film formation is known,
Since heat is applied, there is a problem that carbon remains in the method of irradiating ultraviolet rays after film formation. With a method in which the reaction solution does not contain water and is not irradiated with light, carbon is likely to remain in the thin film after film formation, and it is difficult to remove carbon even after irradiation with ultraviolet rays. Also, the previous 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 low temperature. Further, formation of a composite film or a multilayer film having a predetermined shape has not been considered.

The method of irradiating light by adding a photoactivating catalyst to various silanes is intended to increase three-dimensional cross linking by this, and removal of organic substances from the film has not been considered. The same applies when a reactive silane and a metal ester are used. Further, in the case where a metal oxide is dispersed in an organic compound to obtain a material that makes use of the characteristics of both, since it is merely a mixture, the 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, it 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 deposition of a large area with a simple device. Further, it is intended to obtain a multilayer film or a composite film by the means described above. Another object of the present invention is to provide a method for forming an inorganic material or an inorganic / organic composite material having a predetermined shape, an inorganic material or an inorganic / organic composite material having a multilayer structure at a low temperature, which has not been achieved by the conventional methods.

Another object of the present invention is to obtain a high-quality oxide thin film that does not require heat treatment and apply it to an electronic device to obtain a high-performance thin film capacitor, electroluminescent element and display device thereof. Semiconductor device,
To get an optical disc. Further, another object of the present invention is to provide a corrosion-resistant metal member having an amorphous or polymer metal oxide thin film formed on the surface of the metal member as an environment-resistant protective film.

[0018]

The above object can be achieved by the means of the present invention described below.

The present invention 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 solution comprises a bond between a metal atom of the organometallic compound and an organic group. Irradiating an electromagnetic wave containing a component having a specific wavelength necessary for destroying, to promote hydrolysis or thiolysis of the organometallic compound to form a prepolymer of a metal oxide or a metal sulfide in the solution, and It is intended to provide a method for forming an inorganic polymer thin film, which comprises a step of applying a solution of the prepolymer onto the substrate and drying.

The present invention also provides a method of forming an inorganic polymer thin film on a substrate from a solution containing a low molecular weight organometallic compound and water, wherein the solution contains metalloxane between the metal atom and the metal atom of the organometallic compound. Irradiating an electromagnetic wave containing a component of a specific wavelength necessary for the formation of a bond, to form 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, which comprises the steps of applying a solution of the prepolymer to the substrate and drying.

The present invention further 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. Light energy including light to accelerate hydrolysis or thiolysis to form a prepolymer of a metal oxide or a metal sulfide in the solution, and a solution of the prepolymer is applied onto the substrate and dried. Provided is a method for forming an inorganic polymer thin film, which includes a step.

A preferred embodiment 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 step of applying the solution onto the substrate, the solution being wet. The coating film is irradiated with light energy containing light of a specific wavelength necessary to break the bond between the metal atom and the organic group of the organometallic compound and accelerate the hydrolysis of the organometallic compound while in the state. The present invention relates to a method for forming an inorganic polymer thin film, which includes a step of forming a prepolymer of a metal oxide 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 onto the substrate, Irradiating light energy including light of a specific wavelength necessary to promote the thiolysis of the organometallic compound by breaking the bond between the metal atom and the organic group of the organometallic compound while the solution is in a wet state, The present invention relates to a method for forming an inorganic polymer thin film, which includes a step of forming a prepolymer of a metal sulfide in a coating film and a step of exposing the coating film to an atmosphere containing hydrogen sulfide to sulfurize organic substances in the film to reduce the organic substances.

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 step of applying the solution onto the substrate, A step of arranging a pattern mask having a desired pattern on the substrate, rupturing the bond between the metal atom and the organic group of the organometallic compound and promoting the hydrolysis or thiolysis of the organometallic compound while the solution is in a wet state. Irradiating through the pattern mask with light energy including light of a specific wavelength necessary for forming a prepolymer of a metal oxide or a sulfide on a selected portion of the coating film,
A metal including a step of removing a non-selected portion of the coating film from the substrate and a step of exposing the pattern film remaining on the substrate to an atmosphere containing ozone or hydrogen sulfide to oxidize or sulfurize the organic matter in the film to reduce the organic matter. It is a method of 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 may contain an organic acid and an alcohol.

The electromagnetic wave is light energy and is, for example, ultraviolet light or laser light.

According to still another aspect of the present invention, in a method for 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 containing light of a specific wavelength necessary for breaking the bond between the metal atom and the organic group is sequentially irradiated to the solution so as to correspond to each metal alkoxide, and the prepolymer of the metal oxide is added to the solution. The step of forming a solution, the step of applying the solution of the prepolymer to the substrate, and the step of irradiating the coating film with light energy of a specific wavelength necessary for generating ozone to oxidize and remove organic substances in the coating film. Provided is a method for forming a metal oxide multilayer film including a step.

The present invention further comprises the step of coating a solution containing a metal alkoxide and water on a substrate, and a coating solution having a specific wavelength necessary for breaking the bond between a metal atom and an alkoxy group while the coating solution is in a wet state. A step of irradiating light energy to hydrolyze the alkoxide to form a precursor of an inorganic polymer, irradiating a selected portion of the coating liquid by relatively moving the position of the substrate and the irradiation source, and The step of forming a predetermined pattern of the body on the substrate and the step of exposing the pattern to an atmosphere containing ozone to oxidize and remove the organic matter in the precursor, and convert the inorganic polymer to substantially an inorganic polymer consisting of a metal oxide. The present invention provides a method for forming an inorganic polymer thin film, which includes steps.

The metal polymer obtained by the present invention is an amorphous inorganic polymer having a carbon content of 0.01 to 4 atom% and containing a small amount of C--H bond and consisting essentially of a metal oxide. According to the present invention, the carbon content of the metal polymer thin film formed on the substrate having a decomposition initiation temperature of 300 ° C. or lower, particularly 200 ° C. or lower is 0.01 to 4 atom%, and a small amount of C
It is possible to obtain an inorganic polymer thin film which is an amorphous noble metal polymer substantially containing a -H bond and composed of a metal oxide.

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

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

In carrying out the present invention, a solution containing a metal alkoxide as an active ingredient is put into a container, and the solution has a specific wavelength necessary for breaking the bond between the metal and the alkoxy group, and the metal-metal gap. A light irradiation device for irradiating light energy of a specific wavelength required for the production of a metalloxane or a specific wavelength required for the condensation polymerization of the metal alkoxide,
A metal alkoxide solution treatment device provided with a monochromator which makes the light emitted from the light irradiation device mainly the light having the specific wavelength can be used.

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

As a specific application example of the present invention, in an electroluminescence device having a light emitting layer on a substrate,
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 device which is composed of an inorganic polymer having a carbon content of 0.01 to 4 atomic% and a small amount of C—H bond and consisting essentially of a metal oxide.

In addition, in a thin film capacitor formed on a substrate, the thin film capacitor is composed of a polymer amorphous metal oxide thin film, has an oxygen content of 85 atomic% or more in a stoichiometric composition, and / or has a residual carbon amount of the thin film. Of 0.01 to 4 atom%, having a polymer metal oxide thin film on the surface thereof, the thin film having an oxygen content of 85 atom% or more in a stoichiometric composition and / or 0.01 to 4 atom. % Residual carbon content, a transparent electrode, 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, and the light emitting layer is formed on a lattice. In the display device described above, the transparent electrode, the first insulating layer and the second insulating layer are polymer metal oxide thin films, and the thin films contain oxygen of 85 atomic% or more in a stoichiometric composition and carbon. Amount is 0.01 to 4 atoms In substantially consist of inorganic polymer comprising a metal oxide containing a small amount of C-H bonds, 200
It can be applied to a display device characterized by being driven by a voltage of not more than a volt.

Furthermore, in an optical disc having 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 is the stoichiometric composition of the metal oxide. There is an application to an optical disk in which the residual carbon amount is 85 atomic% or more and / or the residual carbon amount is 0.01 to 4 atomic%.

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

The solution containing a metal alkoxide as an active ingredient may be a plurality of solutions consisting of a single component or a solution containing a plurality of components, and may contain a resin or the like which undergoes polymerization upon irradiation with light. Further, in the case of forming an organic / inorganic composite having a multilayer structure, the solution for forming the organic material layer is made to contain a resin or the like which undergoes polymerization by light irradiation.

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

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

Since the amount of C can be reduced by the light irradiation in the first step, the light irradiation in the second step can be performed in an atmosphere having a low oxygen concentration. Therefore, the generated ozone concentration can be suppressed to a low level, and the substrate damage of 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 content of 4 atomic% or less. Further, C-H having a carbon content of 0.01 to 4 atomic%
It has a bond 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 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, etc.

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

It can be used as a polymer metal oxide thin film having a withstand voltage between the substrate and the light emitting layer of 2.8 MV / cm or more in an electroluminescence device having the substrate and the light emitting layer.

It can be used as a dielectric film of a thin film capacitor on a metal substrate, a printed circuit board 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 the 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, and
A second insulating layer and an upper electrode are sequentially formed, the light emitting layer is formed in a grid pattern, and the transparent electrode, the first insulating layer, and the second insulating layer of a display device driven by a voltage of 200 V or less, 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 polymer metal oxide on a transparent substrate.

An antireflection film and a heat ray reflective film are produced by forming the polymer metal oxide multilayer film of the present invention on a substrate having a small coefficient of thermal expansion difference from an organic substrate or film having no heat resistance. 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.

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

[0056]

The present invention will be described by taking a metal alkoxide as an example. The metal alkoxide has the general formula M (OR) _n (M: metal,
R: alkyl group, n: integer).
The metal alkoxide absorbs the reaction energy in the presence of water to cause a hydrolysis reaction to form a compound having a structure in which a part of the alkoxy group represented by (RO) _n-1 MOH is substituted with a hydroxyl group. The intermediate thus produced by partial hydrolysis reacts with other metal alkoxide molecules,

[0057]

[Chemical 1]

The resulting condensation product grows. The sol-gel method is a method of synthesizing 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 the cleavage of the metal-alkoxy group bond during the hydrolysis reaction.

The present invention selectively severs the metal-alkoxy group bond by irradiating a solution containing a metal alkoxide as an active ingredient with an electromagnetic wave having a specific wavelength necessary for destroying the metal-alkoxy group bond, particularly light energy. , The hydrolysis reaction, which is the rate-determining step of the sol-gel reaction, is promoted to make it highly polymerized, and the sol-gel reaction is attempted to be completed in an ideal stoichiometric composition state as a metal oxide. As the light energy, various lasers other than ultraviolet rays are suitable. For example, He-Cd laser is 325 nm
The Kr-F laser emits light with a wavelength of 249 nm, and the Ar-F laser emits light with a wavelength of 193 nm. Further, the thin film formed on the substrate using the above reaction solution is irradiated with light having a wavelength for generating ozone, by oxidizing a small amount of organic matter remaining in the film by ozone, To reduce the amount of oxygen in the metal oxide of the film to 85% or more of the stoichiometric composition, or to reduce the residual carbon amount to 0.01%.
~ 4 atomic%. In particular, it is preferable from the viewpoint of characteristics that the amount of oxygen is 95% or less of the stoichiometric composition and the amount of residual carbon is 0.2 atom% or more. Further, such a film can be obtained in a short time.

By adding the above light irradiation step to the solution in the sol-gel reaction, an oxide thin film having a uniform stoichiometric composition can be obtained at a low temperature. For this reason, heat treatment for improving the film quality is not required after the film formation, and it is possible to form an oxide thin film on a substrate such as 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 atom%. Also, the oxide composition MOx
In the above, a thin film having an oxygen content of 85 atomic% or more of the stoichiometric composition can be obtained, and a thin film having excellent electrical characteristics can be obtained.

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

[0062]

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

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

[0064]

[Chemical 3]

In the above-mentioned reaction, the reaction proceeds three-dimensionally in all directions, so that an inorganic polymer is produced.

Further, by irradiating with light energy having a specific wavelength necessary for breaking the metal-alkoxy group bond, the metal-alkoxy group bond is selectively cleaved to promote the reaction and highly polymerize. A metal oxide having a stoichiometric composition can be obtained. The solution irradiated with light energy contains no water, and the reaction can be carried out in a non-aqueous solvent system.

Therefore, since the obtained metal oxide does not contain water, the use of this method is effective for application to electronic devices and the like where water is a problem.

Similarly, among the techniques utilizing light, photo CVD
Although the reaction rate is improved by the method, heat application is indispensable for the decomposition reaction of the raw material and substrate heating is necessary. 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 addition, in the method of adding a photoactivation catalyst to various silanes and increasing three-dimensional cross linking by light irradiation, an organic chain compound is generated in the cross linking part to remove organic substances in the film. It does not meet the purpose of the invention.

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

The light for irradiating the solution has a specific wavelength necessary for breaking the bond between the metal and the alkoxy group, a specific wavelength necessary for forming a metalloxane bond between the metal and the metal, or a metal alkoxide. It is necessary to use the light of the specific wavelength required for the condensation polymerization of. Therefore, it is possible to obtain a polymer having a higher purity by irradiating only the light having the specific wavelength. Irradiation with light having another wavelength may result in obtaining a substance other than the polymer of the target molecule due to the light having another wavelength, and thus a substance having a high degree of purity cannot be obtained.

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

Use of the present invention makes it possible to obtain a metal oxide thin film having a low stoichiometric content and a uniform stoichiometric ratio at low temperature.
Since this metal oxide thin film exhibits good performance as a dielectric and an insulator, it has a high capacity thin film capacitor, a low-voltage driven electroluminescent device, a coating protective film with good environment resistance, and a protective film for semiconductor devices. , Optical disk recording media, plastic optical fiber protective film, plastic lens protective film, capacitors deposited on printed circuit boards, STN liquid crystal polarizers, Cu or Cu-based alloys with metal oxide films for semiconductor mounting It is suitable as a substrate. For example, when this method is used for liquid crystal production,
It can be applied to the production of the transparent electrode 141, the phase compensation plate 146, etc. shown in FIG. 24, and since low-temperature film formation is possible, a high quality product can be obtained without heat treatment.

If a laser having a strong directivity is used for light irradiation, it is possible to form a fine pattern of an oxide thin film on the substrate.

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

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

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

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

[0079]

[Chemical 4]

Here, one proton is released and a resonance phenomenon occurs, the whole β-diketone is negatively charged, and oxygen is coordinated to the metal. The number of β-diketones coordinated to the metal is the kind of metal,
It changes depending on the valence. In particular,

[0081]

[Chemical 5]

[0082]

[Chemical 6]

[0083]

[Chemical 7]

And the like.

On the other hand, the β-keto ester complex means β-keto ester.

[0086]

[Chemical 8]

[0087]

[Chemical 9]

R ⁰ is represented by a methyl group, but the same applies to other alkyl groups. It is similar in nature to the β-diketone complex. In particular

[0089]

[Chemical 10]

And the like.

It is necessary to irradiate these reaction solutions with light having the above-specified wavelength. This wavelength is appropriately selected depending on the substance. It is preferable to mainly irradiate the following Ti alkoxide 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 applied, not only the thin film but also the constituent member having a predetermined shape can be formed. At that time, if the wavelength of the emitted light is changed by the device with the monochromator installed,
The formed article can have various functions. For example,
After the formation process of a structure having a predetermined shape or after the formation of the structure, it is left in the formation body by irradiating with light energy of a wavelength necessary for generating ozone in addition to light energy of a wavelength for promoting the reaction. Organic matter can be reduced.

Not only the position of the light source but also the formation may be moved, or both may be moved to form a formation having a predetermined two-dimensional or three-dimensional shape.

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

As a solution for forming a predetermined shape, in addition to the above-mentioned solution mainly containing metal alkoxide, a solution mainly containing a plurality of metal alkoxides, a solution mainly containing organic polymers, and a metal alkoxide. There are solutions based on a mixture with an organic polymer, solutions based on an organometallic compound other than metal alkoxide, and the like. By using these solutions alone or in combination, a formed product having various functions and having a predetermined shape can be obtained.
Similarly, when the solution contains various fillers, the present invention can be effectively utilized.

When the technique of the present invention is applied to a solution containing a mixture of a metal alkoxide and an organic polymer as a main component, the metal alkoxide is uniformly dispersed in the organic polymer on a molecular order, so that the resulting structure is obtained. The characteristics of are higher and more reliable than those of the prior art. The metal oxide, which is a derivative of the dispersed metal alkoxide, does not agglomerate like that obtained by the addition of powder or the like according to the conventional method, and is uniformly dispersed at a maximum of 0.05 μm.

As described above, the constitution in which the metal oxide is uniformly dispersed in the organic polymer according to the application of the present invention has a higher dielectric constant than that of the organic polymer alone, and is used for a high-performance film capacitor or the like. 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.

Example 1 FIG. 1 is a block diagram 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 base 7 for fixing the monochromator, and a substrate 9 for immersing the substrate 9 in the reaction solution in the beaker 6 The immersion device 4 is installed.
The light emitted from the light irradiation device 2 is subjected to wavelength selection by the monochromator 3, reflected by the mirror 8 and applied to the reaction solution contained in the beaker 6. The reaction solution is installed on the stirrer 5 and is stirred by the rotation of the stirrer 10. After allowing the sol-gel reaction to proceed sufficiently by irradiation with light for a certain period of time, the mirror 8 is pulled up above 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 a position where the light is best irradiated after passing through the mono-macrometer, and the light is irradiated for a certain period of time. At this time, ozone is generated in the air, and the thin film thus formed is oxidized by 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. 2 ml of this solution was added with 8 ml of 0.5 mol / l ethanol solution of water (H ₂ O) and 2.5 ml of 0.1 mol / l ethanol solution of hydrochloric acid.
3 ml of the solution prepared by adding 2 ml of ethanol to the mixed solution of
The mixture was added dropwise at a rate of minutes to obtain a transparent and homogeneous mixed solution. 254 nm of a mercury lamp corresponding to the absorption position of the tantalum-ethoxy group was applied to this mixed solution by using the film forming apparatus shown in FIG.
Was irradiated for 30 minutes and 1 hour.

This light irradiation causes Ta by the following reaction.
It is believed that the 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]

[Chemical 11]

Thereafter, the reaction solution containing the prepolymer having a high degree of polymerization was used for SiO 2 by using a dipping device 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]

[Chemical 12]

FIG. 3 is an absorption spectrum diagram of the reaction solution when the tantalum ethoxide ethanol solution was irradiated with light of a mercury lamp having a wavelength of 254 nm. As shown in the figure,
Compared to before the solid line light irradiation, the spectral line shifts to the short wavelength side by the irradiation of the dotted line from 0.5 hour to the dotted line for 1 hour, and it is formed in the reaction solution by monitoring the absorption spectrum. 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 wavelength of the peak value of the absorbance and the light irradiation time of each of FIG.

The peak value of each wavelength is 250 n without light irradiation.
m, 30 minutes irradiation is 224 nm, 60 minutes irradiation is 208 nm
And the peak value is considered to be that the prepolymerization is almost completed in about 100 minutes. About 50% prepolymerization occurs at 30 minutes and about 80% at 60 minutes. Therefore, the higher the degree of pre-polymerization, the more preferable the light irradiation to the reaction solution is, but the degree of pre-polymerization is preferably 50% or more, more preferably 80% or more.

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

FIG. 5 is an infrared absorption spectrum diagram of the obtained film. In the figure, (a) does not irradiate light with the reaction solution or after film formation, (b) shows irradiation with light according to the present invention, (c) shows film formation without irradiating light with the above-mentioned reaction solution. After that, it was heat-treated at 400 ° C. in the atmosphere. 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 Because there exists. Further, in (a), C based on organic matter is used.
H vibration is required. In addition, the Ta oxide polymer film has the same absorption spectrum.

6 to 9 show the relative dielectric constant (ε), withstand voltage (MV / cm), and TaO of Ta oxide films obtained by various manufacturing methods.
It is a figure which shows x composition and C content in a film. 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 Light irradiation, a sol-gel film having a reaction time of 6 hours without light irradiation, a photo CVD film formed at 200 to 300 ° C., and a thermal CVD film formed at 350 ° C.

Each sol-gel film was repeated 4 times and had a thickness of about 2000Å.

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

As shown in FIG. 7, the membrane of the present invention is 2.7M.
A withstand voltage of V / cm or more can be obtained.

As shown in FIG. 8, the amount of C in the film according to the present invention is as low as 4 atom% particularly in the O ₂ medium light associative film, and a film having a low amount of C equivalent to that of the heat-treated film can be obtained.

As shown in FIG. 9, the TaOx composition of the photo-oxidized in-oxygen film of the present invention is 2.2 and 88% of the theoretical oxygen amount of 2.5 is 88% of that of the heat-treated film. It can be seen that a film with a stoichiometric ratio higher than% is obtained.

The resistivity of the photo-ascito film in oxygen of the present invention is as high as 10 ¹¹ Ωcm.

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

As a result of analyzing the film irradiated with ultraviolet rays for 3 hours at an irradiation intensity of 40 mW / cm ² , the C content was 0.01.
It was atm%.

On the other hand, the film not irradiated with light had a CH bond, and the residual amount of organic matter was 11.0 atomic% in terms of C content and the TaOx composition ratio (O / Ta) was 1.6. The film irradiated with light showed a residual organic content of 1 / 2.8 and a TaOx composition ratio (O / Ta) of 1.4 times that of the film not irradiated with light, and the stoichiometric amount of organic residue was small. A film close to the theoretical ratio was obtained. Residual amount of organic matter, Ta, similar to light-irradiated film
In order to obtain a thin film having an Ox composition ratio, it was necessary to perform heat treatment at 400 ° C. or higher on the film that was not irradiated with light.

Using the same technique, the heat resistant temperature is 30
Polyester film at 0 ° C or lower, mylar sheet, organic substrate such as acrylic resin, or stainless steel having a difference in thermal expansion coefficient of 5 × 10 ^-6 K ^-1 or more (coefficient of thermal expansion 1
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 amount of residual organic matter and the TaOx composition ratio (O / Ta) of these films are
The value was similar to that of the film formed on the SiO ₂ substrate.

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

Using this glass substrate, as shown in FIG.
Electroluminescent element (EL element) shown in (b)
Was produced.

A tantalum pentoxide film was similarly prepared by using the method of Example 1 in which the reaction solution was irradiated with light for 60 minutes on the glass substrate 13 having the transparent conductive film 14 described above. The steps of the method described in Example 1 were repeated 4 times to form an amorphous polymer Ta ₂ O ₅ film to be the first insulating layer 15 of the EL element on the transparent conductive film at 2000 Å. Next, ZnS containing 0.5 wt% of Mn was deposited as a light emitting layer 16 by 5,000 Å electron beam evaporation, and then 1 at 2.6 × 10 ⁻⁴ Pa and 300 ° C.
Vacuum heat treatment was performed for an hour. Further, BaTa ₂ O ₆ was deposited as the second insulating layer 17 by the 2000Å sputtering method. Aluminum was vapor-deposited by 2000 Å resistance heating as the upper electrode 18, and then electrode terminals were attached to obtain an EL device.

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 3-5 MV / cm is used for the first insulating layer and the second insulating layer, the driving voltage of the EL element is increased. Is about
High voltage of 200V 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 a low voltage drive at 170 V was possible. On the other hand, in the EL device using the Ta ₂ O ₅ film which is not irradiated with light as the first insulating layer, the characteristic of the Ta ₂ O ₅ film of the first insulating layer is that the dielectric constant is 14 even after the heat treatment at 300 ° C. after the light emitting layer deposition. ，
Since the withstand voltage is as low as 2.3 MV / cm, a driving voltage of 210 V was necessary.

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

As the insulating layer, a polymer film of SiO ₂ or Y ₂ O ₃ can be used. Similar to the above, these compositions have a high oxygen content of 85% or more with respect to the stoichiometric composition. An amorphous film can be obtained.

As the transparent conductive film 14 described above, a tin alkoxide Sn (OC ₂ H ₅ ) ₄ and indium alkoxide In (OCH ₃ ) ₃ solution was used, and 230 to 24 was added to this solution.
Irradiation with light having a wavelength of 0 nm is performed for 60 minutes to prepare a prepolymer solution of tin oxide and indium oxide, and the glass substrate 13 is dipped in this solution to form a film.
The step of irradiating the ultraviolet ray of 84 nm was repeated to form the transparent conductive film 14 having a predetermined film. Then, 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 similarly formed.

The EL element has a large number of pixels formed on a substrate and is driven by a high frequency power supply. A protective film of SiO ₂ is further formed on the entire surface of the EL element, and the EL element is composed 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 this example, the transparent conductive film and the insulating film except the light emitting layer and the upper electrode can be formed by the polymer amorphous film by the sol-gel method which does not require heat treatment, so that the EL device has a thermal expansion coefficient. There is an effect that manufacturing can be performed with less thermal influence due to the difference.

Example 3 As shown in FIG. 11, as a substrate 19, Si [(P-type surface index
(100), specific resistance 1.2 to 1.8 Ω · cm)], and using the method shown in Example 1 on this substrate, Ta ₂ O ₅
A membrane was prepared. Using the method shown in Example 1 in which the reaction solution was irradiated with light for 60 minutes, the process was repeated 4 times, and T
An a ₂ O ₅ film 20 was formed on a 2000ÅSi substrate. Furthermore, after vacuum-depositing the Al electrode 21 on the insulating film to a thickness of 1000Å, similarly deposit the Al electrode 21 on the back side of the substrate,
A thin film capacitor was produced.

The dielectric constant of the insulating layer is 28, which is about five times as large as that of SiO ₂ , and the withstand voltage is 2.8 MV / cm, which is a large value as compared with the conventional Ta ₂ O ₅ . Using the insulating film according to the present invention, a thin film capacitor having a large capacitance per unit area and good withstand voltage characteristics could be obtained.

Similar thin film capacitors could also be formed directly on or in a printed circuit board. The printed circuit board in this case is effective as a measure against noise in the high frequency circuit.

Example 4 Beaker 22 made of SUS304 stainless steel (inner diameter 50 mm, depth 60)
The same process was repeated 4 times by the method shown in Example 3 on the inner surface of (mm) to coat a Ta ₂ O ₅ film 23 of about 2000 Å. 3N hydrochloric acid 20 in this stainless beaker
ml was put in, the entrance was sealed with a 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. Corrosion resistance was improved by coating a Ta ₂ O ₅ film by this method.

When the film was not irradiated with light, the durability of the film on the stainless steel was poor, and when a similar experiment was conducted, film peeling occurred and corrosion also occurred after 7 days. Further, when heat treatment was carried out at 200 ° C. in order to improve the adhesion of the film, film peeling which is considered to be due to the difference in thermal expansion coefficient between the stainless steel and the thin film occurred.

In addition to SUS304 stainless steel, it is effective as a protective film against carbon steel for oxidation and corrosion in the atmosphere and for other metals or alloys such as Al and Cu as well as for oxidation and corrosion resistance. Although the example of the Ta ₂ O ₅ film is shown in the present embodiment, the film material of the above-mentioned kind can be selected for other oxide films depending on the kind of material.

Example 5 A 0.5 mol / l ethanol solution of silicon tetraethoxide was prepared. 20 ml of this solution was added with 0.5 mol / l of water
A mixed solution of 80 ml of an ethanol solution and 10 ml of a 0.1 mol / l hydrochloric acid ethanol solution was added dropwise at a rate of 3 ml / min to obtain a transparent homogeneous solution. This mixed solution was irradiated with light of 210 nm corresponding to the absorption position of the silicon-ethoxy group for 60 minutes using the film forming apparatus shown in FIG. Then, using a dipping device attached to the film forming apparatus, a semiconductor element having a thin film integrated circuit formed on the silicon substrate 24 shown in FIG.
After being immersed in the solution to form a thin film 27 on the integrated circuit, the film was irradiated with 184 nm light necessary for ozone generation in the air for 10 minutes. In FIG. 12, 24 is a Si substrate,
Reference numeral 25 is SiO ₂ , 26 is an Al electrode, and 27 is a polymer film of a SiO ₂ film produced by the method of the present invention. 27
Is a SiO ₂ polymer film, which is a protective film (passivation) for protecting the thin film integrated circuit from disturbance elements. Since this film has an extremely pure composition close to the stoichiometric ratio and is further polymerized, a highly protective film can be obtained. Further, unlike the conventional method, since heat treatment is not performed after film formation, stress is not generated in the heat treatment step and impurities such as Na + are not diffused, and the semiconductor element is not adversely affected. For this reason, reduction of the soft error of an element having a fit of 75 or less is achieved. SiO
_{The second} film 25 is formed by thermal oxidation, and the Al electrode 26 is formed by vapor deposition, sputtering or the like.

Incidentally, 27 is Ta 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 tripropoxy antimony was prepared. 1 ml of water is added to 30 ml of this solution.
l / l 15 ml of isopropyl alcohol solution and hydrochloric acid 0.
A mixed solution of 1 mol / l isopropyl alcohol 5 ml was added dropwise at a rate of 3 ml / min to obtain a transparent homogeneous solution. This 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. Next, the polymethylmethacrylate resin (PMMA) substrate 28 (diameter 13
(0 cm, thickness 1 mm) is immersed in a solution using a dipping device attached to the film forming apparatus to form a thin film 29 on the PMMA substrate, and then necessary for ozone generation in air.
Irradiation with 4 nm light was performed for 10 minutes. In this way, a recording medium layer having a thickness of 1000 Å was formed on the PMMA substrate. Similarly, a thin film was formed on another PMMA substrate. The two substrates are bonded via the spacer 30,
An optical disc having the structure shown in FIG. 12 was produced.

This optical disk has a high long-term reliability because an antimony oxide thin film having a stoichiometric composition with good adhesion to the substrate is formed without a heat treatment step.

By the same method, a metal alkoxide was used as a memory material, the Te oxide was mainly used, and Ga, G
It is possible to obtain an oxide containing at least one and 10 to 10% by weight of e and As and at least 10 to 20% by weight of In, Sn and Sb.

In some cases, a protective film may be provided on the recording medium,
As this protective film, Si is formed by the same method as in this embodiment.
A polymer film of O ₂ can be formed. The SiO ₂ film can be obtained in the same manner as in Example 5. Further, a protective film can be formed on the entire disc by this method.

As the substrate, it is also possible to use polycarbonate or epoxy resin.

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. 0.5 mol / l of water was added to this solution.
0.2 ml of a mixed solution prepared by adding 1 ml of a 0.1 mol / l ethanol solution of hydrochloric acid to 20 ml of an ethanol solution of
Slowly added at the rate of minutes. The polyethylene substrate (50 × 20 × 2) was placed in the homogeneous mixed solution thus prepared.
(Thickness) mm) was set at a position 5 mm below the liquid surface. Then, from the upper part of the liquid surface, the absorption wavelength of silicon ethoxide corresponding to 21
After irradiating with 0 nm light for 10 minutes, pull out from the liquid,
The substrate was irradiated with 184 nm light necessary for ozone oxidation for 10 minutes. This substrate was set again at a position 5 mm below the liquid surface, and this time it corresponds to the absorption wavelength of titanium ethoxide.
It was irradiated with light of nm for 10 minutes. Then pull up the board,
The light of 184 nm required for ozone oxidation was irradiated. The process of irradiating the light of 210 nm, 184 nm, 260 nm, and 184 nm was repeated 5 times by turns. FIG. 14 shows the structure of the multilayer film thus manufactured. Figure (with TiO ₂₎ layer containing a polyethylene substrate 31, SiO ₂ in a large amount 32, (having a SiO ₂₎ layer containing TiO ₂ in a large amount is 33. In this way, the multilayer film produced on the polyethylene substrate showed good performance as a lightweight and high-strength antireflection film. In addition, ESCA enables SnO
As a result of fixing the chemical species of ₂ and TiO ₂ , SnIV and TiIV were 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 the solution was 0.2 ml / min.
Was slowly added. The polyethylene substrate (50 × 50 × 2) was placed in the homogeneous mixed solution thus prepared.
(Thickness) mm) was set at a position 5 mm below the liquid surface. Then, after irradiating 270 nm light corresponding to the absorption wavelength of indium ethoxide from above the liquid surface for 10 minutes, the liquid was pulled out from the liquid and the 184 nm light necessary for ozone oxidation was irradiated on the substrate.
Irradiated for minutes. This substrate was placed again at a position 5 mm below the liquid surface, and this time, light of 230 nm corresponding to the absorption wavelength of tin (tin) ethoxide was irradiated for 10 minutes. Then, the substrate was pulled up and irradiated with 184 nm light necessary for ozone oxidation for 10 minutes. The steps of the light irradiation in the solution and the light irradiation in the air were repeated 5 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 produced on this polyethylene substrate shows good performance as a light-weight and high-strength infrared reflecting film.

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

Irradiation position for forming a predetermined shape body,
A light source 61 having a system for controlling the scanning speed, the beam diameter wavelength, etc., a substrate 62 for forming a shape body,
It holds the substrate 62, allows it to be dipped in and pulled up from the sample solutions 64 and 65, and enables the formation of a predetermined shape body in cooperation with the light source 61. A substrate supporting device 63 provided with a vertical movement mechanism, an agitator 66 for keeping the sample solution homogeneous, and a stirrer 67 are installed in a box 68. The box is equipped with an atmosphere control section 69 that allows it to be maintained in an inactive state or the like.

The light generated from the light source 61 is dipped in each sample solution, and the substrate 6 coated with it is dipped.
2 is irradiated. The irradiation position is a system that automatically moves under the set conditions.

Example 10 Indium ethoxide 0.5 mol / l ethanol solution 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 in this solution
1, 30 ml of an ethanol solution, 0.1 mol / l of hydrochloric acid and 2 ml of an ethanol solution were added slowly at a rate of 0.2 ml / min. Thus, the homogeneous mixed solution A was prepared. Next, epoxy acrylate resin (specific gravity
1.14, viscosity 200 cps (20 ° C)), and B were prepared.

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

The above A was put in 64 of FIG. 16, and B was put in 65. Acrylic resin was used as the substrate 62. First, the substrate 62 is dipped in 64 and then pulled up to scan at a scanning speed of 10
A He-Cd laser (output 30 mW) was irradiated at 0 mm / sec. Subsequently, light of 184 nm was scanned at a speed of 10 mm / sec. This operation was repeated 5 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 forming the ITO layer in this way, the substrate is dipped in 55 and the whole surface of the substrate is irradiated with He-Cd laser light, and this is repeated twice to form an epoxy acrylate resin coating layer having a thickness of 0.1 mm. Formed. The formed product formed in this example has a shape shown in FIGS. 17A and 17B, and by energizing both ends of the ITO, it was possible to prevent fogging of the substrate.

Example 11 Ethylseal solution of tantalum ethoxide [Ta (OC ₂ H ₅ ) ₅ ] was added to a solution of polyvinyl butyral dissolved in 1% hydrous ethanol, and the mixture was sufficiently stirred to obtain a mixed solution.
The viscosity of this solution was adjusted while performing vacuum defoaming operation, and after adjusting it to about 5000 cps, it was formed into a sheet on a polyester sheet by a well-known doctor blade method.
At this time, Kr-F laser light is reflected on the surface of the sheet-like formed body at the exit from the blade at a scanning speed of 100 mm / sec,
Then, 184 nm light was irradiated by an ultraviolet lamp at a scanning speed of 10 mm / sec. After proceeding the chemical reaction in this way, it is dried to a thickness of about 30 μm and a length of 1000 mm,
A sheet having a width of 10 mm was obtained. The dielectric constant of this sheet is 6.1
So, it was larger than 3.6 for polyvinyl butyral alone.

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

In the capacitor thus formed, the organic substance and the inorganic substance are uniformly mixed, so that the dielectric constant of the dielectric itself is higher than that of a capacitor using a film made of only an organic substance. Higher 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 produced by the method described below.

First, the mixed solution A was coated on a polyester sheet by the doctor blade method. At this time, the output from the blade causes Kr- on the coating layer on the sheet.
The F laser light was irradiated at a scanning speed of 100 mm / sec, and then the light of 184 nm was irradiated by an ultraviolet lamp at a scanning speed of 10 mm / sec. This operation is repeated 4 times, and a transparent conductive film (ITO) with a thickness of 0.5 μm is formed on the polyester sheet.
Was formed. Next, coat the ITO film with resin B, and irradiate the coated surface with 5 mm intervals at an irradiation light diameter of 0.3 m.
Irradiation with a He—Cd laser of m 2 was performed to form a composition having a cross-sectional shape as shown in FIG.

75 formed of the resin B serves as a spacer for the touch panel.

A member having an ITO film 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 satisfied the application in terms of responsiveness, transparency and other characteristics.

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

After the aluminum conductor electric wire was dipped in the homogeneous mixed solution thus prepared, the electric wire was irradiated with Ar—F laser at the interface of the solution when the electric wire was pulled up from the solution. The speed of pulling up the electric wire was 60 mm / sec. afterwards,
Ultraviolet light of 184 nm was irradiated, and this operation was repeated 5 times to form an insulating film of SiO _{2 on} the surface of the electric wire. It was confirmed that the insulating film thus formed can maintain its insulating property even when used in an environment of 600 ° C. and that it can be used in vacuum without generation of hydrocarbon or carbon dioxide gas. .

Further, it was found that the method of the present example allows the coating layer to be continuously formed on the wire at a low temperature and the present invention is industrially useful.

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

First, a polyester substrate was placed at a position 5 mm below the liquid surface of the solution (I), and 210 nm of light corresponding to the absorption wavelength of silicon ethoxide was irradiated from above the liquid surface for 10 minutes, and then the substrate was moved from the liquid. 18 required for ozone oxidation
Irradiation with 4 nm light was performed for 10 minutes. Then, the substrate was placed at a position 5 mm below the liquid surface of the solution (II), and light of 260 nm corresponding to the absorption wavelength of titanium ethoxide was irradiated for 10 minutes. Then, the substrate was moved from the liquid and irradiated with 184 nm light necessary for ozone oxidation for 10 minutes. Irradiation of 210 nm in solution (I) → Movement of substrate → Light irradiation of 184 nm → Light irradiation of 260 nm in solution (II) → Movement of substrate →
The process of light irradiation of 184 nm was repeated 5 times by turns. As a result, a SiO ₂ layer / TiO ₂ layer is formed on the polyester substrate.
A multilayer film of layers could be formed. This multilayer film exhibited excellent 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 glad part, and 84 is a core part. The method for producing the protective film will be described below.

A 0.5 mol / l ethanol solution of silicon ethoxide was prepared. 0.5 mol of water was added to 20 ml of this solution.
A mixed solution of 80 ml of 1 / l ethanol solution and 10 ml of 0.1 mol / l hydrochloric acid ethanol solution was added dropwise at a rate of 3 ml / min to obtain a transparent uniform solution. This mixed solution was irradiated with 210 nm light for 60 minutes using the film forming apparatus shown in FIG. Plastic optical fiber (thickness: 2
(mmφ) is dipped and the SiO ₂ protective film 8 is placed on the fiber surface.
1 was deposited. Then, the fiber was irradiated with 184 nm light necessary for ozone generation in the air for 10 minutes. An environmental resistance test of the thus obtained plastic optical fiber was conducted at 100 ° C. in engine oil. FIG. 20 shows the result. The vertical axis shows the light amount holding ratio (%), and the horizontal axis shows the elapsed time (hr). In the case without the protective film, the light quantity retention rate decreases to about 40% after 1000 hours due to the diffusion of oil into the fiber, but with the protective film fiber prepared this time, the light quantity retention rate is 80% even after 1000 hours. From the above, it was found that the oil resistance was extremely excellent. Therefore, it is suitable as a plastic fiber for controlling an automobile engine, for example.
Moreover, since the film forming method of this time is excellent as a low temperature process, it is possible to form an inorganic film on a plastic fiber having no heat resistance.

Example 16 In accordance with a usual manufacturing process of a plastic mold type semiconductor element, as shown in FIG. 21, a lead frame, a chip and a pellet were attached, and then an Au wire was wire-bonded. An inorganic film was undercoated on this element by the method described below.

0.5 mol / l of silicon tetraethoxide
An ethanol solution was prepared. To 20 ml of this solution, 80 ml of a 0.5 mol / l ethanol solution of glacial acetic acid, which is an organic acid, was slowly added. This mixed solution was irradiated with light of 210 nm 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, this element was irradiated with 184 nm light in air for 10 minutes. This device was again dipped in the solution to form a film, and then irradiated with 184 nm light in the air for 10 minutes. This process was repeated 10 times to undercoat. The device thus produced was resin-sealed with an epoxy resin to complete a semiconductor device. The structure is shown in FIG. In the figure, 91 is a lead frame,
92 is an Au wire, 93 is an Au-Si alloy, 94 is a chip, 95 is an inorganic protective film, and 96 is an epoxy resin.

Since the element 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 semiconductor element having excellent performance can be obtained. That is, no stress is generated in the heat treatment step, and since the wettability between the Au wire and the inorganic protective film is good, 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 device is achieved.

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

A 0.5 mol / l ethanol solution of tantalum ethoxide was prepared. 20 ml of this solution was added with 0.5 m of glacial acetic acid.
80 ml of an ol / l ethanol solution was added. This mixed solution was irradiated with 254 nm light for 60 minutes. As shown in FIG. 22, Fe-42% Ni with the back surface masked in this solution
A plate (10 × 10 × 0.5t) 101 was dipped to form a film.
The film-formed surface was irradiated with 184 nm light 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. 20 this step
The Ta ₂ O ₅ film 102 having a thickness of 1 μm was repeatedly formed. 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 the high-speed device and the circuit are densely mounted and operated using this thin-film capacitor, it is possible to take measures against noise, which is the largest cause of malfunction.

Example 18 A protective film was formed on a plastic lens. FIG. 23
[Fig. 4] is a cross-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 was added to 20 ml of this solution.
A mixed solution of 80 ml of 1 / l ethanol solution and 10 ml of hydrochloric acid 0.1 mol / l ethanol solution was added dropwise 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 to prevent the solution from sticking was immersed in this solution, and a SiO ₂ protective film 112 was formed on the convex portion surface of the plastic lens 111. . Then, in the air, this lens is necessary for ozone generation.
Irradiation with 84 nm light was performed for 10 minutes. Since the plastic lens thus obtained has a dense and hard protective film, it was possible to significantly extend the service life without causing scratches on the lens in normal use. According to this method, it is possible to form a uniform film even on a convex portion or the like.

Example 19 Ta ₂ O _{5 is formed} on a printed wiring board by using the method of the present invention.
A thin film capacitor was produced. The manufacturing method is as follows.

A 0.5 mol / l ethanol solution of tantalum ethoxide was prepared. 20 ml of this solution was added with 0.5 m of glacial acetic acid.
80 ml of an ol / l ethanol solution was added. This mixed solution was irradiated with 254 nm light for 60 minutes. A printed wiring board masking the position where the ground electrode of the silicon chip is grounded on the entire back surface and the front surface was immersed in this solution to form a Ta ₂ O ₅ film on the surface of the printed wiring board.
The film-formed surface was irradiated with 184 nm light in air for 10 minutes. Then, the substrate was again immersed in the solution to form a film, and then 184 nm light was irradiated in the air for 10 minutes. This step was repeated 10 times to form 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 the mask removed portion to form an electrode. A silicon chip was attached on top of this. Figure 24 shows
It is a sectional view of a silicon chip on a printed wiring board manufactured in this manner. In the figure, 121 is a printed circuit board, 12
2 is an electrode, 123 is a Ta ₂ O ₅ film which is a dielectric layer, 124
Is a silicon chip. The Ta ₂ O ₅ film acts as a thin film capacitor, and changes in capacitance are hardly seen even at 1 GHz. For this reason, the semiconductor element manufactured by the above method was able to take measures against noise, which is the largest cause of malfunction when high-speed devices and circuits were 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 produced.

A 0.5 mol / l ethanol solution of silicon ethoxide was prepared. To 20 ml of this solution, 80 ml of a 0.5 mol / l ethanol solution of glacial acetic acid, which is an organic acid, was slowly added. This mixed solution was irradiated with 210 nm light for 30 minutes. Immerse a copper plate of a predetermined size in this solution
An O ₂ film was formed. Then, add 184n in air to this substrate.
m light was applied for 10 minutes. This process of immersion film formation and light irradiation in air was repeated 20 times to form a SiO ₂ film of about 10 μm on the copper plate. This substrate is suitable as a semiconductor mounting substrate because an insulating layer is formed on copper, which has good thermal conductivity. FIG. 25 shows a semiconductor device manufactured using this substrate. In the figure, 131 is a silicon chip, 132 is a bonding wire, 133 is a lead, 1
Reference numeral 34 is a SiO ₂ film, 135 is a copper substrate, 136 is a 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, it is possible to use, as a semiconductor mounting substrate, a copper glass 135 having a good thermal conductivity and provided with a sealing glass 136 made of an insulating layer SiO ₂ film. Therefore, it is possible to efficiently remove the heat generated when the semiconductor element operates.

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

[0183]

[Table 1]

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

[0185]

According to the present invention, a polymer metal polymer thin film having a small amount of residual organic matter and a uniform stoichiometric ratio can be obtained by a method which does not heat-treat at a low temperature. Further, since the polymer metal oxide thin film obtained by this method exhibits good properties as a dielectric film and an insulating film, it is used as a recording medium for an EL device, a thin film capacitor, a protective film optical disk of a semiconductor device, etc. It is possible to improve the performance of various electronic devices.

Furthermore, since an oxide multilayer film having a uniform stoichiometric ratio can be obtained very easily at low temperature and can be formed on an organic substrate, a lightweight and high-strength antireflection film and heat ray reflection film can be prepared.

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

[Brief description of drawings]

FIG. 1 is a configuration diagram of a film forming apparatus used in an example 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 a relationship between wavelength and light irradiation time.

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

FIG. 6 is a diagram of TaOx composition of relative permittivity, withstand voltage, and C content of metal oxide films formed by various methods.

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

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

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

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 formed on a polyethylene substrate
sectional view of iO ₂ anti-reflection film.

FIG. 15: In ₂ O—S fabricated on a polyethylene substrate
sectional view of nO ₂ heat-reflecting film.

FIG. 16 is a configuration diagram of a molding device for a predetermined shape used in the present invention.

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

FIG. 18 is a schematic cross-sectional view of a touch panel structure 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 a result of an oil resistance test.

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

FIG. 22 is a structural diagram of a Ta ₂ O ₅ thin film capacitor for high frequencies.

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

FIG. 24 is a cross-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]

1 ... Box, 2 ... Light irradiation device, 3 ... Monochromator,
4 ... Immersion device, 4, 67 ... Stirrer, 6 ... Beaker, 7
... Support base, 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 supporting device, 64, 65 ... sample solution,
68 ... Box, 69 ... Atmosphere controlling 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 ... Chip, 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 ... Polarizing plate, 145 ... Color liquid crystal panel, 146 ... Phase compensation plate, 147 ... Reflector plate.

Front page continuation (51) Int.Cl. ⁷ Identification code FI C01G 19/02 C01G 19/02 C 23/04 23/04 C 35/00 35/00 B H01G 4/33 H01L 21/205 H01L 21/205 21/31 A 21/31 21/314 A 21/314 H01G 4/06 102 (72) Inventor Tetsuo Nakazawa 4023 Kuji-cho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Shigeru Tanaka Ibaraki Prefecture Hitachi, Ltd. 4023 Kuji Town, Hitachi Ltd., Hitachi Research Laboratory (72) Inventor Tadahiko Miyoshi 4023 Kuji Town, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (56) Reference JP-A-3-188938 (JP, A) ) JP-A 62-231201 (JP, A) JP-A 62-17701 (JP, A) JP-A 61-91838 (JP, A) JP-A 60-242401 (JP, A) JP-A 60- 88901 (JP, A) JP 60-68319 (JP, A) JP 60-17078 (JP, A) JP 59-50401 (JP, A)

Claims (4)

(57) [Claims] 1. An antireflection film formed on an organic substrate having a decomposition starting temperature of 300 ° C. or lower, containing 85 atomic% or more of oxygen in a stoichiometric composition and having a carbon content of 0.01 to 0.01%. An antireflection film having an amorphous inorganic polymer thin film which is 4 atomic% and contains a small amount of C—H bond and which is substantially composed of a metal oxide. 2. The antireflection film according to claim 1, wherein the organic substrate is made of polyethylene, polyester, acrylic resin, epoxy resin or polycarbonate. 3. The organic substrate has a difference in thermal expansion coefficient between the inorganic polymer thin film and the inorganic polymer thin film of 5 × 10 ⁻⁶ K ⁻¹ or more, the inorganic polymer thin film is a solution containing a metal alkoxide and water, The light energy corresponding to the absorption wavelength of the metal alkoxide is irradiated, the solution in which the metal oxide prepolymer is generated by irradiation with the light energy is applied to the organic substrate, and the applied solution is an organic substance in the solution. The antireflection film according to claim 1, wherein the antireflection film is formed by irradiating light for ozone oxidation and removal of. Wherein said metal alkoxide, LiOCH _3,
NaOCH ₃ , Ca (OCH ₃ ) ₂ , Ba (OC ₂ H ₅ ) ₂ , Zn
_{(OC 2 H 5) 2,} B (OCH 3) 3, Al (i-OC 3 H 7) 3, G
a (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 , S
b (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 (iso-OC ₃ H ₇ ) ₄ ] ₂ , Mg [Al (i
_{so-OC 4 H 9) 4} ] 2, Ni [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} anti-reflection film according to claim 3, characterized in that the.