JPH07309638A - Fluorine-containing metal oxide film and production of metal oxide film - Google Patents

Abstract

PURPOSE:To form a dense film at an extremely low temp. by forming a metal oxide film contg. F on the surface of a base material by using specific metal fluorides under specific conditions. CONSTITUTION:The metal fluorides which have nature to be hydrolyzed and are preferably >=1 kinds selected from SnF2, SnF4, SbF3, SbF5, TiF4, InF3.3H2O, PbF4, COF3, FeF3.3H2O, MnF3, CrF3-nH2O (n is 3 to 9), WF6, NbF5, TaF5, VF3, ZrF4(are used. Such metal fluorides are dissolved into, for example, pure water to prepare a soln. and the base material (for example, glass) is brought into contact with or immersed into this soln. The product by the hydrolysis reaction of the metal fluorides is then deposited on the surface of the base material to form the metal oxide film contg. F in the liquid phase. Further, this film is baked to remove the F, by which the metal oxide film without contg. the F is obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing metal oxide film and a method for producing a metal oxide film. In particular, a novel method for forming a metal oxide coating film containing fluorine in a liquid phase is provided by utilizing the property that a hydrolysis product of a metal fluoride easily deposits on the surface of a substrate. Further, there is provided a method for obtaining a fluorine-free metal oxide coating from the obtained fluorine-containing metal oxide coating.

[0002]

2. Description of the Related Art As a method for wet-forming a metal oxide film, a so-called coating method has been conventionally known in which a metal oxide colloidal solution or a solution containing a metal alkoxide is applied and dried. As a method for forming a metal oxide film in a liquid phase, an additive is added to a solution containing metal and fluorine so that the metal oxide is in a supersaturated state, and the metal oxide is deposited to form a film. Several methods of forming are disclosed. For example, JP-A-59-141441, JP-A-4-26516, and JP-A-4-1300.
No. 17, JP-A-4-132636 discloses a method of forming a titanium oxide coating film by adding an additive such as boric acid to an aqueous solution of titanium hydrofluoric acid or ammonium titanium fluoride. Japanese Patent No. 134667 discloses a tin oxide coating on a solution containing tin and fluorine.
A method of adding additives such as boric acid, zinc oxide, and aluminum chloride to bring tin oxide into a supersaturated state and forming a precipitate is
Further, in JP-A-1-301514, Zn, I
A method of forming oxides of n, V, Cr, Mn, Fe, Co, Ni, and Cu from a solution containing fluorine in which the metal oxide is supersaturated is described.

[0003]

Among the above-mentioned methods for producing a metal oxide film, in the coating method, various methods such as dipping, spin coating, spraying, and roll coating are applied to the surface of the substrate. However, it is difficult to apply a uniform film onto the surface of a complex shape by such a method. Further, there is a problem that it is difficult to obtain a sufficiently dense film with little drying shrinkage.

Further, the method of forming a metal oxide coating film which has already been disclosed is a method of forming a dissolved metal oxide by adding an additive such as boric acid to a solution containing metal and fluorine. Is a method of causing the supersaturated state to precipitate. Since these methods require additives, the control of the precipitation reaction is complicated and difficult, and reproducibility may be difficult to obtain. Further, depending on the type of additive material, treatment of waste liquid may be a problem.

An object of the present invention is to provide a novel manufacturing method capable of forming a dense film containing fluorine in a liquid phase method at an extremely low temperature.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that if an aqueous solution in which only a metal fluoride having a property of hydrolyzing is dissolved is used, dipping It was found that the hydrolysis product of the metal is deposited on the surface of the substrate thus formed, and the metal oxide film containing fluorine can be formed, and the present invention has been completed.

That is, according to the present invention, the base material is brought into contact with or immersed in a solution in which a metal fluoride having a property of being hydrolyzed is dissolved, and a product is deposited on the surface of the base material by a hydrolysis reaction of the metal fluoride. A method for producing a fluorine-containing metal oxide film, which comprises forming a metal oxide film containing fluorine in a liquid phase. Further, the present invention is a production method characterized in that the fluorine-containing metal oxide coating obtained by such a method is baked to remove the fluorine and obtain a fluorine-free metal oxide coating.

Unlike the above-mentioned conventional liquid phase forming method, the method of the present invention does not use any additives and does not require the metal oxide dissolved in a solution containing fluorine to be in a supersaturated state. In other words, this is a method that utilizes only the hydrolysis reaction of the dissolved metal fluoride and water. Hereinafter, the present invention will be described in more detail.

In the present invention, examples of the metal fluoride having a property of hydrolyzing include tin fluoride (Sn).
F _2, SnF _4), antimony fluoride (SbF _3, Sb
F _5), titanium fluoride (TiF _4), indium fluoride hydrate _{(InF 3 · nH 2 O (} n = 3~9)) and the like. In addition, lead fluoride, chromium fluoride hydrate, cobalt fluoride, ferric fluoride hydrate, manganese fluoride, tungsten fluoride, niobium fluoride, tantalum fluoride, vanadium fluoride, zirconium fluoride, etc. Can be mentioned.

There are various kinds of hydrolyzable metal fluorides, but four kinds of tin fluoride, antimony fluoride, titanium fluoride and indium fluoride hydrate show the property of being easily hydrolyzed in an aqueous solution. Therefore, it is particularly preferable.

Specifically, the aqueous solution of tin fluoride is Sn
It can be easily prepared by dissolving F ₂ or SnF ₄ in water. Usually, it is preferable to use SnF ₂ which is inexpensive and easy to synthesize. An aqueous solution of antimony fluoride
It can be easily obtained by dissolving SbF ₃ or SbF ₅ in water. Usually, it is preferable to use SbF ₃ which is easily available. Similarly, as the aqueous solution of titanium fluoride, TiF ₄ which is usually commercially available may be dissolved in water. Further, the aqueous solution of indium fluoride is InF ₃ · nH ₂ O (n = 3 to
It can be easily prepared by dissolving the hydrate of indium fluoride represented by 9) in water. In particular, InF ₃ · 3H ₂ O
Is preferably used. Since indium fluoride anhydride has poor solubility in water, it is preferable to use indium fluoride hydrate.

Lead fluoride is PbF ₄ , chromium fluoride hydrate is CrF ₃ .nH ₂ O (n = 3 to 9), cobalt fluoride is CoF ₃ , and ferric fluoride hydrate is FeF _3.・ 3H
₂ O, MnF ₃ for manganese fluoride, WF ₆ for tungsten fluoride, NbF ₅ for niobium fluoride, Ta for tantalum fluoride.
It is preferable to use VF _{3 for} F ₅ , vanadium fluoride, and ZrF ₄ for zirconium fluoride.

The film forming process can be easily carried out by contacting or immersing the substrate in the aqueous solution of the above-mentioned fluoride and holding it at a predetermined temperature. Usually, in order to prevent evaporation of the liquid, it is carried out in a closed container and kept in a constant temperature bath or the like. At that time, in order to obtain a uniform film, it is preferable to circulate or stir the liquid. In this method, a film is formed by utilizing a reaction in which a hydrolysis product of a metal fluoride is deposited on a surface of a substrate in a solution, and the film is gradually formed thicker in the solution over time. In order to prevent the concentration of fluoride in the liquid from changing with time, it is also a good method to add new fluoride during film formation.

The concentration of the solution capable of forming a film is extremely wide, and the concentration of the metal fluoride can be arbitrarily selected up to about 0.001 to 1 mol / l, but the preferable concentration range is 0.01 to.
It is 0.3 mol / l. As the concentration increases from the order of 10 ^-2 mol / l to the order of 10 ^-1 mol / l, the film formation rate increases, but the crystallinity of the film tends to deteriorate. . On the other hand, at 0.5 mol / l or more, on the contrary, the formation rate decreases. Further, if the concentration is increased, there is a slight tendency to corrode the base material, so film formation may become difficult depending on the type of base material. From the viewpoint of film formation rate, film crystallinity, denseness, and substrate corrosion, the solution concentration is particularly preferably in the range of 0.02 to 0.2 mol / l.

The holding temperature of the solution is from room temperature to 150.
It can be arbitrarily selected up to about ° C. The temperature is added to accelerate the hydrolysis of the fluoride, and the higher the temperature, the faster the film formation rate, and the denser the film quality and the better the crystallinity. However, 80 ℃
At the above temperatures, the corrosion of the base material may become a problem.
For example, if quartz glass is used as the base material, 100 ° C
However, the base material is not corroded and a film can be formed, but in the case of soda lime glass, the film is corroded at 80 ° C. or higher and the film formation is difficult. From such a viewpoint, the preferable holding temperature is 60 to
It is 80 ° C.

The preferred metal fluoride concentrations described above,
The holding temperature is almost independent of the type of metal fluoride and is true for all metal fluorides.

The rate of film formation depends on the type of metal fluoride,
Strongly depends on the fluoride concentration of the solution and the holding temperature,
In the case of tin oxide coating, for example, SnF ₂ concentration 2 × 10
^{-2 to} 5 × 10 ^-2 mol / l solution has a formation rate of about 2 nm / hr when kept at 40 ° C and about 10 nm when kept at 60 ° C.
nm / hr, about 15 to 20 nm / hr when kept at 80 ° C., and a SnF ₂ concentration of 1 × 10 ⁻¹ mol / l of a solution was 80
The formation rate when kept at 0 ° C. is 30 nm / hr.
In the case of an antimony oxide coating, for example, SbF ₃
A solution having a concentration of 2 × 10 ^-2 to 10 × 10 ^-2 mol / l was added to 60
The formation rate when kept at 10 ° C is 10 to 20 nm / hr.

In the case of a titanium oxide film, TiF ₄
A solution having a concentration of 2 × 10 ^{-2 to} 5 × 10 ^-2 mol / l was added at 60 ° C.
The formation rate when kept at 30 nm / hr is 30 nm / hr. In the case of an indium oxide film, for example, the formation rate is 5 to 10 nm / hr when a solution having an InF ₃ concentration of 2 × 10 ^{−2 to} 5 × 10 ⁻² mol / l is held at 60 ° C. In the case of lead oxide, chromium oxide, cobalt oxide, iron oxide, manganese oxide, tungsten oxide, niobium oxide, vanadium oxide, and zirconium oxide, the film formation rate is about 1-50n
m / hr.

Immediately after adding the base material to the prepared metal fluoride aqueous solution and performing a film formation process, aggregated particles of metal acids such as stannic acid, indium acid, and antimonic acid produced by hydrolysis of the fluoride. May adhere to the film formed on the surface of the base material. As a method for preventing this, a method in which the prepared fluoride solution is kept at a predetermined temperature for a certain period of time to promote hydrolysis to promote sedimentation of agglomerated particles, the liquid is clarified, and then equipment is added thereto can be preferably adopted. At this time, the temperature may be room temperature to 150 ° C. and may be held for 0.1 to several tens hours.

As the substrate, glass, plastic,
Many types such as silicon and metal can be used. In particular, it is easy to form a film on a material having excellent corrosion resistance such as quartz glass, general-purpose glass coated with silica, and plastic. In addition, film formation can be easily performed by putting the preparation liquid on the surface of an object having a curved surface such as a container and maintaining the same at a predetermined temperature while stirring.

Another feature of the manufacturing method of the present invention is that
It is possible to produce a multi-component oxide coating such as a solid solution or a complex oxide composed of one or more kinds of metal oxides by using a solution in which a plurality of kinds of metal fluorides are dissolved, according to the same method as described above. It is in. For example,
The antimony-containing tin oxide film containing fluorine is S
It can be easily formed by contacting or immersing the base material in an aqueous solution in which a predetermined amount of nF ₂ and SbF ₃ are dissolved and maintaining the temperature at room temperature to 150 ° C.

In this case, the preferred metal fluoride concentration and holding temperature of the solution are the same as those for forming the respective single-component oxide coatings. In addition, including the case of SnF ₂ + SbF _3, etc., the total concentration of each metal fluoride is 0.01
.About.0.2 mol / l, and the holding temperature is preferably 60 to 80.degree.

The film forming rate is such that, when an aqueous solution of SnF ₂ + SbF ₃ is used, the fluoride concentration is 2 × 10 ^{-2 to} 5
5 x 10 ^-2 mol / l solution held at 60 ° C
nm / hr, 15 to 20 nm / when held at 80 ° C
It is hr.

The ratio of Sb / Sn constituting the coating is almost the same as that in the prepared solution, but when the Sb content is up to 10 mol%, the Sb content in the coating tends to be higher than the Sb content in the solution. At mol% or higher, the opposite tendency is exhibited. For example,
When the Sb / Sn molar ratio in the liquid is 2/100, the film contains 3/100 to 5/100, and when the molar ratio in the liquid is 20/100, the film contains 13 / 100
.About.20 / 100 is included.

Besides the antimony-containing tin oxide coating,
Apply tin-containing indium coating to SnF ₂ and InF ₃ · nH ₂
It can be formed in the same manner from a solution in which O and O are dissolved. In addition, the titanium / niobium / lead-based composite oxide can be easily prepared by immersing the base material in an aqueous solution in which titanium fluoride, niobium fluoride, and lead fluoride are dissolved, and maintaining the temperature at room temperature to 150 ° C. Can be formed into It is also possible to form a desired binary or ternary oxide film by combining other metal fluorides.

A crystalline coating having a perovskite structure can be obtained by increasing the holding temperature during film formation or heating the coating obtained by precipitation.

The coating film deposited on the substrate is composed of a metal oxide containing fluorine. The fluorine contained in this coating is IR
From the spectrum analysis, it is presumed that it is present in the structure in the state of being bound to the metal element. The content of fluorine depends on the concentration of fluoride in the solution used and the holding temperature,
In particular, it strongly depends on the concentration. For example, in the case of tin oxide, when the SnF ₂ concentration is 0.01 mol / l, it is 5 to 7 at.
m% fluorine is contained in the coating, and 0.1 to 0.3 mol /
1 contains 10 to 16 atm% of fluorine. The amount of fluorine contained varies slightly depending on the type of metal fluoride, but this concentration dependence is common, and it is possible to contain 3 to 18 atm% of fluorine in all oxide films of the present invention. However, it is difficult to contain fluorine exceeding 18 atm.

The fluorine-containing metal oxide coating film obtained by the present invention has high fluorine-free crystallinity because fluorine is removed by firing in a normal atmosphere such as air, oxygen, or an inert gas. It can be a metal oxide coating.
The temperature at which fluorine is removed is not significantly affected by the type of oxide, and 90% or more of fluorine is removed at a heating temperature of 300 ° C., and almost all is removed at 500 ° C. The coating film obtained by the manufacturing method of the present invention is dense and has a submicron thickness.
At the thickness of the dare, no cracking or peeling due to firing was observed.

[0029]

EXAMPLES The present invention will be further described below with reference to examples. However, the present invention is not limited to these examples.

Example 1 40 g of SnF ₂ was added to 100 parts of pure water.
By using a liquid dissolved in 0 ml and pure water and mixing both at a predetermined amount at room temperature, Sn concentrations of 0.005 and 0.01
100 ml of 0, 0.030, and 0.100 mol / l solutions were prepared. After depressurizing this solution once and degassing it, quartz glass, silicon substrate, and soda are used as the base material.
Dalime glass is soaked and sealed, each at 60 ℃,
It was kept for 15 hours in a thermostat at 80 ° C and 110 ° C. The pH of the liquid after the treatment hardly depends on the concentration and is 2.8 to 3.
It was 0. The substrate was taken out and washed with water, and it was confirmed that a film was formed on the substrate surface. At 80 ° C. and 110 ° C., peeling of the film was partially observed on substrates other than quartz glass, but at 60 ° C., films adhered to all substrates were formed. The film thickness and the like were determined by SEM observation. In addition, as a result of analyzing the film composition by ESCA and EPMA, Sn, O, and F were detected as the main components, the atomic ratio of Sn and O was 1: 1.7 to 1.9, and the F amount was in the table. As shown in 1, it was 5 atm% or more. From this result, it was found that a fluorine-containing tin dioxide film was formed. The above results are summarized in Table 1.

[0031]

[Table 1]

Example 2 A fluorine-containing tin oxide film was obtained in the same manner as in Example 1 except that the solution concentration was changed and the film forming treatment was carried out at 40 ° C. for 110 hours.
The results are shown in Table 2. As shown in Table 2, silicon,
Films could be applied to all base materials of dhalime glass and quartz glass.

[0033]

[Table 2]

Example 3 1.57 g of SnF _{2 was} added to pure water 1
The liquid dissolved in 00 ml was kept at 80 ° C. for 24 hours to generate a precipitate by hydrolysis. Quartz glass and silica-coated soda lime glass were immersed as a substrate in the supernatant liquid that left a precipitate on the bottom of the container, and the soda lime glass was left to stand at 80 ° C. for 10 hours for film formation. When the obtained samples were observed by SEM, it was found that a film having a thickness of 0.3 μm was formed on each of the samples with very few adhered particles on the film surface. The sample was baked at 300 ° C. or 500 ° C. for 1 hour in the air, and analyzed by EPMA. The sample fired at 300 ° C. contained Sn and O in an atomic ratio of 1: 2, and other than that, 0.4 atm% of F was detected. 500 ° C
Sample No. 1 contained Sn and O at a ratio of 1: 2, and nothing else was detected. In addition, it was confirmed by X-ray diffraction that a tin dioxide film was formed in each of the samples baked at 300 ° C or 500 ° C.

(Example 4) A predetermined amount of SbF ₃ was weighed and dissolved in 100 ml of pure water to prepare a liquid. The Sb concentrations of the liquid were set to 0.01, 0.03, and 0.100 mol / l, respectively. After depressurizing this liquid once and degassing,
Quartz glass, a silicon substrate, and
Dalime glass is soaked and sealed, each at 60 ℃,
It was kept in a constant temperature bath at 85 ° C. for 15 hours. Take out the base material,
It was washed with water, and it was confirmed that a film was formed on the surface of the substrate. The film thickness and the like were determined by SEM observation. As a result of ESCA analysis of the film composition, Sb, O, and F were detected. IR spectrum analysis shows that fluorine is Sb-F
It was found that they were present in the structure of antimony oxide in the bound state. F was detected at 5 atm% or more in all the films, and it was found that the film was a fluorine-containing antimony oxide film. In addition, each film was sufficiently dense and had good crystallinity. The above results are summarized in Table 3.

Further, each fluorine-containing antimony oxide film is formed into 50
When baked at 0 ° C. for 1 hour and identified by X-ray diffraction,
It was found to be Sb ₂ O ₅ . In addition, in the baked film,
F was not detected. No cracking or peeling was observed, and a dense film having good crystallinity was obtained.

[0037]

[Table 3]

Example 5 40 g of TiF ₄ was added to 100 parts of pure water.
By using a solution dissolved in 0 ml and pure water and mixing both at a predetermined amount at room temperature, Ti concentrations of 0.005 and 0.0
100 ml of 10, 0.030 and 0.100 mol / l solutions were prepared. Quartz glass, silicon substrate, and soda lime glass were immersed therein as a substrate, sealed, and kept in a constant temperature bath at 60 ° C. for 15 hours. The substrate was taken out and washed with water, and it was confirmed that a film was formed on all the substrate surfaces. The results are shown in Table 4. The thickness of the film is S
It was determined from EM observation. As a result of analyzing the film composition by ESCA and EPMA, Ti,
O and F are detected, and the atomic ratio of Ti and O is 1: 1.7-
It was 1.9, and the F amount was 5 atm% or more, as shown in Table 4. According to the IR spectrum analysis, fluorine was present in the structure of titanium oxide in the state of Ti—F bond. From this result, it was found that the fluorine-containing titanium oxide film was formed.

[0039]

[Table 4]

(Embodiment 6) All the films formed on the quartz glass of Embodiment 5 were heated to 300 ° C. or 500 ° C. in the atmosphere.
Firing was performed for 1 hour at each temperature. The film composition after firing is EPM
As a result of analysis by A, the molar ratio of Ti and O is approximately 1: 2.
No other elements were detected. Further, it was found from the X-ray diffraction that the film after firing was anatase type titanium dioxide.

Example 7 InF ₃ .nH ₂ O (n = 3)
Was weighed in a predetermined amount to prepare a liquid dissolved in 100 ml of pure water. In concentration of the liquid is 0.009, 0.018,
It was set to 0.035 and 0.100 mol / l.
After depressurizing this solution by depressurizing it once, immersing quartz glass, silicon substrate and soda lime glass as a base material, sealing them, and keeping them in a constant temperature bath at 60 ° C, 80 ° C and 110 ° C respectively.
Hold for 5 hours. The substrate was taken out and washed with water, and it was confirmed that a film was formed on the substrate surface. 80 ℃ and 110 ℃
Although peeling of the film was partially observed on substrates other than quartz glass, at 60 ° C., films adhered to all substrates were formed. The film thickness and the like were determined by SEM observation. Also,
As a result of analyzing the film composition by ESCA, In, O, F
Was detected. F was detected at 3 atm% or more in all the films, and it was found that a fluorine-containing indium oxide film was formed. The above results are summarized in Table 5.

Further, when the fluorine-containing indium oxide film formed on the surface of the base material was baked at 500 ° C. for 1 hour and identified by X-ray diffraction, it was found to be an In ₂ O ₃ film.
In addition, F was not detected in the baked film.

[0043]

[Table 5]

Example 8 InF ₃ .nH ₂ O (n = 3)
A solution prepared by dissolving 1.6 g in 100 ml of pure water is used at 60 ° C for 2
It was held for 4 hours to generate a precipitate by hydrolysis. This precipitate settled to the bottom of the container, and the liquid became very clear. There, as a base material, quartz glass and silica core
Immerse the soda lime glass that has been dipped,
After standing for 0 hour, a film forming process was performed. The obtained sample is SE
When observed by M, very few particles adhered to the film surface,
It was found that a film having a thickness of 0.1 μm was formed. The samples were fired at 300 ° C. or 500 ° C. for 1 hour in air, respectively. When analyzed by ESCA, the unbaked film had 1
Although 3.0 atm% F was contained, the 300 ° C. calcined film contained only 0.5 atm%, and F was not detected in the 500 ° C. calcined film. When the fired film at 300 ° C. or 500 ° C. was identified by X-ray diffraction, it was confirmed to be I ₂ O ₃ having a C-type crystal structure.

(Example 9) SnF ₂ and SbF ₃ were weighed in predetermined amounts in the molar ratio range of 99: 1 to 70:30 and simultaneously dissolved in 100 ml of pure water at room temperature. Quartz glass, silicon substrate and soda lime glass are immersed therein as a base material and sealed, and the temperature is 60 ° C or 80 ° C, respectively.
Hold at 24 ° C for 24 hours. The substrate was taken out and washed with water, and it was confirmed that a film was formed on the substrate surface. The film thickness and the like were determined by SEM observation. Moreover, as a result of analyzing the film composition by EPMA, Sn, Sb, and F were detected. Furthermore, the relationship between the amount of Sb contained in the coating and that of the prepared liquid was determined. The above results are summarized in Tables 6 and 7.

[0046]

[Table 6]

[0047]

[Table 7]

Example 10 SnF ₂ 9.9 × 10 ⁻⁴ m
ol and SbF ₃ 1.0 × 10 ⁻⁵ mol, SnF ₂ 9.0
× 10 ⁻⁴ mol and SbF ₃ 1.0 × 10 ⁻⁴ mol, and SnF ₂ 9.6 × 10 ⁻³ mol and SbF ₃ 4.0 ×
Three of 10 ⁻⁴ mol were weighed and dissolved in 100 ml of pure water to prepare a liquid. This solution was once depressurized and deaerated, and then quartz glass, a silicon substrate, and soda lime glass as a base material were immersed therein, sealed, and kept at 60 ° C. for 24 hours. No. Only 3 experiments were kept at 80 ° C. The substrate was taken out and washed with water, and it was confirmed that a film was formed on the surface of each substrate. The film thickness and the like were determined by SEM observation. Moreover, as a result of analyzing the film composition by ESCA, Sn
And Sb were detected. This film at 500 ℃, 1 in the atmosphere
As a result of firing for a time and measuring the electric conductivity, electronic conductivity was confirmed. In addition, F was not detected in the baked film.
The results are shown in Table 8.

[0049]

[Table 8]

(Example 11) A predetermined amount of NbF ₅ was weighed,
A solution dissolved in 100 ml of pure water was prepared. The Nb concentration of the liquid is 0.01, 0.03, 0.100 mol / l, respectively.
So that Quartz glass, a silicon substrate, and soda lime glass as a base material were immersed therein, sealed, and kept in a constant temperature bath at 60 ° C. for 15 hours. The solution was cloudy due to the formation of hydrolyzed colloids.

The substrate was taken out of the solution and washed with water, and it was confirmed that a film was formed on the surface of the substrate. The film thickness and the like were determined by SEM observation. As a result of ESCA analysis of the film composition, Nb, O, and F were detected. F was detected in all films at 3 atm% or more, and it was found that the film was a fluorine-containing niobium oxide film. The above results are shown in Table 9.

Further, each fluorine-containing niobium oxide film was formed in the atmosphere 5
It was baked at 00 ° C. for 1 hour. As a result of analyzing the film composition by ESCA, F was not detected and only Nb and O were confirmed. From X-ray diffraction, it was found to be a crystalline film of niobium oxide.

[0053]

[Table 9]

(Example 12) Except that TaF ₅ was used, the same experiment as in Example 11 was conducted, and it was confirmed that a fluorine-containing tantalum oxide film was obtained. The results are shown in Table 10.

[0055]

[Table 10]

Example 13 The same experiment as in Example 11 was conducted except that MnF ₃ was used and the holding temperature of the solution was 80 ° C., and it was confirmed that a fluorine-containing manganese oxide film was obtained. The results are shown in Table 11.

[0057]

[Table 11]

[0058] (Example 14) CoF ₃ and FeF ₃ · 3H ₂
A predetermined amount of O was weighed so that the molar ratio was 9/1, and pure water 10
A solution dissolved in 0 ml was prepared. The Co + Fe concentration of the liquid was set to 0.01, 0.03, and 0.100 mol / l, respectively. Quartz glass and silicon were immersed therein as a substrate, sealed, and kept in a constant temperature bath at 85 ° C. for 15 hours. The base material was taken out and washed with water, and it was confirmed that a film was formed on the surface of the base material. The film thickness and the like were determined by SEM observation. As a result of analyzing the film composition by EPMA, Co, Fe, O and F were detected. In all the films, F was detected in an amount of 3 atm% or more, and it was found that the film was a fluorine-containing cobalt oxide / iron film. The above results are shown in Table 12.
Are shown together.

Further, a fluorine-containing cobalt oxide / iron coating is used.
It was confirmed that a fluorine oxide-free cobalt oxide / iron-based coating film was formed by heating in the atmosphere at 00 ° C. for 1 hour.

[0060]

[Table 12]

(Example 15) PbF ₄ and TiF ₄ were weighed in predetermined amounts so that the molar ratio was 1/1, and a solution dissolved in 100 ml of pure water was prepared. The Pb + Ti concentrations of the liquid were set to 0.01, 0.03, and 0.100 mol / l, respectively. Quartz glass as a substrate was immersed therein, sealed, and kept in a constant temperature bath at 60 ° C. for 15 hours. The base material was taken out and washed with water, and it was confirmed that a film was formed on the surface of the base material. The film thickness and the like were determined by SEM observation. In addition, as a result of analyzing the film composition by EPMA, Pb, Ti,
O and F were detected. In all the films, F was detected at 3 atm% or more, and it was found that the film was a fluorine-containing lead oxide / titanium film. The above results are summarized in Table 13.

Also, a fluorine-containing lead oxide / titanium coating is used.
After heating at 0 ° C. for 1 hour in the atmosphere, it was confirmed that a fluorine-free lead titanate composite oxide film was formed.

[0063]

[Table 13]

[0064]

The method for producing a fluorine-containing metal oxide film of the present invention uses an aqueous solution consisting of a metal fluoride alone, and the microcolloid produced during the hydrolysis of this solution is polymerized on the surface of the substrate. This is based on the principle that a film is formed. The feature of this method is that a dense film can be formed at a low temperature, and a large-area film can be easily formed.
It is possible to apply a large amount of film at one time, to form a film on a surface having an arbitrary shape, to form a film with a multi-component composition, and to simplify the manufacturing apparatus, which is economical.

The fluorine-containing metal oxide film obtained by the method of the present invention is a transparent conductive film, an infrared / ultraviolet selective absorption film, an antistatic film, a gas sensor, a functional film utilizing photocatalysis, a piezoelectric material, a magnetic thin film. It can be used for a wide range of purposes.

The obtained fluorine-containing metal oxide film is
A metal oxide film containing no fluorine can be easily formed. The use as described above is also conceivable for this coating. Therefore, it is an industrially valuable method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-249219 (32) Priority date Hei 5 (1993) October 5 (33) Priority claim country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 5-257076 (32) Priority Date No. 5 (1993) October 14 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-53556 (32) Priority Hihei 6 (1994) March 24 (33) Priority claiming countries Japan (JP)

Claims (5)

[Claims] 1. A substrate is brought into contact with or immersed in a solution in which a metal fluoride having a property of being hydrolyzed is dissolved, and a product of the hydrolysis reaction of the metal fluoride is deposited on the surface of the substrate to thereby remove fluorine. A method for producing a fluorine-containing metal oxide film, which comprises forming the contained metal oxide film in a liquid phase. 2. As a metal fluoride having a property of being hydrolyzed, tin fluoride, antimony fluoride, titanium fluoride,
Indium fluoride hydrate, lead fluoride, chromium fluoride hydrate, cobalt fluoride, ferric fluoride hydrate, manganese fluoride, tungsten fluoride, niobium fluoride, tantalum fluoride, vanadium fluoride And / or zirconium fluoride is used. 3. A solution containing two or more kinds of metal fluorides having a property of hydrolyzing is used, and a base material is dipped or brought into contact therewith, and the surface thereof is composed of two or more kinds of metal oxides containing fluorine. The manufacturing method according to claim 1, wherein a coating film is formed. 4. The method according to claim 3, wherein tin fluoride and antimony fluoride are used as the metal fluoride to form a fluorine-containing antimony-containing tin oxide film. 5. A fluorine-containing metal oxide coating obtained by the method according to claim 1 is baked to remove fluorine to obtain a fluorine-free metal oxide coating. A method for producing a metal oxide film, comprising: