JPH0729769B2 - Silicon oxide film manufacturing method - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silicon oxide film used for an insulating film or a dielectric film of a semiconductor device or the like.

2. Description of the Related Art Conventional methods for producing a silicon oxide film are roughly classified into a method using a vacuum device and a method not using a vacuum device.

As a method of using a vacuum device, a sputtering method of forming a thin film by sputtering using a bulk sintered body as a target, a vapor deposition method using an electron beam, a mixed gas of silane gas and an oxidizing gas with light or electromagnetic waves, etc. There is a CVD method in which a film is formed by causing a chemical reaction in a plasma state.

As a method that does not use a vacuum device, plasma spraying method in which oxide is melted and vaporized by high temperature plasma to form a thin film on the substrate and then annealed, and paste containing oxide is screen-printed on the substrate to form a thin film and then annealed Screen printing method, sol-gel method in which a gelled product obtained by hydrolyzing a metal alkoxide is applied to a substrate and thermally decomposed, and then an organic acid salt solution is applied to a substrate and annealed after thermal decomposition A thermal decomposition method, a spray pyrolysis method in which a metal salt solution is applied to a substrate by spraying and then annealed after thermal decomposition, and the like are performed.

However, although the oxide film obtained by the method using a vacuum device has a dense film quality, it requires large-scale equipment to form a uniform film in a large area, which causes a cost increase. It's one.

On the other hand, an oxide film obtained by a method that does not use a vacuum device has a low cost, but since it has to be thermally decomposed at a high temperature of 400 ° C. or higher, it may have an adverse effect depending on the type of film-forming substrate,
Moreover, since it is difficult to sufficiently heat the details, there is a problem that the film quality is non-uniform and lacks in fineness.

The present invention has been made in order to improve such drawbacks of the conventional example, and an object thereof is to provide a method for producing a silicon oxide film capable of obtaining a uniform and dense film at a low cost at a low temperature. It is a thing.

Means for Solving the Problems In order to achieve the above object, the present invention comprises (a) an amic acid compound and / or an imide compound containing a silicon atom having a hydrolyzable group, and (b) a general formula (a). Represented disilazane compound (In the formula, R ^{1 to} R ⁶ are the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.) By treating with an oxidizing atmosphere obtained by irradiating with ultraviolet rays in the presence of a gas containing at least one of oxygen and ozone,
It is characterized by producing a silicon oxide film.

Hereinafter, the manufacturing method of the present invention will be described in detail for each constituent element.

The component (a) is hydrolyzed by water generated by this reaction or water outside the system when an amic acid compound containing a hydrolyzable silicon atom is dehydrated and condensed by heating or standing at room temperature to become an imide compound. A degradable silicon atom (that is, a hydrolyzable group on the silicon atom) is hydrolyzed, and dehydration and condensation are repeated to form a high molecular weight substance.

The component (a) can be obtained by the following reaction A or B.

A: Reaction of tetracarboxylic dianhydride with a silicon compound having an amino group and / or an imino group and a hydrolyzable group (hereinafter, simply referred to as a silicon compound).

B: Reaction of a diamino compound and a dicarboxylic acid anhydride having a hydrolyzable silicon atom (hereinafter referred to as a silicon atom-containing dicarboxylic acid anhydride).

Examples of the tetracarboxylic dianhydride used in the reaction A include aromatic, aliphatic, and alicyclic tetracarboxylic dianhydrides such as pyromellitic dianhydride and phenyltetracarboxylic dianhydride. , 3,3 ', 4,4'-biphenyltetracarboxylic anhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic Acid dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3'
-Benzophenone tetracarboxylic dianhydride, bis (3,
4-dicarboxyphenyl) -ether dianhydride, bis (3,4-dicarboxyphenyl) -sulfone dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,
Aromatic tetracarboxylic acids such as 6,7-naphthalenetetracarboxylic dianhydride; butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynolbornane-2-acetic acid dianhydride, 5- (2,5- Dioxotetrahydrofur)-
Examples thereof include aliphatic and alicyclic tetracarboxylic acid dianhydrides such as 3-methyl-cyclohexene dicarboxylic acid dianhydride and bicyclo (2,2,2) -oct-7-enetetracarboxylic acid dianhydride. it can.

Among these tetracarboxylic dianhydrides, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic dianhydride , 3,3'4,4'-benzophenone tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride , 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and the like are preferable.

These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Further, examples of the silicon compound used in the reaction A include those represented by the following general formulas (1) to (6).

However, in the above general formulas (1) to (6), R to R ″ are the same or different and are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n.
An aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a pentyl group, an i-pentyl group and a neopentyl group; an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a xylyl group, a nitrophenyl group and an α-naphthyl group. Show. X ^{1 to} X ³ are the same or different and each represents an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group; and a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom. Y is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms such as methylene group, ethylene group, propylene group, tetramethylene group; phenylene group, tolylene group, xylylene group, nitrophenylene group, α-naphthylene group, etc. A divalent aromatic hydrocarbon group having 6 to 10 carbon atoms; a group in which the divalent aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded to each other.

Specific examples of the silicon compound include those represented by the following structural formula.

_{NH 2 - (CH 2) 3} -Si (OCH 3) 3 NH 2 - (CH 2) 3 -Si (OC 2 H 5) 3 NH 2 - (CH 2) 3 -Si (CH 3) (OCH 3) _{2 NH 2 - (CH 2)} 3 -Si (CH 3) (OC 2 H 5) 2 NH 2 - (CH 2) 3 -Si (C 2 H 5) (OC 3 H 7) NH 2 - (CH 2 ) _4- Si (OCH ₃ ) ₃ NH _2- (CH ₂ ) _4- Si (OC ₂ H ₅ ) ₃ NH _2- (CH ₂ ) _4- Si (CH ₃ ) (OC ₂ H ₅ ) _{2 NH 2 - (CH 2) 3} -Si (CH 3) 2 (OC 2 H 5) NH 2 - (CH 2) 4 -Si (CH 3) 2 (OC 2 H 5) _{NH (CH 3) - (CH} 3) 2 -Si (OC 2 H 5) 3 NH (C 2 H 5) - (CH 2) 3 -Si (CH 3) (OCH 3) 2 Among these silicon compounds, preferred ones are:
Examples thereof include aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, p-aminophenyltrimethoxysilane and p-aminophenylmethyldiethoxysilane.

These silicon compounds can be used alone or in combination of two or more kinds, and further, a monoamine and a compound can be used in combination.

Specific examples of the monoamine compound include lower alkylamine compounds such as methylamine, ethylamine, propylamine, n-butylamine, i-butylamine, n-pentylamine, i-pentylamine, n-hexylamine and cyclohexylamine; aniline Arylamine compounds such as toluidine, naphthylamine and the like. These monoamine compounds can be used in an amount of 10 to 90 mol% of the total amount of the silicon compound and the monoamine compound. If it is less than 10 mol%, the storage stability of the obtained composition may be poor. On the other hand, if it exceeds 90 mol%, the curability of the obtained composition will be insufficient.

The molar ratio of the tetracarboxylic dianhydride and the silicon compound in the reaction A is usually 1/1 to 1/3, preferably 1 /
The reaction temperature is 0 to 60 ° C., preferably 0 to 40 ° C., and the reaction time is 5 to 500 minutes, preferably 30 to 120 minutes.

The polystyrene reduced weight average molecular weight of the reaction product obtained by the reaction of A is usually 500 to 50,000, and the temperature is 25 ° C.
The viscosity at is 5 to 2,000 cps.

In the reaction of A, for example, when 3-aminopropyltriethoxysilane and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride are used, the following reaction occurs.

On the other hand, examples of the diamino compound used in the reaction of B include aliphatic, alicyclic and aromatic diamines.

Specific examples of diamines include paraphenylenediamine,
Metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1 5,5'-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether,
3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, octamethylenediamine, nonamethylenediamine, 4,4'-dimethylheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylene. Diamine, tricyclo [6,2,1,
0 ^2.7 ] -undecylenedimethyldiamine, and (In the formula, R ⁷ is a methyl group or a phenyl group, m is an integer of 1 to 3, and n is an integer of 1 to 20.) and the like.

Further, as diamines other than the above, bis (4-aminophenyl) fluorene, diaminotetraphenylthiophene, 4,4'-phthalide-3,3'-diaminodiphenyl ether, 4,4'-phthalide-3,3'-diamino Diphenylmethane, 4,4'-phthalide-3,3'-diaminobenzophenone, 4,4'-acetamido-3,3'-diaminodiphenyl ether, 4,4'-acetamido-3,3'-diaminodiphenylmethane, 4,4 '-Acetamido-3,3'-diaminobenzophenone, 4-sulfonamido-1,3-phenylenediamine, 4,6-bis (aminophenyl) -1,3-phenylenediamine, 5-amino-1 (4'- Aminophenyl) -1,3,3-trimethylindane, 6-amino-1
Other examples include (4'-aminophenyl) -1,3,3-trimethylindane.

These diamino compounds can be used alone or in combination of two or more kinds.

Examples of the silicon atom-containing dicarboxylic acid anhydride used in the reaction B include compounds represented by the following general formulas (α) to (γ).

However, in the general formulas (α) to (γ), R to R ′,
X ^{1 to} X ³ are the same as those in the general formulas (1) to (6), and Y ′
Is a trivalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group in which they are bonded.

Specific examples of the silicon atom-containing dicarboxylic acid anhydrides represented by the above general formulas (α) to (γ) include those represented by the following structural formulas.

Among these silicon atom-containing dicarboxylic acid anhydrides, 3-trimethoxysilyl-1,
2,5,6-tetrahydrophthalic anhydride, 3-trimethoxysilylphthalic anhydride, 3-methyldimethoxysilylphthalic anhydride, 3-dimethylmethoxysilylphthalic anhydride and the like can be mentioned.

These silicon atom-containing dicarboxylic acid anhydrides can be used alone or in combination of two or more kinds.

Furthermore, dicarboxylic acid anhydrides such as phthalic anhydride, maleic anhydride, and succinic anhydride (hereinafter, these are referred to as other dicarboxylic acid anhydrides) are prepared by using the above-mentioned silicon atom-containing dicarboxylic acid anhydrides and other dicarboxylic acid anhydrides. And 10 to 90 mol% of the total amount thereof can be used. 10 mol%
If it is less than 1, the storage stability of the resulting composition may be poor. On the other hand, if it exceeds 90 mol%, the curability of the obtained composition may be insufficient.

The molar ratio of the diamino compound and the silicon atom-containing dicarboxylic acid anhydride in the reaction of B is usually 1/1 to 1/2, preferably 1 / 1.5 to 1 / 2.5, and the reaction temperature is 0 to 60 ° C. , Preferably 0 to 40 ° C., reaction time 5 to 500 minutes, preferably 3
It is about 0 to 120 minutes.

The polystyrene equivalent weight average molecular weight of the reaction product obtained by the reaction of B is usually 500 to 100,000, and the temperature is 25 ° C.
The viscosity at is 5 to 2,000 cps.

The reaction of B is, for example, become that way.

A reaction solvent can be used in the above reactions A and B, and examples of the reaction solvent include various organic solvents used for adjusting the concentration of the composition described below.

The amount of the reaction solvent used is usually 50 to 1,000 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by weight in total of various compounds used in the reaction system.

(B) Disilazane Compound The disilazane compound serves to improve the storage stability of the component (a) and the adhesion to the substrate.

R ^{1 to} R ⁶ in the general formula (a) are the same or different, and include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, i-pentyl group, neopentyl group, n
-Hexyl group, cyclohexyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group; or phenyl group, tolyl group, xylyl group, nitrophenyl group, naphthyl group, and other alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 10 carbon atoms is there.

Specific examples of the disilazane compound include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexa-n-putyldisilazane, hexa-
n-pentyldisilazane, ethylpentamethyldisilazane, diethyltetramethyldisilazane, trimethyltriethyldisilazane, n-propylpentamethyldisilazane, di-n-propyltetramethyldisilazane, tri-
Examples thereof include n-propyltrimethyldisilazane, tetramethyldiphenyldisilazane, trimethyltriphenyldisilazane, dimethyltetraphenyldisilazane, triethyltritolyldisilazane, and pentamethyl-α-naphthyldisilazane, and preferably hexamethyldisilazane. , Hexaethyldisilazane, hexapropyldisilazane and the like.

The amount of the component (b) used is usually 5 to 200 mol%, preferably 10 to 1 with respect to the carboxyl group in the component (a).
It is 50 mol%. If it is less than 5 mol%, the composition has poor storage stability. On the other hand, if it exceeds 200 mol%, the hardness of the obtained coating film may be lowered.

The composition used in the present invention contains the above-mentioned components (a) and (b) as main components, but is usually used by dissolving it in an organic solvent which is a concentration adjusting agent.

As the organic solvent, alcohols, esters, ethers, ketones, amides and the like can be used.

Here, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, sec-butyl alcohol,
t-butyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, butyl cellosolve , Ethyl cellosolve, carbitol and the like.

Examples of the esters include ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, r-butyrolactone, carbitol acetate. , Ethyl acetate cellosolve, butyl acetate cellosolve and the like.

Examples of ethers include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether.

Examples of ketones include acetone, methyl ethyl ketone, diisopropyl ketone, and cyclohexanone.

Examples of the amides include tetramethylurea, hexamethylphosphoramide, methylformamide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

Of these organic solvents, alcohols, esters and ketones are preferable.

These organic solvents may be used alone or in combination of two or more.

The composition used in the present invention may further be mixed with a nonionic surfactant. This nonionic surfactant shortens the reaction time of the composition after the component (a) is mixed, improves the wettability of the composition to an object to be coated, and improves the leveling property of the composition, It prevents the occurrence of crushing of the coating film and the occurrence of orange peel, facilitates repeated coating, and helps stabilize the composition.

Examples of such nonionic surfactants include fluorine-based surfactants having a fluorinated alkyl group or perfluoroalkyl group, or polyether alkyl-based surfactants having an oxyalkyl group.

Examples of the fluorine-based surfactant include C ₉ F ₁₉ CONHC ₁₂ H ₂₅ C ₈ F ₁₇ SO ₂ NH- (C ₂ H ₄ O) ₆ HC ₉ F ₁₇ O (Pluronic L-35) C ₉ F ₁₇ C ₉ F ₁₇ O (Pluronic P-84) C ₉ F ₁₇ C ₉ F ₇ O (Tetronic-704) (C ₉ F ₁₇ ) ₂ (where Pluronic L-35: Asahi Denka Kogyo Co., Ltd., Polyoxy Propylene-polyoxyethylene block copolymer, average molecular weight 1,900; Pluronic P-84: Asahi Denka Kogyo KK, polyoxypropylene-polyoxyethylene block copolymer, average molecular weight 4,200; Tetronic-70
4: Asahi Denka Kogyo KK, N, N, N ', N'-tetrakis (polyoxypropylene-polyoxyethylene block copolymer), average molecular weight 5,000) and the like can be mentioned.

Specific examples of these fluorine-based surfactants include Ftop EF301, EF303, and EF352 (Shin-Akita Kasei Co., Ltd.).
Made), Megafac F171, F173 (Dainippon Ink Co., Ltd.)
Manufactured by Asahi Guard AG710 (manufactured by Asahi Glass Co., Ltd.), Florard FC-170C, FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC101, SC102, S
C103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.)
Made), BM-1000, 1100 (made by BM-Chemie), Schsego-F
luor (manufactured by Schwegmann) and the like can be mentioned.

Further, as the polyether alkyl-based surfactant, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethyleneoxypropylene A block polymer etc. can be mentioned. Specific examples of these polyether alkyl-based surfactants include Emulgen 105, 430, 810, 920, Leodol SP-40S, and Emulgen 105.
TW-L120, Emanor 3199, Same 4110, Exel P-40S, Bridge 30, Same 52, Same 72, Same 92, Arassel 20, Emazol 320, Tween 20, Same 60, Merge 45 (all of these companies)
Kao), Noniball 55 (manufactured by Sanyo Kasei Co., Ltd.) and the like.

Nonionic surfactants other than the above include, for example, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyalkylene oxide block copolymer, and the like, specifically Chemistat 25
Examples include 00 (manufactured by Sanyo Chemical Industry Co., Ltd.), SN-EX9228 (manufactured by San Nopco Co., Ltd.), and Nonal 530 (manufactured by Toho Chemical Industry Co., Ltd.).

The amount of the nonionic surfactant used is (a) + (b)
With respect to 100 parts by weight of the component, preferably 0.01 to 10 parts by weight,
Particularly preferred is 0.1 to 5 parts by weight. If it is less than 0.01 part by weight, the effect of the nonionic surfactant cannot be exhibited, while
If the amount exceeds 10 parts by weight, the resulting composition is likely to foam, and thermal discoloration may occur, which is not preferable.

The composition used in the present invention may contain an anionic surfactant or a cationic surfactant in addition to the nonionic surfactant.

It is also possible to add colloidal silica dispersed in water and / or a hydrophilic organic solvent to the composition used in the present invention.

This colloidal silica is used for increasing the solid content concentration of the composition used in the present invention, and the thickness of the resulting coating film can be controlled by the amount of this component used.

When colloidal silica is used, the solvent is selected and used in consideration of the compatibility with the organic solvent used in the present invention.

Further, the composition used in the present invention, for the purpose of preventing gelation and thickening of the composition, heat resistance of the resulting cured product, chemical resistance, hardness, improvement of adhesion, and further antistatic, Fine powders of metal oxides such as aluminum oxide, zirconium oxide, and titanium oxide can be appropriately mixed.

Further, in the composition used in the present invention, other polymers compatible with the composition, for example, polyamide, polyimide, silicone resin, epoxy resin, acrylate resin, urethane resin and the like can be mixed and used.

When adjusting the composition used in the present invention, the adjusting method is not particularly limited, but usually, the component (b) is added to the component (a) obtained by the reaction of A or B, and the above surfactant is further added. Etc. are added to prepare.

As described above, the composition used in the present invention has the above (a)
~ (B) component and optionally other components are mixed appropriately, and the total solid content concentration is preferably 10 to 50% by weight,
It is particularly preferably 15 to 40% by weight. If it is less than 10% by weight, the solid content may be too thin, so that various properties such as heat resistance, water resistance, chemical resistance, and weather resistance of the resulting protective film may not be exhibited. Holes may occur. On the other hand, if it exceeds 50% by weight, the solid content concentration may be too high and storage stability of the composition may be deteriorated, or it may be difficult to form a uniform protective film.

In addition, the composition used in the present invention can be made into a uniform dispersion liquid by a method such as high-speed stirring when the above-mentioned additive is blended.

In the present invention, the composition is used as a composition solution on a substrate, and the film thickness after drying is preferably by a method such as a spray method, a roll coating method, a curtain coating method, a spin coating method, a screen printing or an offset printing. 0.01
˜50 μm, particularly preferably about 0.1 to 10 μm, and apply this using a heating means such as a hot plate or an oven at a temperature of about 50 to 300 ° C., preferably about 100 to 200 ° C. It is cured by heating for about 120 minutes or by drying at room temperature for about 1 to 7 days.

The cured film obtained as described above is treated in an oxidizing atmosphere obtained by irradiating ultraviolet rays in the presence of a gas containing at least one of oxygen and ozone to produce a silicon oxide film. is there.

Action The silicon oxide film of the present invention obtained in the above-mentioned structure is low in cost because it does not require a vacuum device, and moreover, because heat is generated in detail by irradiation with ultraviolet rays, it is possible to uniformly cause an oxidation reaction in a minute portion. As a result, the film quality is uniform and dense.

Furthermore, compared with the conventional method that requires heating at a high temperature of 400 ° C. or higher, the oxidation reaction can be performed at a low temperature, so there are few restrictions on the type of substrate.

Further, by selectively irradiating ultraviolet rays, it is also possible to selectively form a silicon oxide film in a cured film of a silicon-containing organic compound. That is, by changing the film thickness of the insulating film arbitrarily, it is possible to form the thin film portion made of the silicon oxide film in an arbitrary pattern.

Examples Examples of the present invention will be described below.

(Example 1) In a round bottom flask equipped with a dropping funnel and a stirrer, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 3
Charge 22 grams and methyl cellosolve 644 grams,
360 g of aminopropyltriethoxysilane from the dropping funnel
After slowly dripping at 20 ° C, the mixture was further stirred at 20 ° C for 2 hours. To the reaction mixture thus obtained, 161 g of hexamethyldisilazane and 5 g of a fluorosurfactant (BM-1000, manufactured by BM-Amy Co., Ltd.) were added, and a homogeneous solution was prepared with a membrane filter having a pore size of 0.2 μm. Then, a preparation liquid was obtained.

This prepared solution was spin-coated on a silicon substrate at a rotation speed of 1000 rpm and heat-treated at 180 ° C for 1 hour to give a dry film thickness of 1.8μ.
A cured film of m was obtained.

Next, the above-mentioned substrate is placed in a reaction vessel equipped with a low pressure mercury lamp and an ozonizer to cause an oxidation reaction. At this time, the substrate is heated to 200 ° C. After 20 minutes, a 900 Å silicon oxide film was obtained.

Etching rate of the obtained silicon oxide film (etching rate at HF / H ₂ O = 1/200) to test the denseness of the film quality
Was measured to be 200 Å / min. On the other hand, the etching rate of the thermal oxide film under the above-mentioned etching conditions performed as a comparative example was 300 Å / min.

(Example 2) Next, a method for forming a pattern of a silicon oxide film on a cured film using the preparation liquid prepared in the same manner as in Example 1 will be described.

In the same manner as in Example 1, the above-mentioned preparation liquid was applied to the substrate and Example 1 was applied.
A similar process is performed to obtain a cured film.

The low-pressure mercury lamp of the reaction vessel of Example 1 was provided with a mask,
Selectively allow UV light to pass through.

The substrate after the above treatment is heated to 200 ° C.
Perform 0 minute processing. A cured film of a silicon oxide film having a thickness of 0.08 μm was formed on the portion irradiated with the ultraviolet rays, and a cured film having a thickness of 1.7 μm was formed on the non-irradiated portion.

EFFECTS OF THE INVENTION Since the present invention has the above-described structure and action, it is possible to manufacture a silicon oxide film having a uniform and precise film quality at low cost, and it is possible to expand the types of film-forming substrates,
It is extremely useful for manufacturing electronic materials and electronic devices.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriko Iwamoto 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Incorporated (72) Inventor Yukihiro Hosaka 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (56) Reference JP-A-63-289939 (JP, A) JP-A-63-248710 (JP, A) JP-A-59-111333 (JP, A)

Claims (1)

[Claims] 1. (a) An amic acid compound and / or imide compound containing a silicon atom having a hydrolyzable group,
(B) Disilazane compound represented by the general formula (a) (In the formula, R ^{1 to} R ⁶ are the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.) By treating with an oxidizing atmosphere obtained by irradiating with ultraviolet rays in the presence of a gas containing at least one of oxygen and ozone,
A method for producing a silicon oxide film, which comprises producing a silicon oxide film.