JP2858960B2 - Silica-based coating-type insulating film forming material, method of manufacturing the same, silica-based insulating film, semiconductor device, and method of manufacturing semiconductor device - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a material for forming a silica-based coating-type insulating film used for forming an interlayer insulating film of a multilayer wiring in, for example, an VLSI, a manufacturing method thereof, and a silica-based insulating film. More specifically, the present invention provides a material for forming a silica-based coating-type insulating film which can form a thick film on various substrates such as a semiconductor substrate and a glass plate and has good oxygen plasma resistance, a method for producing the same, and a silica-based insulating film. About.

2. Description of the Related Art In recent years, rapid increase in density and integration of VLSI has progressed, and there is a demand for a multilayer aluminum wiring and a reduction in a minimum processing line width due to miniaturization of its wiring pattern. Therefore, there is a demand for a flattening technique for filling the fine wiring intervals without voids in the interlayer insulating film of the multilayer wiring used in these LSIs and for flattening the surface.

Conventionally, as an interlayer insulating film requiring this planarization,
A coating solution obtained by hydrolyzing an alkoxysilane and an alkylalkoxysilane in an organic solvent such as an alcohol by adding water and a catalyst is applied by a spin coating method, and then flattened by curing by a heat treatment. A so-called spin-on-glass (SOG) film (SOG film) is employed. Above all, a side chain of an organic component (an alkyl group such as methyl) is bonded to a main chain of a siloxane bond, that is, a thin film is formed to suppress crack generation and improve flattening characteristics. SO with organic components (alkyl groups such as methyl) remaining on the surface
G film is mainly used.

This organic SOG film has advantages such as low volume shrinkage during curing, hydrophobicity, and low dielectric constant.However, during the LSI manufacturing process, the contact hole between the lower and upper aluminum wiring of the insulating film was used. When dry etching with oxygen plasma to peel off the photosensitive resist for formation,
The oxygen plasma causes the alkyl groups in the film to be desorbed, thereby causing cracks. Therefore, rather than a single layer as an insulating film, as the organic SOG film during oxygen plasma treatment is not exposed to the surface, formation of the SiO ₂ film by plasma CVD underlying the SOG film coating, coating and etchback of the organic SOG film SiO by plasma CVD to be treated and overcoated
It is based on a three-layer structure consisting of _two films.

FIG. 1 shows an example of a method for manufacturing a semiconductor device using such an organic SOG film.

In FIG. 1, reference numeral 11 denotes a semiconductor chip substrate on which circuit electrons, which are elements constituting an electronic circuit such as a transistor, a diode, a resistor, and a capacitor, are formed; 12, a first aluminum wiring formed on the semiconductor chip substrate;
13 is SiO ₂ by plasma CVD which is the base of organic SOG film coating
The film 14 is an organic SOG film (FIG. 1A). Organic SOG film 14
Perform an etch-back process to treat the entire surface with oxygen plasma,
The plasma CVD SiO ₂ film in the aluminum wiring 12 is exposed (FIG. 1B). An SiO ₂ film 15 is formed on the entire processing surface subjected to the etch-back process by plasma CVD as an overcoat,
A predetermined etching resist 16 is formed (FIG. 1C),
Etching is performed to remove the plasma CVD SiO ₂ film 15 in the portion of the aluminum wiring 12 not covered with the etching resist 16 by etching to expose the aluminum wiring 12 and remove the etching resist (FIG. 1 (d)). A second aluminum wiring 17 connected to the wiring 12 is formed (FIG. 1E) to manufacture a semiconductor device.

However, due to the high density and high integration of the VLSI, the space between the aluminum wirings has become fine, and the conventional three-layer structure has
By forming SiO ₂ film of plasma CVD which is the base of G coating,
Since the space between the fine aluminum wiring spaces is further narrowed, the SOG coating liquid is less likely to flow between the aluminum wiring spaces, and as a result, a defective filling of the organic SOG film occurs. For this reason, it has become more difficult to form an interlayer insulating film with the conventional three-layer structure as the minimum processing line width accompanying the miniaturization of the aluminum wiring is reduced. Therefore, an SOG film that has good oxygen-resistant plasma and can form an interlayer insulating film even with a single layer is expected.

In addition, in order to shorten the semiconductor device manufacturing process with the goal of reducing costs, a non-etch-back type SOG film that does not require an etch-back process is required. Therefore, based on an inorganic SOG film having excellent asher resistance (a film basically containing no organic components), addition of SiO ₂ fine particles,
The use of O and Mg—O bonds and the introduction of a Si—N skeleton have been studied, but have not been solved yet.

DISCLOSURE OF THE INVENTION The present invention provides a material for forming a silica-based coating-type insulating film which can be applied to a thick film for improving the flattening characteristics and has excellent oxygen plasma resistance, a method for producing the same, and a silica-based insulating film. Is what you do.

The first invention of the present application relates to (a) an alkoxysilane and / or
Or (b) a fluorine-containing alkoxysilane, (c) an alkoxide of a metal other than Si and / or a derivative thereof, (d) a silica-based coating-type insulating film forming material obtained from an organic solvent, and The manufacturing method.

The second invention of the present application relates to (a) an alkoxysilane and / or
Or a partially hydrolyzed product thereof, (e) an alkylalkoxysilane, (c) an alkoxide of a metal other than Si and / or a derivative thereof, and (d) a silica-based coating-type insulating film-forming material obtained from an organic solvent and a method for producing the same. It is.

The third invention of the present application relates to (a) an alkoxysilane and / or
Or a partially hydrolyzed product thereof, (b) a fluorine-containing alkoxysilane, (f) water and a catalyst, (d) a silica-based coating-type insulating film-forming material obtained from an organic solvent, and a method for producing the same.

The fourth invention of the present application provides (a) an alkoxysilane,
(E) alkylalkoxysilane and / or (b) fluorine-containing alkoxysilane, (c) alkoxide of metal other than Si and / or derivative thereof, (d) organic solvent,
(F) A method for producing a silica-based coating-type insulating film forming material obtained from water and a catalyst, wherein an alkylalkoxysilane and / or a fluorine-containing alkoxysilane in an organic solvent, water and a catalyst are provided. Is mixed, then an alkoxide of a metal other than Si and / or a derivative thereof is added, and after mixing the alkoxysilane, water and a catalyst are added. .

The fifth invention of the present application provides (e) an alkylalkoxysilane and / or (b) a fluorine-containing alkoxysilane, (c) an alkoxide of a metal other than Si and / or a derivative thereof, (d) an organic solvent, 6.) A silica-based coating-type insulating film forming material obtained from water and a catalyst, and a method for producing the same. The sixth invention of the present application provides (a) an alkoxysilane and / or
Or (e) an alkylalkoxysilane and / or (b) a fluorine-containing alkoxysilane, (c) an alkoxide of a metal other than Si and / or a derivative thereof, (d) an organic solvent, (g) A silica-based coating-type thin film forming material obtained from a photoacid generator and a method for producing the same.

 The first invention of the present application will be described.

Examples of the alkoxysilane (a) include monomers or oligomers such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, each of which can be used alone or in combination of two or more.

In addition, a partial hydrolyzate of alkoxysilane is obtained by adding a catalyst such as water and an organic acid in an organic solvent such as alcohol to a monomer or oligomer of each alkoxysilane, and then reacting at a temperature equal to or lower than the boiling point of the organic solvent for a predetermined time. Obtained by:

As a catalyst, an acid or alkali can be used for hydrolysis. Acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Inorganic acids such as boric acid and carbonic acid, formic acid, acetic acid, propionic acid, lactic acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Organic acids such as fumaric acid, maleic acid, and oleic acid, and acid anhydrides and derivatives thereof are exemplified. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, methylamine, ethylamine, ethanolamine and the like.

The addition amount of water is preferably in the range of 2 mol to 4 mol per 1 mol of alkoxysilane, and if it is less than 2 mol, a film is hardly formed at the time of coating due to insufficient hydrolysis of alkoxysilane, and exceeds 4 mol. The hydrolysis rapidly occurs, and the coating solution is apt to gel. The addition amount of the catalyst is preferably from 0.1 to 5 parts by weight based on 100 parts by weight of the alkoxysilane. If the amount is less than 0.1 part by weight, the hydrolysis of the alkoxysilane is insufficient, so that a film is hardly formed at the time of coating. When the amount is more than the weight part, the coating solution is easily gelled because hydrolysis occurs rapidly. The reaction temperature during the hydrolysis is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and is particularly preferably from 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited, but a method using a liquid chromatograph is simple and preferable.

(B) The fluorine-containing alkoxysilane of the component includes fluorine-containing alkylalkoxysilane, and includes alkoxysilane, alkylalkoxysilane Si
And a compound in which at least a part of the alkyl group of the alkylalkoxysilane is fluorinated. Specifically, fluorotrimethoxysilane, fluorotriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane,
Trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, fluoromethyldimethoxysilane , Fluoromethyldiethoxysilane, trifluoromethylmethyldimethoxysilane, trifluoromethylmethyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyl Diethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyl An ethoxy silane and the like, which may be used either alone or in combination of two or more kinds.

As the alkoxide of a metal other than Si of the component (c),
Li, Na, Cu, Mg, Ca, Sr, Ba, Zn, B, Al, Ga, In, Y, Ge, Sn, Pb, Ti, Z
r, P, Sb, V, Ta, Nb, W, such as metal methoxide, ethoxide,
Propoxide, butoxide and the like can be mentioned, and derivatives thereof include acetylacetonate derivatives thereof, and these can be used alone or in combination of two or more. Among these, Al, Ti, Zr, which are particularly easy to obtain as commercial products, are inexpensive, and easy to handle
The use of alkoxides of the above or their acetylacetonate derivatives is preferred.

As the organic solvent of the component (d), methyl alcohol,
Monohydric alcohols such as ethyl alcohol and isopropyl alcohol and ethers or esters thereof, polyhydric alcohols such as ethylene glycol and glycerin and ethers or esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone And the like, each of which alone,
Alternatively, two or more kinds can be used in combination.

The silica-based coating-type insulating film forming material obtained from the four components (a), (b), (c) and (d) is obtained by mixing alkoxysilane and fluorine-containing alkoxysilane in an organic solvent. , An alkoxide of a metal other than Si and / or a derivative thereof is added, and the molecular weight is increased at room temperature or under heating. Here, water and an organic acid can be added to promote the increase in the molecular weight. Further, water and a catalyst are added to the alkoxysilane in an organic solvent to synthesize a partial hydrolyzate thereof in advance, and after mixing with the fluorine-containing alkoxysilane, an alkoxide of a metal other than Si and / or a derivative thereof is added. It can also be manufactured by adding and proceeding the reaction.

Here, the total amount of the components (a) and (b) is preferably in the range of 1 to 40 parts by weight based on 100 parts by weight of the organic solvent (d). If the total amount of the components (a) and (b) is less than 1 part by weight, it is difficult to form a film at the time of coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. The amount of the component (b) added is preferably from 0.1 mol to 10 mol per 1 mol of the component (a). If the amount of the component (b) is less than 0.1 mol, cracks are likely to occur during heat curing after coating, and if it exceeds 10 mol, it is difficult to obtain a uniform film. Component (c) is added in an amount of 0.01 to 1 mole of the total of components (a) and (b).
A range from moles to 0.5 moles is preferred. If the amount of the component (c) is less than 0.01 mol, the film becomes difficult to be formed at the time of coating because the high molecular weight is insufficient, and if it exceeds 0.5 mol, the high molecular weight is rapidly generated and the coating liquid tends to gel. Become.

The reaction temperature at the time of increasing the molecular weight is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

 The second invention will be described.

(A) an alkoxysilane and / or a partial hydrolyzate thereof, (c) an alkoxide of a metal other than Si and / or a derivative thereof, and (d) an organic solvent used in the second invention,
It is similar to the above.

As the alkylalkoxysilane of the component (e), methyltrimethoxysilane, methyltriethoxysilane,
Methyl tripropoxy silane, methyl tributoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tripropoxy silane, ethyl tributoxy silane, propyl trimethoxy silane, propyl triethoxy silane, propyl tripropoxy silane, propyl tributoxy silane, Phenyltrimethoxysilane,
Phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiethyl Butoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, aminopropyltrimethoxysilane , Aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropyldimethylmethoxysila , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl dimethyl methoxy silane, 3-methacryloxypropyl trimethoxy silane,
3-methacryloxypropyltriethoxysilane, 3-
Methacryloxypropylmethyldimethoxysilane, 3-
Methacryloxypropyl dimethyl methoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl dimethyl methoxy silane, etc., can be used alone or in combination of two or more.

The silica-based coating-type insulating film forming material obtained from the four components (a), (e), (c), and (d) is obtained by mixing alkoxysilane and alkylalkoxysilane in an organic solvent,
It is produced by adding an alkoxide of a metal other than Si and / or a derivative thereof and increasing the molecular weight at room temperature or under heating. Here, water and / or a catalyst can be added to promote the polymerization. In addition, water and a catalyst are added to alkoxysilane in an organic solvent to synthesize a partial hydrolyzate thereof in advance, and after mixing with alkylalkoxysilane, an alkoxide of a metal other than Si and / or a derivative thereof is added. Can also be manufactured.

Here, the total amount of the components (a) and (e) is preferably in the range of 1 to 40 parts by weight based on 100 parts by weight of the organic solvent (d). If the total amount of the components (a) and (e) is less than 1 part by weight, it is difficult to form a film at the time of coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. The amount of component (e) added is preferably from 0.1 mol to 10 mol per 1 mol of component (a). If the amount of component (e) is less than 0.1 mol, cracks are likely to occur during heat curing after coating, and if it exceeds 10 mol, it is difficult to obtain a uniform film. Component (c) is added in an amount of 0.01 to 1 mole of the total of components (a) and (e).
A range from moles to 0.5 moles is preferred. If the amount of the component (c) is less than 0.01 mol, the film is hardly formed at the time of coating due to insufficient high molecular weight. If the amount exceeds 0.5 mol, the high molecular weight is rapidly generated and the coating liquid gels. It will be easier.

The reaction temperature at the time of increasing the molecular weight is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

 The third invention will be described.

The (a) alkoxysilane and / or its partial hydrolyzate, (b) fluorine-containing alkoxysilane, and (d) organic solvent used in the third invention are the same as those described above.

As the catalyst of the component (f), an acid or an alkali can be used. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, and carbonic acid, formic acid, acetic acid, propionic acid, lactic acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid,
Organic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, and oleic acid, and acid anhydrides or derivatives thereof. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, methylamine, ethylamine, ethanolamine and the like.

The silica-based coating-type insulating film forming material obtained from the four components (a), (b), (f), and (d) is obtained by mixing alkoxysilane and fluorine-containing alkoxysilane in an organic solvent, and adding water and It is produced by adding a catalyst and reacting at room temperature or under heating. In addition, water and a catalyst are added to alkoxysilane in an organic solvent to synthesize a partial hydrolyzate thereof in advance, mixed with fluorine-containing alkoxysilane, and then water and a catalyst are added to proceed with the reaction. Can also.

Here, the total amount of the components (a) and (b) is preferably in the range of 1 to 40 parts by weight based on 100 parts by weight of the organic solvent (d). If the total amount of the components (a) and (b) is less than 1 part by weight, it is difficult to form a film during coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. The amount of the component (b) added is preferably from 0.1 mol to 10 mol per 1 mol of the component (a). If the amount of the component (b) is less than 0.1 mol, cracks are likely to occur during heat curing after coating, and if it exceeds 10 mol, it is difficult to obtain a uniform film. The amount of water (f) added is 2 per mole of the total of components (a) and (b).
The range of from 4 mol to 4 mol is preferable, and if it is less than 2 mol, the film is hardly formed at the time of coating due to insufficient hydrolysis of the components (a) and (b). As a result, the coating liquid tends to gel. The amount of the catalyst (f) to be added is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the components (a) and (b), and if less than 0.1 part by weight, the components (a) and (b) Is insufficiently formed to form a film at the time of coating. When the amount exceeds 5 parts by weight, hydrolysis occurs rapidly and the coating solution tends to gel.

The reaction temperature during the hydrolysis is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and is particularly preferably from 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. The reaction time during the hydrolysis is not particularly limited,
The reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited, but a method using a liquid chromatograph is simple and preferable.

As described above, the silica-based coating-type insulating film forming material of the first, second, and third inventions is applied on a substrate, the organic solvent is removed by drying, and the mixture is cured by heating at 300 ° C. or more. An insulating film is formed. Here, examples of the coating method include a spin coating method, a spraying method, and a dip coating method, and are not particularly limited. The drying temperature is not particularly limited, but is set at 100 ° C. to promote the evaporation of the organic solvent.
To 300 ° C. is preferred. The heat-curing temperature is not particularly limited to 300 ° C. or higher, but there is an upper limit depending on the substrate to be used. For example, 500 ° C. or lower is preferable for an aluminum wiring provided by an LSI or the like. The heating and curing time is not particularly limited, and the heating is terminated when the physical properties of the cured film have almost reached equilibrium. The determination method at this time is not particularly limited, but measurement of the surface hardness of the film, the thickness of the film, and the like is simple and preferable. The atmosphere at the time of heat curing is not particularly limited, but an inert gas such as nitrogen or argon may be introduced to reduce the elimination of the alkyl group in the component (b) or (e) during heating. preferable.

 A fourth description will be described.

(A) an alkoxysilane used in the fourth invention,
(E) alkylalkoxysilane and / or (b) fluorine-containing alkoxysilane, (c) alkoxide of metal other than Si and / or derivative thereof, (d) organic solvent,
(F) Water and catalyst are the same as described above.

The amount of water to be added is preferably less than 75% with respect to 100% of each alkoxy group of alkoxysilane, alkylalkoxysilane and / or fluorine-containing alkoxysilane. If it is 75% or more, alkoxysilane, alkylalkoxysilane and / or The hydrolysis of the alkoxysilane containing fluorine rapidly occurs, so that the coating solution gels or becomes cloudy. The amount of the catalyst to be added is preferably 0.1 to 5 parts by weight based on 100 parts by weight of alkoxysilane, alkylalkoxysilane and / or fluorine-containing alkoxysilane, and if less than 0.1 part by weight, alkoxysilane, alkylalkoxysilane A film is not formed at the time of application because of insufficient hydrolysis of the alkoxysilane containing fluorine and / or fluorine. If the amount is more than 5 parts by weight, hydrolysis occurs rapidly and the coating solution gels. The reaction temperature during the hydrolysis is not particularly limited,
The boiling point of the organic solvent used is preferably lower than or equal to 5 ° C. to 70 ° C. in order to control the molecular weight of the obtained hydrolyzate.
Is preferred. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

(A) alkoxysilane, (e) alkylalkoxysilane and / or (b) fluorine-containing alkoxysilane, (c) alkoxide of metal other than Si and / or derivative thereof, (d) organic solvent, (f) A) A silica-based coating-type insulating film forming material obtained from water and a catalyst is produced as follows. First, a predetermined amount of alkylalkoxysilane and / or fluorine-containing alkoxysilane is dispersed in an organic solvent, mixed with water and a catalyst, stirred for a while, and then an alkoxide of a metal other than Si and / or a derivative thereof is added. Let it be added. The mixture is further stirred for a while to advance the reaction, and then alkoxysilane is added thereto, mixed well, and then water and / or a catalyst are added, and the mixture is made to have a high molecular weight at room temperature or under heating. .

Here, the total amount of the component (a) and the components (e) and / or (b) is from 1 part by weight to 4 parts by weight based on 100 parts by weight of the organic solvent (d).
A range of 0 parts by weight is preferred. (A) component and (e) and / or
Alternatively, if the total amount of component (b) is less than 1 part by weight, it is difficult to form a film during coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. The amount of component (e) and / or component (b) added is preferably from 0.1 mol to 10 mol per 1 mol of component (a). (E) and / or (b) component added amount is 0.1
If the amount is less than 10 mol, cracks are liable to be generated during the heat curing after application, and if the amount exceeds 10 mol, it is difficult to obtain a uniform film.
The addition amount of the component (c) is preferably in the range of 0.01 mol to 1 mol based on 1 mol of the total amount of the component (a) and the components (e) and / or (b). When the amount of the component (c) is less than 0.01 mol, the film is hardly formed at the time of coating because the high molecular weight is insufficient, and when it exceeds 1 mol, the high molecular weight is rapidly generated and the coating liquid easily gels. Become.

The reaction temperature at the time of increasing the molecular weight is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

The silica-based insulating film is formed by applying the thus-prepared material for forming a silica-based coating-type insulating film on a substrate, removing the organic solvent by drying, and heating and curing at 300 ° C. or higher. Here, examples of the coating method include a spin coating method, a spraying method, and a dip coating method, and are not particularly limited. The drying temperature is not particularly limited, but is preferably in the range of 100 ° C to 300 ° C in order to promote the evaporation of the organic solvent. The heat curing temperature is not particularly limited at 300 ° C. or higher, but there is an upper limit depending on the substrate to be used, for example, 500 mm for an aluminum wiring with an LSI or the like.
C. or less is preferred. The heating and curing time is not particularly limited, and the heating is terminated when the physical properties of the cured film have almost reached equilibrium. The determination method at this time is not particularly limited, but measurement of the surface hardness of the film, the thickness of the film, and the like is simple and preferable. The atmosphere during the heat curing is not particularly limited, but an inert gas such as nitrogen or argon is introduced to reduce the elimination of the alkyl group in the component (e) and / or (b) during the heating. Is preferred.

 The fifth invention will be described.

(E) alkylalkoxysilane and / or (b) fluorine-containing alkoxysilane, (c) alkoxide of a metal other than Si and / or a derivative thereof, (d) organic solvent, f) Water and catalyst are as described above.

The amount of water to be added is preferably less than 75% with respect to 100% of the alkoxy group of each of the alkylalkoxysilane and / or the fluorine-containing alkoxysilane.
Above, the hydrolysis of the alkylalkoxysilane and / or the alkoxysilane containing fluorine rapidly occurs, so that the coating solution gels or becomes cloudy. The addition amount of the catalyst is preferably from 0.1 to 5 parts by weight based on 100 parts by weight of the alkylalkoxysilane and / or the fluorine-containing alkoxysilane, and if less than 0.1 part by weight, the alkylalkoxysilane and / or fluorine is contained. A film is not formed at the time of coating due to insufficient hydrolysis of the alkoxysilane to be formed. If the amount is more than 5 parts by weight, hydrolysis occurs rapidly and the coating solution gels. The reaction temperature during the hydrolysis is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably from 5 ° C to 70 ° C for controlling the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited, but a method using a liquid chromatograph is simple and preferable.

(E) alkylalkoxysilanes and / or (b) fluorine-containing alkoxysilanes, (c) alkoxides of metals other than Si and / or derivatives thereof, (d)
The silica-based coating-type insulating film forming material obtained from the organic solvent, (f) water and the catalyst is produced as follows. First, a predetermined amount of alkylalkoxysilane and / or fluorine-containing alkoxysilane is dispersed in an organic solvent, water and a catalyst are mixed therein, and the mixture is stirred for a while. Then, an alkoxide of a metal other than Si and / or a derivative thereof is further added. Is added, and the molecular weight is increased at room temperature or under heating.

Here, the component (e) and / or the component (b) is preferably in the range of 1 part by weight to 40 parts by weight based on 100 parts by weight of the organic solvent (d). If the amount of component (e) and / or (b) is less than 1 part by weight, it is difficult to form a film at the time of coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. Component (c) is added in an amount of 0.1 to 1 mole of component (e) and / or (b).
A range from 01 mole to 1 mole is preferred. When the amount of the component (c) is less than 0.01 mol, the film is hardly formed at the time of coating because the high molecular weight is insufficient, and when it exceeds 1 mol, the high molecular weight is rapidly generated and the coating liquid easily gels. Become.

The reaction temperature at the time of increasing the molecular weight is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

A silica-based insulating film is formed by applying the silica-based coating-type insulating film forming material manufactured by the above method on a substrate, removing the organic solvent by drying, and heating and curing at 300 ° C. or higher. Here, examples of the coating method include a spin coating method, a spraying method, and a dip coating method, and are not particularly limited. The drying temperature is not particularly limited, but is preferably in the range of 100 ° C to 300 ° C in order to promote the evaporation of the organic solvent. The heat curing temperature is not particularly limited at 300 ° C. or higher, but there is an upper limit depending on the substrate to be used, for example, 500 mm for an aluminum wiring with an LSI or the like.
C. or less is preferred. The heating and curing time is not particularly limited, and the heating is terminated when the physical properties of the cured film have almost reached equilibrium. The determination method at this time is not particularly limited, but measurement of the surface hardness of the film, the thickness of the film, and the like is simple and preferable. The atmosphere at the time of heat curing is not particularly limited, but an inert gas such as nitrogen or argon is introduced to reduce the elimination of the alkyl group of component (e) and / or (b) during heating. Is preferred.

The sixth invention of the present application provides (a) an alkoxysilane and / or
Or (e) an alkylalkoxysilane and / or (b) a fluorine-containing alkoxysilane, (c) an alkoxide of a metal other than Si and / or a derivative thereof, (d) an organic solvent, (g) A silica-based coating-type thin film forming material obtained from a photoacid generator and a method for producing the same.

(A) an alkoxysilane and / or a partial hydrolyzate thereof, (e) an alkylalkoxysilane and / or (b) a fluorine-containing alkoxysilane, and (c) a metal other than Si used in the sixth invention. The alkoxide and / or derivative thereof and (d) the organic solvent are the same as those described above.

Examples of the photoacid generator (g) include diphenyliodonium salts such as diphenyliodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl).
Bis (4-t-butylphenyl) iodonium salts such as iodonium hexafluoroantimonate; triphenylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate; and 2,4,6-tris (trichloromethyl) -1,3,5 Triazines such as triazine; sulfonic acid esters such as benzoin tosylate; and the like, each of which can be used alone or in combination of two or more.

These (a), (e) and / or (b), (c),
The material for forming a silica-based coating type thin film obtained from the components (d) and (g) is obtained by mixing an alkoxysilane and an alkylalkoxysilane and / or a fluorine-containing alkoxysilane in an organic solvent, and then mixing a metal other than Si. It is produced by adding an alkoxide and / or a derivative thereof, and adding a photoacid generator to a polymer having a high molecular weight at room temperature or under heating.

Here, water and an organic acid can be added to promote the increase in the molecular weight. Further, water and a catalyst are added to the alkoxysilane in an organic solvent to synthesize a partial hydrolyzate thereof in advance, and the resultant is mixed with an alkylalkoxysilane and / or a fluorine-containing alkoxysilane, and then mixed with an alkoxide of a metal other than Si. And / or a derivative thereof may be added.

Here, the total amount of the component (a) and the components (e) and / or (b) is from 1 part by weight to 4 parts by weight based on 100 parts by weight of the organic solvent (d).
A range of 0 parts by weight is preferred. (A) component and (e) and / or
Alternatively, if the total amount of component (b) is less than 1 part by weight, it is difficult to form a film during coating, and if it exceeds 40 parts by weight, it is difficult to obtain a uniform film. The amount of component (e) and / or component (b) added is preferably from 0.1 mol to 10 mol per 1 mol of component (a). (E) and / or (b) component added amount is 0.1
If the amount is less than 10 mol, cracks are liable to be generated during the heat curing after application, and if the amount exceeds 10 mol, a uniform film is difficult to obtain.
The addition amount of the component (c) is preferably in the range of 0.01 mol to 0.5 mol based on 1 mol of the total amount of the component (a) and the components (e) and / or (b). When the amount of the component (c) is less than 0.1 mol, the film becomes difficult to be formed at the time of coating due to insufficient high molecular weight, and when the amount exceeds 0.5 mol, the high molecular weight is rapidly generated and the coating solution is easily gelled. Become. The amount of the component (g) added is preferably 0.1 mol% or more based on the total amount of the component (a) and the components (e) and / or (b). If the amount of the component (g) is less than 0.1 mol%, the patterning becomes insufficient because the amount of acid generated upon light irradiation is small.

The reaction temperature at the time of increasing the molecular weight is not particularly limited, but is preferably equal to or lower than the boiling point of the organic solvent used, and particularly preferably 5 ° C to 70 ° C in order to control the molecular weight of the obtained hydrolyzate. There is no particular limitation on the reaction time at the time of hydrolysis, and the reaction is terminated when a predetermined molecular weight is reached. The method for measuring the molecular weight at this time is not particularly limited,
A method using a liquid chromatograph is simple and preferred.

The material for forming a silica-based coating-type thin film formed by such a method is coated on a substrate, and after removing an organic solvent by drying, it is patterned by irradiating with light and developing by heating and curing. The resulting silica-based thin film is formed. Here, examples of the coating method include a spin coating method, a spraying method, and a dip coating method, and are not particularly limited. The drying temperature is not particularly limited, but is preferably 40 ° C. or higher in order to promote the evaporation of the organic solvent. As a light irradiation method, a contact method, a proximity method, a projection method, a reduced projection exposure method, or the like is used, and there is no particular limitation. The heat curing temperature after light irradiation is not particularly limited at 80 ° C. or higher, but there is an upper limit depending on the substrate used, for example, 100 ° C. for a plastic substrate such as polycarbonate.
The following is preferred. There is no particular limitation on the heat curing time,
The heating is stopped when the physical properties of the cured film have almost reached equilibrium. The determination method at this time is not particularly limited, but measurement of the surface hardness of the film, the thickness of the film, and the like is simple and preferable. The atmosphere during the heat curing is not particularly limited, but an inert gas such as nitrogen or argon is introduced to reduce the elimination of the alkyl group in the component (e) and / or (b) during the heating. Is preferred. Examples of the developing method, which are used for conventional resist materials, include an alkali developing method using an ammonium hydroxide-based aqueous solution, and a solvent developing method using an organic solvent such as alcohols and ketones.
There is no particular limitation. Further, in order to increase the degree of curing of the obtained thin film, heat treatment may be performed again after development.

FIG. 2 shows an example of a method for manufacturing a semiconductor device using the material for forming a silica-based coating type insulating film of the present invention.

In FIG. 2, reference numeral 21 denotes a semiconductor chip substrate on which circuit elements, which are elements constituting an electronic circuit such as a transistor, a diode, a resistor, and a capacitor, are formed. Reference numeral 22 denotes a first aluminum wiring formed on the semiconductor chip substrate. Reference numeral 23 denotes an SiO ₂ film formed by plasma CVD, and reference numeral 24 denotes an insulating film formed using the silica-based coating-type insulating film forming material of the present invention (FIG. 2A). An SiO ₂ film 25 is formed on the entire surface of the insulating film 24 of the present invention by plasma CVD, a predetermined etching resist 26 is formed (FIG. 2B), and an etching process by dry etching such as oxygen plasma is performed. The uncovered portion of the insulating film 24 is removed by etching to expose the first wiring 22, the etching resist is removed (FIG. 2C), the second aluminum wiring connected to the first wiring 22, and the like. Is formed (FIG. 2D) to manufacture a semiconductor device.

The SiO ₂ film 25 formed by plasma CVD on the entire surface of the insulating film 24 of the present invention can be omitted.

Further, the SiO ₂ film 23 formed on the surfaces of the semiconductor chip substrate 21 and the first wiring 22 by plasma CVD can be omitted.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view showing a method for manufacturing a semiconductor device using a conventional organic SOG film.

FIG. 2 is a cross-sectional view illustrating a method for manufacturing a semiconductor device using the insulating film of the present invention.

FIG. 3 is a graph showing the measurement results of the surface roughness of the patterned silica-based thin film prepared in Example 19.

BEST MODE FOR CARRYING OUT THE INVENTION Example 1 Into 345 g (7.5 mol) of ethyl alcohol, 152 g (1 mol) of tetramethoxysilane and 54.5 g (0.25 mol) of trifluoropropyltrimethoxysilane were thoroughly mixed, and then stirred. 42.5 g of tetrabutoxy titanium while continuing to cook
(0.125 mol) in 230 g (5 mol) of ethyl alcohol was added. Furthermore, while continuing stirring
By reacting for 24 hours, a silica-based coating-type insulating film forming material was produced. With respect to this insulating film forming material, the molecular weight distribution was measured using tetrahydrofuran as an eluent using an HPLC (high performance liquid chromatography) apparatus (manufactured by Hitachi, Model 6000), and the number average molecular weight in terms of polystyrene was calculated from the result ( Column used: Gelpack GL-R420 (trade name, manufactured by Hitachi Chemical Co., Ltd., flow rate: 1.75 ml / min).
640 was indicated. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
After applying for 20 seconds at 1,500 rpm with a spin coater on a silicon wafer with mirror-polished one side,
Drying for a minute removed the solvent. Next, by heating and curing at 400 ° C. for 30 minutes in a nitrogen atmosphere using a tubular firing furnace, a transparent and uniform silica-based insulating film was obtained. The thickness of this insulating film was measured using an automatic ellipsometer (manufactured by Mizojiri Optical Industrial Co., Ltd.) and found to be 537 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

For this silica-based insulating film, using a barrel-type isotropic plasma etching apparatus, oxygen: 1 Torr, output: 400 W, time: after performing oxygen plasma treatment under the conditions of 20 minutes, the thickness was measured 521 nm It was confirmed that the film thickness was reduced only by about 3% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Example 2 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, the mixture was cooled to room temperature, and trifluoropropyltrimethoxysilane 54.5 was added.
g (0.25 mol), mix well, and then add 42.5 g (0.125 mol) of tetrabutoxytitanium to 230 g of ethyl alcohol.
(5 mol) was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 2,910. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 597 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 573 nm,
It was recognized that the film thickness was reduced only by about 4% when exposed to oxygen plasma.

When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found. Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Example 3 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, it was cooled to room temperature, and then trifluoropropyltrimethoxysilane 109 g.
(0.5 mol) and mixed well, and then a solution of 45.5 g (0.125 mol) of titanium dipropoxybisacetylacetonate dissolved in 230 g (5 mol) of ethyl alcohol was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was found to be about 1,650. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 749 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 704 nm,
It was observed that the film thickness after exposure to oxygen plasma was reduced by only about 6%. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Example 4 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol and mixed well. Then, 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while stirring was continued.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, it was cooled to room temperature, and then trifluoropropyltrimethoxysilane 109 g.
(0.5 mol) and mixed well, and then a solution of 54.4 g (0.125 mol) of dibutoxybisacetylacetonatozirconium dissolved in 230 g (5 mol) of ethyl alcohol was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. Example 1 of this insulating film forming material
As a result of calculating the number average molecular weight in the same manner as in the above, it was found to be about 2,300. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 654 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 608 nm,
It was recognized that the film thickness was reduced only by about 7% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Example 5 152 g (1 mol) of tetramethoxysilane and methyltrimethoxysilane in 345 g (7.5 mol) of ethyl alcohol
After 136 g (1 mol) was added and mixed well, a solution of 42.5 g (0.125 mol) of tetrabutoxytitanium dissolved in 230 g (5 mol) of ethyl alcohol was added with continued stirring.
Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 3,260. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 622 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 585 nm, and the film thickness was reduced only by about 6% even when exposed to oxygen plasma. Was observed. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 6 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and while stirring, 2.45 g (0.025 mol) of maleic anhydride was added to distilled water.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, cool to room temperature, add 136 g (1 mol) of methyltrimethoxysilane, mix well, and further add 42.5 g of tetrabutoxytitanium.
(0.125 mol) in 230 g (5 mol) of ethyl alcohol was added. Furthermore, while continuing stirring
By reacting for 24 hours, a silica-based coating-type insulating film forming material was produced. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 3,190. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 639 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 594 nm,
It was recognized that the film thickness was reduced only by about 7% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 7 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, cool to room temperature, add 136 g (1 mol) of methyltrimethoxysilane, mix well, and further add 45.5 g (0.125 mol) of titanium dipropoxybisacetylacetonate to ethyl alcohol.
A solution dissolved in 230 g (5 mol) was added. further,
The reaction was carried out for 24 hours while continuing the stirring to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 1,180. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 570 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 532 nm,
It was recognized that the film thickness was reduced only by about 7% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 8 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, the mixture was cooled to room temperature, 136 g (1 mol) of methyltrimethoxysilane was added, mixed well, and 54.5 g (0.125 mol) of dibutoxybisacetylacetonatozirconium was added to 230 g of ethyl alcohol ( (5 mol) was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. As a result of calculating the number average molecular weight of this insulating film forming material in the same manner as in Example 1, it was found to be about 1,390. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 514 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 478 nm,
It was recognized that the film thickness was reduced only by about 7% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 9 152 g (1 mol) of tetramethoxysilane and 54.5 g (0.25 mol) of trifluoropropyltrimethoxysilane were added to 575 g (12.5 mol) of ethyl alcohol and mixed well. g (0.031 mol) in 85.5 g (4.75 mol) of distilled water was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 1,040. This material did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 537 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 516 nm, and the film thickness was reduced only by about 4% even when exposed to oxygen plasma. Admitted. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Example 10 152 g (1 mol) of tetramethoxysilane was added to 575 g (12.5 mol) of ethyl alcohol and mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, the mixture was cooled to room temperature, and trifluoropropyltrimethoxysilane 54.5 was added.
g (0.25 mol) was added and mixed well, and then an aqueous solution in which 0.59 g (0.006 mol) of maleic anhydride was dissolved in 13.5 g (0.75 mol) of distilled water was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 1,880. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 538 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 511 nm,
It was recognized that the film thickness was reduced only by about 5% when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Comparative Example 1 152 g (1 mol) of tetramethoxysilane and methyltrimethoxysilane in 575 g (12.5 mol) of ethyl alcohol
After 136 g (1 mol) was added and mixed well, an aqueous solution in which 4.9 g (0.05 mol) of maleic anhydride was dissolved in 126 g (7 mol) of distilled water was added while stirring was continued. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this insulating film forming material was calculated in the same manner as in Example 1, and as a result, it was about 780. This insulating film forming material is
Even if left at room temperature for one month, no gelation or the like occurred.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 1, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 489 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 391 nm,
The film thickness is about 20 when exposed to oxygen plasma.
% Was also found to decrease. In addition, as a result of observing the surface of the insulating film using an optical microscope, it was confirmed that many cracks were generated over the entire surface.

Also, as a result of measuring the IR spectrum of this insulating film, 40
No absorption peak attributed to the alkyl group (methyl group) observed after baking at 0 ° C. was observed at all after the oxygen plasma treatment, indicating that the alkyl group was desorbed by oxygen plasma.

Comparative Example 2 152 g (1 mol) of tetramethoxysilane was added to 575 g (12.5 mol) of ethyl alcohol and mixed well. Then, while stirring, 2.45 g (0.025 mol) of maleic anhydride was added to distilled water.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, cooling to room temperature, 136 g (1 mol) of methyltrimethoxysilane was added and mixed well, and then maleic anhydride 2.
An aqueous solution in which 45 g (0.025 mol) was dissolved in 54 g (3 mol) of distilled water was added. Further, the mixture was reacted for 24 hours while continuing to stir to prepare a silica-based coating-type insulating film forming material. As a result of calculating the number average molecular weight of this insulating film forming material in the same manner as in Example 1, about 980 was obtained.
showed that. The material for forming an insulating film did not cause gelation even when left at room temperature for one month. Using 1.5 ml of this silica-based coating-type insulating film forming material, a transparent and uniform silica-based insulating film was obtained on a silicon wafer whose one surface was mirror-polished in the same manner as in Example 1. The thickness of this insulating film is 48
It was 9 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 1, the film thickness was 395 nm,
The film thickness is about 20 when exposed to oxygen plasma.
% Was also found to decrease. In addition, as a result of observing the surface of the insulating film using an optical microscope, it was confirmed that many cracks were generated over the entire surface.

Also, as a result of measuring the IR spectrum of this insulating film, 40
No absorption peak attributed to the alkyl group (methyl group) observed after sintering at 0 ° C. was observed at all after the oxygen plasma treatment, indicating that the alkyl group was desorbed by the oxygen plasma.

Example 11 136.0 g (1 mol) of methyltrimethoxysilane was added to 460.0 g (10 mol) of ethyl alcohol, mixed well, and 1.6 g of nitric acid (0.025 mol) was added to 27.0 g of distilled water while stirring was continued.
(1.5 mol), and the mixture was reacted at room temperature for 2 hours. Further, 170.0 g (0.5 mol) of tetrabutoxytitanium was converted to 460.0 g (10
Mol) and stirred for 2 hours, and then 304.0 g (2 mol) of tetramethoxysilane and 460.
0 g (10 mol) was added and mixed well.
An aqueous solution prepared by dissolving 5 mol) in 72.0 g (4 mol) of distilled water was added thereto, and the mixture was reacted for 24 hours while stirring to prepare a silica-based coating-type insulating film forming material. With respect to this insulating film forming material, the molecular weight distribution was measured using tetrahydrofuran as an eluent using an HPLC (high performance liquid chromatography) apparatus (manufactured by Hitachi, Model 6000), and the number average molecular weight in terms of polystyrene was calculated from the result ( Column: Gelpack GL-R42 (trade name, manufactured by Hitachi Chemical Co., Ltd.)
0, flow rate: 1.75 ml / min) As a result, about 2,140 was shown. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
The solution was applied on a silicon wafer having a mirror-polished surface on one side at 2,000 rpm for 20 seconds by a spin coater, and then dried on a hot plate at 150 ° C. for 30 seconds and on a hot plate at 250 ° C. for 30 seconds to remove the solvent. Next, by heating and curing at 430 ° C. for 30 minutes in a nitrogen atmosphere using a tubular firing furnace, a transparent and uniform silica-based insulating film was obtained. Optical interference film thickness meter (trade name: Lambda Ace, manufactured by Dainippon Screen Mfg. Co., Ltd.)
Was used to measure the thickness of this insulating film, and as a result, it was 279 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

About this silica-based insulating film, using a barrel-type isotropic plasma etching apparatus, oxygen: 1 Torr, output: 400 W, time: after performing oxygen plasma treatment under the conditions of 20 minutes, the thickness was measured 272 nm It was confirmed that the film thickness was reduced by only about 2% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 12 136.0 g (1 mol) of methyltrimethoxysilane was added to 460.0 g (10 mol) of ethyl alcohol, mixed well, and 1.6 g of nitric acid (0.025 mol) was added to 27.0 g of distilled water while stirring was continued.
(1.5 mol), and the mixture was reacted at room temperature for 2 hours. Further, a solution prepared by dissolving 182.0 g (0.5 mol) of titanium dipropoxybisacetylacetonate in 460.0 g (10 mol) of ethyl alcohol was added and stirred for 2 hours. Then, 304.0 g (2 mol) of tetramethoxysilane and 460.0 g of ethanol were added. g (10 mol) was added and mixed well, and an aqueous solution in which 3.2 g (0.05 mol) of nitric acid was dissolved in 72.0 g (4 mol) of distilled water was added thereto.
By reacting for hours, a silica-based coating-type insulating film forming material was produced. As a result of calculating the number average molecular weight of this insulating film forming material in the same manner as in Example 11, approximately 1,430
showed that. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 11, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 246 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 11, the film thickness was 234 nm,
It was recognized that the film thickness was reduced only by about 5% when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 13 216.0 g (1 mol) of trifluoropropyltrimethoxysilane was added to 460.0 g (10 mol) of ethyl alcohol, mixed well, and then 1.6 g (0.025 mol) of nitric acid while stirring was continued.
Was dissolved in 27.0 g (1.5 mol) of distilled water, and the mixture was allowed to react at room temperature for 2 hours. Further, a solution prepared by dissolving 170.0 g (0.5 mol) of tetrabutoxytitanium in 460.0 g (10 mol) of ethyl alcohol was added and stirred for 2 hours. Then, 304.0 g (2 mol) of tetramethoxysilane and 460.0 g (10 mol) of ethanol were added. ) Was added and mixed well, and an aqueous solution in which 3.2 g (0.05 mol) of nitric acid was dissolved in 72.0 g (4 mol) of distilled water was added. A material for forming an insulating film was manufactured. The number average molecular weight of this insulating film forming material was calculated to be about 1,520 in the same manner as in Example 11.
The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 11, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 259 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 11, the film thickness showed 246 nm,
It was recognized that the film thickness was reduced only by about 5% when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Comparative Example 3 136.0 g (1 mol) of methyltrimethoxysilane was added to 920.0 g (20 mol) of ethyl alcohol, mixed well, and 1.6 g (0.025 mol) of nitric acid was added to 27.0 g of distilled water while stirring was continued.
(1.5 mol), and the mixture was reacted at room temperature for 2 hours. Furthermore, 304.0 g (2 mol) of tetramethoxysilane and 460.0 g (10 mol) of ethanol
Is added and mixed well, and an aqueous solution in which 3.2 g (0.05 mol) of nitric acid is dissolved in 72.0 g (4 mol) of distilled water is added thereto. The mixture is allowed to react for 24 hours with continuous stirring, so that the silica-based coating type insulation is obtained. A film forming material was prepared. The number average molecular weight of this insulating film forming material was calculated to be about 780 in the same manner as in Example 11. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 11, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 259 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of performing the oxygen plasma treatment on the silica-based insulating film in the same manner as in Example 11, the thickness thereof was 195 nm,
The film thickness is about 24 when exposed to oxygen plasma.
% Was also found to decrease. In addition, as a result of observing the surface of the insulating film using an optical microscope, it was confirmed that many cracks were generated over the entire surface.

In addition, as a result of measuring the IR spectrum of this insulating film, 43
No absorption peak attributed to the alkyl group (methyl group) observed after baking at 0 ° C. was observed at all after the oxygen plasma treatment, indicating that the alkyl group was desorbed by oxygen plasma.

Example 14 408.0 g (3 mol) of methyltrimethoxysilane was added to 920.0 g (20 mol) of ethyl alcohol, mixed well, and 4.7 g of nitric acid (0.075 mol) was added to 81.0 g of distilled water while stirring was continued.
(4.5 mol), and the mixture was reacted at room temperature for 2 hours. Further, 170.0 g (0.5 mol) of tetrabutoxytitanium was converted to 460.0 g (10
Mol) is added, and stirring is continued for 24 hours.
By reacting for hours, a silica-based coating-type insulating film forming material was produced. About this insulating film forming material,
Using tetrahydrofuran as an eluent, the molecular weight distribution was measured using an HPLC (high performance liquid chromatography) apparatus (Hitachi, model 6000), and the number average molecular weight in terms of polystyrene was calculated from the results (column used: Hitachi Chemical Co., Ltd.) ) Product name Gelpack GL-R420, flow rate: 1.75ml / min)
550 was shown. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
The solution was applied on a silicon wafer having a mirror-polished surface on one side at 2,000 rpm for 20 seconds by a spin coater, and then dried on a hot plate at 150 ° C. for 30 seconds and on a hot plate at 250 ° C. for 30 seconds to remove the solvent. Next, by heating and curing at 430 ° C. for 30 minutes in a nitrogen atmosphere using a tubular firing furnace, a transparent and uniform silica-based insulating film was obtained. Optical interference film thickness meter (trade name: Lambda Ace, manufactured by Dainippon Screen Mfg. Co., Ltd.)
As a result of measuring the film thickness of this insulating film using, it was 305 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

For this silica-based insulating film, using a barrel-type isotropic plasma etching apparatus, after performing oxygen plasma treatment under the conditions of oxygen: 1 Torr, output: 400 W, time: 20 minutes, and measured the film thickness 292 nm It was confirmed that the film thickness was reduced only by about 4% even when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 15 408.0 g (3 mol) of methyltrimethoxysilane was added to 920.0 g (20 mol) of ethyl alcohol, mixed well, and 4.7 g of nitric acid (0.075 mol) was added to 81.0 g of distilled water while stirring was continued.
(4.5 mol), and the mixture was reacted at room temperature for 2 hours. Further, a solution prepared by dissolving 182.0 g (0.5 mol) of titanium dipropoxybisacetylacetonate in 460.0 g (10 mol) of ethyl alcohol was added, and the mixture was reacted for 24 hours while stirring was continued.
A silica-based coating type insulating film forming material was prepared. Example 14
The number average molecular weight of this insulating film forming material was calculated in the same manner as in the above. As a result, it was found to be about 1,520. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 14, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 292 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting the silica-based insulating film to oxygen plasma treatment in the same manner as in Example 14, the film thickness was 281 nm,
It was recognized that the film thickness was reduced only by about 4% when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (methyl group) was observed even after the oxygen plasma treatment, indicating that the oxygen plasma resistance was good.

Example 16 648.0 g (3 mol) of trifluoropropyltrimethoxysilane was added to 920.0 g (20 mol) of ethyl alcohol, mixed well, and then, while stirring, 4.7 g (0.075 mol) of nitric acid was continued.
Was dissolved in 81.0 g (4.5 mol) of distilled water, and the mixture was allowed to react at room temperature for 2 hours. Further, a solution prepared by dissolving 170.0 g (0.5 mol) of tetrabutoxytitanium in 460.0 g (10 mol) of ethyl alcohol was added, and the mixture was reacted for 24 hours while stirring to obtain a silica-based coating type insulating film forming material. Produced. The number average molecular weight of this insulating film forming material was calculated to be about 1,230 in the same manner as in Example 14. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 14, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 303 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting this silica-based insulating film to oxygen plasma treatment in the same manner as in Example 14, the film thickness was 292 nm,
It was recognized that the film thickness was reduced only by about 4% when exposed to oxygen plasma. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Further, as a result of measuring the IR spectrum of this insulating film, an absorption peak attributed to an alkyl group (trifluoropropyl group) was observed even after the oxygen plasma treatment, and it was found that the oxygen plasma resistance was good.

Comparative Example 4 136.0 g (1 mol) of methyltrimethoxysilane was added to 920.0 g (20 mol) of ethyl alcohol, mixed well, and 1.6 g (0.025 mol) of nitric acid was added to 27.0 g of distilled water while stirring was continued.
(1.5 mol) was added, and the mixture was reacted at room temperature for 2 hours to prepare a silica-based coating-type insulating film forming material. The number average molecular weight of this material for forming a membrane was calculated in the same manner as in Example 14, and as a result, it was found to be about 880. The material for forming an insulating film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating type insulating film forming material,
In the same manner as in Example 14, a transparent and uniform silica-based insulating film was obtained on a silicon wafer having one surface subjected to mirror polishing. The thickness of this insulating film was 206 nm. When the surface of the insulating film was observed using an optical microscope, no defects such as cracks and pinholes were found.

As a result of subjecting the silica-based insulating film to oxygen plasma treatment in the same manner as in Example 14, the film thickness was 129 nm,
Exposure to oxygen plasma results in a film thickness of about 37
% Was also found to decrease. In addition, as a result of observing the surface of the insulating film using an optical microscope, it was confirmed that many cracks were generated over the entire surface.

In addition, as a result of measuring the IR spectrum of this insulating film, 43
No absorption peak attributed to the alkyl group (methyl group) observed after baking at 0 ° C. was observed at all after the oxygen plasma treatment, indicating that the alkyl group was desorbed by oxygen plasma.

Example 17 152 g (1 mol) of tetramethoxysilane and methyltrimethoxysilane in 345 g (7.5 mol) of ethyl alcohol
After 136 g (1 mol) was added and mixed well, a solution of 42.5 g (0.125 mol) of tetrabutoxytitanium dissolved in 230 g (5 mol) of ethyl alcohol was added with continued stirring.
Further, after reaction for 24 hours while continuing stirring, 16.5 g of triphenylsulfonium trifluoromethanesulfonate
(0.04 mol) and completely dissolved,
A silica-based coating type thin film forming material was prepared. For this insulating film forming material, an HPLC (high performance liquid chromatography) device (Hitachi,
The molecular weight distribution was measured using 6000 type), and the number average molecular weight in terms of polystyrene was calculated from the results (column used: Gelpack GL-R420, manufactured by Hitachi Chemical Co., Ltd., flow rate: 1.75 ml / min). , About 3,260. The material for forming a thin film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating-type thin film forming material, it was applied on a mirror-polished silicon wafer on one side at 3,000 rpm for 30 seconds by a spin coater, and then dried on an 80 ° C hot plate for 1 minute to remove the solvent. did. A metal mask (stainless steel plate punched out in a stripe pattern) was placed on this silicon wafer, irradiated with light from a low-pressure mercury lamp (strongest wavelength: 254 nm) for 10 minutes, and then heated and cured on a hot plate at 120 ° C. for 2 minutes. . This was developed in a methyl isobutyl ketone solution for 2 minutes, and then washed with cyclohexane, whereby a silica-based thin film having a pattern matching the pattern of the metal mask was formed on the silicon wafer. When the surface of this thin film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Example 18 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and while stirring, 2.45 g (0.025 mol) of maleic anhydride was added to distilled water.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, cool to room temperature, add 136 g (1 mol) of methyltrimethoxysilane, mix well, and further add 42.5 g of tetrabutoxytitanium.
(0.125 mol) in 230 g (5 mol) of ethyl alcohol was added. Furthermore, while continuing stirring
After reacting for 24 hours, 16.5 g (0.04 mol) of triphenylsulfonium trifluoromethanesulfonate was added and completely dissolved to prepare a silica-based coating-type thin film forming material. Examples of this thin film film forming material
As a result of calculating the number average molecular weight in the same manner as 17, about 3,190
showed that. The material for forming a thin film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating-type thin film-forming material, a silica-based thin film patterned on a silicon wafer having one surface mirror-polished in the same manner as in Example 17 was obtained. Also,
When the surface of this thin film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Example 19 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, cool to room temperature, add 136 g (1 mol) of methyltrimethoxysilane, mix well, and further add 45.5 g (0.125 mol) of dipropoxybisacetylacetonate to 230 g of ethyl alcohol.
(5 mol) was added. Furthermore, after reaction for 24 hours while stirring, 16.5 g (0.04 mol) of triphenylsulfonium trifluoromethanesulfonate
Was added and completely dissolved to prepare a silica-based coating-type thin film forming material. The number average molecular weight of this thin film forming material was calculated in the same manner as in Example 17, and as a result, it was found to be about 1,180. The material for forming a thin film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating-type thin film-forming material, a silica-based thin film patterned on a silicon wafer having one surface mirror-polished in the same manner as in Example 17 was obtained. When the surface of this thin film was observed using an optical microscope, no defects such as cracks and pinholes were found. FIG. 3 shows the results of the surface roughness of this silica-based thin film measured by a contact type step meter. From these results, it was confirmed that the thickness of the obtained silica-based thin film was about 400 nm, and a pattern corresponding to the metal mask was formed on this surface.

Example 20 152 g (1 mol) of tetramethoxysilane was added to 345 g (7.5 mol) of ethyl alcohol, mixed well, and 2.45 g (0.025 mol) of maleic anhydride was added to distilled water while continuing to stir.
An aqueous solution dissolved in 72 g (4 mol) was added, and the temperature was raised to 60 ° C. After heating at 60 ° C. for 1 hour, it was cooled to room temperature, and then trifluoropropyltrimethoxysilane 109 g.
(0.5 mol) and mixed well, and then a solution of 54.5 g (0.125 mol) of dipropoxybisacetylacetonate dissolved in 230 g (5 mol) of ethyl alcohol was added. After 24 hours of reaction with continuous stirring, triphenylsulfonium trifluoromethanesulfonate 1
6.5 g (0.04 mol) was added and completely dissolved to prepare a silica-based coating-type thin film forming material. The number average molecular weight of this thin film forming material was calculated in the same manner as in Example 17, and as a result, it was found to be about 1,650. The material for forming a thin film did not cause gelation even when left at room temperature for one month.

Using 1.5 ml of this silica-based coating-type thin film-forming material, a silica-based thin film patterned on a silicon wafer having one surface mirror-polished in the same manner as in Example 17 was obtained. When the surface of this thin film was observed using an optical microscope, no defects such as cracks and pinholes were found.

Comparative Example 5 152 g (1 mol) of tetramethoxysilane and methyltrimethoxysilane in 575 g (12.5 mol) of ethyl alcohol
After 136 g (1 mol) was added and mixed well, an aqueous solution in which 4.9 g (0.05 mol) of maleic anhydride was dissolved in 126 g (7 mol) of distilled water was added while stirring was continued. Furthermore, the reaction was carried out for 24 hours while continuing to stir to prepare a silica-based coating-type thin film forming material. The number average molecular weight of this thin film forming material was calculated in the same manner as in Example 17, and as a result, it was found to be about 780. The molecular weight of the material for forming a thin film gradually increased by being left at room temperature, and a precipitate began to be generated in about one month.

Using 1.5 ml of this silica-based coating-type thin film forming material, a silica-based thin film was formed on a silicon wafer whose one surface was mirror-polished in the same manner as in Example 17. As a result of observing the surface of this thin film using an optical microscope, no defects such as cracks and pinholes were found, but no pattern corresponding to the metal mask was found at all. Even from the results of measuring the surface roughness with the step gauge, no irregularities corresponding to the metal mask were found at all.

The silica-based coating-type insulating film forming materials of the first to fifth aspects of the present invention have storage stability and can easily form a thick film by spin coating or the like. Further, the silica-based insulating film formed using the material for forming a silica-based coating-type insulating film is a transparent and uniform film, and has no defects such as cracks and pinholes. Furthermore, the thickness of this insulating film does not decrease so much even when subjected to the oxygen plasma treatment.
In addition, since defects such as cracks and pinholes do not appear on the surface, and little change is found in the components of the film, it is recognized that the film has excellent oxygen plasma resistance.

The silica-based coating-type thin film forming material according to the sixth aspect of the present invention has storage stability and can easily form a thick film by spin coating or the like. In addition, the silica-based thin film produced using the silica-based coating-type thin film-forming material is a transparent and uniform film, and has no defects such as cracks and pinholes. Further, when a thin film is manufactured, patterning is possible by irradiating light.

Claims (15)

(57) [Claims] 1. An alkoxysilane and / or a partial hydrolyzate thereof, (b) a fluorine-containing alkoxysilane, (c) an alkoxide of Ti and / or a derivative thereof, and an alkoxide of Zr and / or a derivative thereof. (D) an organic solvent; and a silica-based coating-type insulating film forming material. 2. Mixing of alkoxysilane and fluorine-containing alkoxysilane in an organic solvent, and then adding at least one of Ti alkoxide and / or derivative thereof and Zr alkoxide and / or derivative thereof. The method for producing a silica-based coating-type insulating film forming material according to claim 1. 3. A partial hydrolyzate of an alkoxysilane is synthesized in an organic solvent, mixed with a fluorine-containing alkoxysilane, and mixed with a Ti alkoxide and / or a derivative thereof and a Zr alkoxide and / or a derivative thereof. The method for producing a material for forming a silica-based coating type insulating film according to claim 1, wherein at least one of the following is added. (4) at least one of (a) an alkoxysilane and / or a partial hydrolyzate thereof, (e) an alkylalkoxysilane, (c) an alkoxide of Ti and / or a derivative thereof, and an alkoxide of Zr and / or a derivative thereof. (D) An organic solvent, wherein the material is a silica-based coating-type insulating film-forming material. 5. A method of mixing an alkoxysilane and an alkylalkoxysilane in an organic solvent, and then adding at least one of a Ti alkoxide and / or a derivative thereof and a Zr alkoxide and / or a derivative thereof. A method for producing the silica-based coating type insulating film forming material according to claim 4. 6. A partial hydrolyzate of an alkoxysilane is synthesized in an organic solvent, and after mixing with an alkylalkoxysilane, at least an alkoxide of Ti and / or a derivative thereof and an alkoxide of Zr and / or a derivative thereof are mixed. 5. The method for producing a silica-based coating type insulating film forming material according to claim 4, wherein any one of them is added. 7. (a) alkoxysilane, (e) alkylalkoxysilane and / or (b) fluorine-containing alkoxysilane, (c) alkoxide of Ti and / or derivative thereof, alkoxide of Zr and / or Or (d) an organic solvent; (f) water and a catalyst; and a method for producing a silica-based coating-type insulating film forming material, comprising: After mixing the alkylalkoxysilane and / or alkoxysilane containing fluorine with water and the catalyst,
A silica-based coating type insulating film characterized by adding at least one of an alkoxide of Ti and / or a derivative thereof and an alkoxide of Zr and / or a derivative thereof, further mixing an alkoxysilane, and then adding water and a catalyst. Manufacturing method of forming material. 8. At least one of (e) an alkylalkoxysilane and / or (b) a fluorine-containing alkoxysilane, (c) an alkoxide of Ti and / or a derivative thereof, and an alkoxide of Zr and / or a derivative thereof. And (d) an organic solvent; and (f) water and a catalyst. 9. After mixing an alkylalkoxysilane and / or a fluorine-containing alkoxysilane with water and a catalyst in an organic solvent, at least one of an alkoxide of Ti and / or a derivative thereof and an alkoxide of Zr and / or a derivative thereof is mixed. 9. The method for producing a silica-based coating type insulating film forming material according to claim 8, wherein any one of them is added. 10. An alkoxysilane and / or a partial hydrolyzate thereof, (e) an alkylalkoxysilane and / or (b) an alkoxysilane containing fluorine, and (c) an alkoxide of Ti and / or A derivative, at least one of an alkoxide of Zr and / or a derivative thereof, (d) an organic solvent, and (g) a photoacid generator. . 11. After mixing an alkoxysilane and an alkylalkoxysilane and / or a fluorine-containing alkoxysilane in an organic solvent, at least one of a Ti alkoxide and / or a derivative thereof and a Zr alkoxide and / or a derivative thereof. 11. The method for producing a silica-based coating-type insulating film forming material according to claim 10, further comprising adding a photoacid generator. 12. A partial hydrolyzate of alkoxysilane is synthesized in an organic solvent, and mixed with alkylalkoxysilane and / or alkoxysilane containing fluorine.
11. The silica-based coating-type insulation according to claim 10, wherein at least one of a Ti alkoxide and / or a derivative thereof and a Zr alkoxide and / or a derivative thereof is added, and a photoacid generator is further added. Manufacturing method of film forming material. 13. The material for forming a silica-based coating type insulating film according to any one of claims 1, 4, 8, and 10, or
13. A silica-based insulating material obtained by applying a silica-based coating-type insulating film forming material produced by the method according to any one of 3, 5, 6, 7, 9, 11, and 12 onto a substrate, drying, and heat-curing. film. 14. A semiconductor chip substrate on which a circuit element is formed, a first wiring formed on the semiconductor chip substrate, and the material for forming a silica-based coating type insulating film according to claim 1, 4, 8 or 10. A semiconductor device having a silica-based insulating film obtained by applying, drying, and heat-curing a substrate, and a second wiring connected to the first wiring. 15. A first wiring is formed on a semiconductor chip substrate on which a circuit element is formed, and the material for forming a silica-based coating-type insulating film according to claim 1, 4, 8, or 10 is coated on the substrate. Drying, heating and curing to form a silica-based insulating film, forming a predetermined etching resist, performing an etching treatment to expose a portion of the first wiring not covered with the etching resist, and removing the etching resist. A method for manufacturing a semiconductor device, comprising: forming a second wiring connected to a first wiring.