KR101316200B1 - Silicon-Containing Film-Forming Composition, Silicon-Containing Film, Silicon-Containing Film-Bearing Substrate, and Patterning Method - Google Patents

Abstract

The present invention is a silicon-containing compound obtained by hydrolytically condensing a hydrolyzable silicon compound using (A) acid as a catalyst,

(B) a compound represented by the following formula (1) or (2),

≪ Formula 1 >

L _a H _b X

(L is Li, Na, K, Rb or Ce, X is a hydroxyl group or an organic acid group, a is at least 1, b is 0 or at least 1)

(2)

M _a H _b A

(M is sulfonium, iodonium or ammonium and A is the X or non-nucleophilic counter ion)

(C) organic acid,

(D) an alcohol having a cyclic ether as a substituent,

(E) Organic solvents

It provides a composition for forming a thermosetting silicon-containing film comprising a.

By using the silicon-containing intermediate film formed from the composition for thermosetting silicon-containing film formation of this invention, favorable pattern formation is possible. In addition, the photoresist pattern can be transferred, and the substrate can be processed with high precision.

Silicon-containing compound, silicon-containing film, resist pattern

Description

Silicon-containing film forming composition, silicon-containing film, silicon-containing film forming substrate and pattern forming method using same {Silicon-Containing Film-Forming Composition, Silicon-Containing Film, Silicon-Containing Film-Bearing Substrate, and Patterning Method}

The present invention is a silicon-containing film used as an intermediate layer of a multilayer resist method used for microfabrication in manufacturing processes of semiconductor devices and the like, in particular, a silicon-containing film-forming composition suitable for forming an intermediate layer by rotation coating, and silicon formed by using the same. A containing film, a silicon containing film formation board | substrate, and the pattern formation method using the same.

With high integration and high speed of LSI, miniaturization of pattern dimensions is rapidly progressing. Lithography techniques have achieved the formation of fine patterns by shortening the wavelength of the light source and appropriate selection of the resist composition therefor in accordance with this miniaturization. The centerpiece is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton having an etching resistance to dry etching by chlorine or fluorine-based gas plasma in the resist resin, and has a resist mechanism in which the exposed portion dissolves, thereby dissolving the exposed portion to form a pattern. The substrate to which the resist composition is applied using the remaining resist pattern as an etching mask is subjected to dry etching.

 By the way, when the film thickness of the photoresist film to be used is miniaturized as it is, that is, the pattern width is made smaller, the resolution performance of the photoresist film is lowered, and when the pattern development of the photoresist film is performed by the developer, the so-called aspect ratio becomes too large, and as a result, Pattern collapse occurs. For this reason, the thickness of the photoresist film has become thin with the miniaturization.

On the other hand, in the processing of the substrate, a method of processing a substrate by dry etching using a patterned photoresist film as an etching mask is generally used. However, in practice, a dry type which can take complete etching selectivity between the photoresist film and the substrate to be processed is used. Since there is no etching method, the resist film is also damaged during substrate processing, the resist film collapses during substrate processing, and the resist pattern cannot be accurately transferred to the substrate to be processed. Therefore, high dry etching resistance has been required by the resist composition as the pattern becomes finer.

In addition, since the resin used for the photoresist composition by shortening the exposure wavelength required a resin having a small light absorption at the exposure wavelength, novolak resin, polyhydroxystyrene, Although it has been changed to a resin having an aliphatic polycyclic skeleton, in reality, the etching rate under the dry etching conditions is increasing, and the recent photoresist composition having high resolution tends to have low etching resistance.

As a result, dry etching processing of the substrate to be processed with a thinner and less etch resistant photoresist film is essential to secure materials and processes in this processing step.

One of the methods for solving this problem is the multilayer resist method. In this method, a photoresist film, i.e., an intermediate film having a different etching selectivity from an upper resist film, is interposed between the upper resist film and the substrate to be processed, the pattern is obtained on the upper resist film, and the upper resist pattern is subjected to dry etching as a dry etching mask. The pattern is transferred to the intermediate film by the method, and the pattern is transferred to the substrate to be processed by dry etching using the intermediate film as a dry etching mask.

In the two-layer resist method which is one of the multilayer resist methods, for example, there is a method of using a resin containing silicon as the upper layer resist composition and using a novolak resin as the intermediate film (for example, Patent Document 1: Japanese Patent Publication No. 6-95385). Silicon resins exhibit good etching resistance to reactive dry etching by oxygen plasma, but are easily etched away using a fluorine-based gas plasma. On the other hand, novolak resins are easily etched away in reactive dry etching with oxygen gas plasma, but exhibit good etching resistance to dry etching with fluorine gas plasma or chlorine gas plasma. Therefore, a novolak resin film is formed as a resist intermediate film on a to-be-processed substrate, and the resist upper layer film using silicon containing resin is formed on it. Subsequently, pattern formation is performed on the silicon-containing resist film by post-treatment such as irradiation and development of energy rays, and the novolak resin in a portion where the resist pattern is removed by reactive dry etching by oxygen plasma as a dry etching mask is dried. By removing the etching, the pattern is transferred to the novolak film, and the pattern transferred to the to-be-processed substrate is etched using a fluorine gas plasma or a chlorine gas plasma as a dry etching mask.

In the pattern transfer by dry etching, when the etching resistance of the etching mask is sufficient, since the transfer pattern is obtained in a relatively good shape, problems such as pattern collapse due to friction by a developer during development of the resist, etc. are unlikely to occur. A relatively high aspect ratio pattern can be obtained. Therefore, for example, when the resist film using a novolak resin is made into a thickness corresponding to the film thickness of the intermediate film, the above-described two layers also have a fine pattern that cannot be formed directly due to the pattern collapse during development from the aspect ratio problem. According to the resist method, a novolak resin pattern having a sufficient thickness can be obtained as a dry etching mask of a substrate to be processed.

As the multilayer resist method, there is a three-layer resist method that can be performed using a general resist composition used in the single layer resist method. For example, an organic film made of novolac or the like is formed on the substrate as a resist underlayer film, a silicon-containing film is formed on the substrate as a resist intermediate film, and a normal organic photoresist film is formed thereon as a resist upper layer film. With respect to the dry etching by the fluorine-based gas plasma, since the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, the resist pattern is transferred to the silicon-containing resist intermediate film by using dry etching with the fluorine-based gas plasma. According to this method, a pattern having a sufficient film thickness for directly processing a substrate to be processed can be patterned on a silicon-containing film even if a resist composition having difficulty in forming a resist composition or a resist composition having insufficient dry etching resistance for processing a substrate is used. If it can be transferred, a pattern of a novolak film having dry etching resistance sufficient for processing can be obtained as in the two-layer resist method.

As the silicon-containing resist intermediate film used in the three-layer resist method as described above, a silicon-containing inorganic film by CVD, for example, a SiO ₂ film (for example, Patent Document 2: Japanese Patent Laid-Open No. 7-183194) Publication), a SiON film (for example, Patent Document 3: Japanese Patent Application Laid-Open No. Hei 7-181688, etc.) and an SOG (spin-on glass) film (for example, a film obtained by rotating coating) , Patent Document 4: Japanese Patent Application Laid-Open No. 5-291208, etc., Non-Patent Document 1: J. Appl.Polym. Sci., Vol. 88, 636-640 (2003)) and crosslinkable silsesquioxane Membrane (for example, Patent Document 5: Japanese Patent Laid-Open No. 2005-520354, etc.), and the like, and a polysilane film (for example, Patent Document 6: Japanese Patent Laid-Open No. Hei 11-60735, etc.) Could also be used. Among them, the SiO ₂ film and the SiON film have a high performance as a dry etching mask when dry etching the underlying organic film, but require a special apparatus for film formation. In contrast, the SOG film, the crosslinkable silsesquioxane film, and the polysilane film can be formed only by rotation coating and heating, and are considered to have high process efficiency.

The application range of the multilayer resist method does not remain only in an attempt to raise the resolution limit of the resist film. In the case where the processing intermediate substrate has a large step like the first method of substrate processing, there is a large difference in the thickness of the resist film when a pattern is formed by a single resist film, so that the focus cannot be accurately focused at the time of resist exposure. Problems occur. In such a case, after the step is filled with a sacrificial film to be flattened, a resist film is formed thereon and a resist pattern is formed. In this case, however, the multilayer resist method as described above is inevitably used (for example, , Patent Document 7: Japanese Patent Application Laid-Open No. 2004-349572, etc.).

There exist some problems with the silicon containing film conventionally used by such a multilayer resist method. For example, when it is going to form a resist pattern by optical lithography, it is well known that exposure light reflects to a board | substrate, and interferes with incident light, and causes a problem of what is called a standing wave, and the fine pattern which does not have the edge roughness of a resist film is known. In order to obtain, it is necessary to put an anti-reflection film as an intermediate film. In particular, reflection control is an essential condition in the highest NA exposure conditions.

Therefore, in order to perform reflection control, in the process of forming a silicon-containing film as an intermediate layer in a multilayer resist method, especially CVD, it is necessary to put an organic antireflection film between the upper resist film and the silicon-containing intermediate film. However, when the organic antireflective film is added, it is necessary to pattern the organic antireflective film as a dry etching mask as a resist upper layer, and dry etching the antireflective film as a mask as a mask at the time of dry etching, followed by processing of the silicon-containing intermediate layer. Will be transferred to. For this reason, a load of dry etching is applied to the upper photoresist only by processing the antireflection film. In particular, in the uppermost photoresist film, the film thickness becomes thin, and this dry etching load cannot be overlooked. Therefore, the three-layer resist method which applies the light absorbing silicon containing film which does not produce the above-mentioned etching load as an intermediate film attracts attention.

As such a light absorbing silicon containing intermediate film, the rotation coating type light absorbing silicon containing intermediate film is known. For example, the method of having an aromatic structure as a light absorption structure is disclosed (patent document 8: Unexamined-Japanese-Patent No. 2005-15779). However, since the aromatic ring structure that absorbs light efficiently has a function of lowering the dry etching rate in the dry etching process by fluorine-based gas plasma, it is an unfavorable direction for dry etching the intermediate film without applying a load to the photoresist film. . Therefore, since it is not preferable to add such a light absorbing substituent in large quantities, it is necessary to suppress it with the minimum introduction amount.

In addition, the dry etching rate for the reactive dry etching by the oxygen gas plasma generally used when processing the resist underlayer film as a dry etching mask is preferably smaller because it increases the etching selectivity of the interlayer film and the underlayer film. A high intermediate film is desired as long as it is silicon content which is highly reactive with respect to a fluorine-type etching gas. Thus, it can be said that the component which has high reactivity with respect to fluorine gas, and the intermediate | middle film with high silicon content is desirable as a request | requirement from the processing conditions with any film of the upper photoresist film and the lower organic film.

However, the actual composition for forming a spin coating silicon-containing interlayer film contains an organic substituent so that the silicon-containing compound can be dissolved in an organic solvent. Among the known silicon-containing interlayers, a composition for forming an SOG film is disclosed in Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)) in lithography using KrF excimer laser light. have. However, since there is no description regarding a light absorber in this composition, the silicon-containing film obtained from this composition is expected to have no antireflection function. For this reason, since the reflection at the time of exposure cannot be suppressed with the lithography using the highest NA exposure machine of the highest stage, there exists a possibility that a high-precision pattern shape may not be obtained.

In addition to the demand for dry etching properties and antireflection effects such as these, storage stability of the composition is particularly problematic in compositions for forming interlayers having a high silicon content. In this case, with storage stability, the silanol group in the silicon containing compound contained in a composition may condense and the molecular weight of a composition may change. This results in variations in film thickness or in lithographic performance. In particular, since fluctuations in lithographic performance are sensitive, even when silanol groups in a molecule are condensed and cannot be observed as an increase in film thickness or a change in molecular weight, they are observed as a change in a highly precise pattern shape.

In the related art, non-patent document 2 (CJ Brinker and GW Scherer, "Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)). In addition, Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)), Patent Document 9 (Japanese Patent Laid-Open No. 2004-157469), and Patent Document 10 (Japanese Patent Laid-Open) Japanese Patent Application Laid-Open No. 2004-191386) discloses adding water in order to improve storage stability. However, in the silicon-containing compound prepared by the method shown in the patent document, even if such a measure is taken, it is impossible to completely stop the condensation reaction of the silanol groups, and the silicon-containing compound in the composition slowly changes and changes over time. The properties of the silicon-containing film obtained from one composition also change. For this reason, it was stored by refrigeration or freezing until just before use, and it had to return to use temperature (usually 23 degreeC), and to use it quickly when using.

[Patent Document 1] Japanese Unexamined Patent Publication No. 6-95385

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-183194

[Patent Document 3] Japanese Patent Application Laid-Open No. 7-181688

[Patent Document 4] Japanese Patent Application Laid-Open No. 5-291208

[Patent Document 5] Japanese Patent Publication No. 2005-520354

[Patent Document 6] Japanese Patent Application Laid-Open No. 11-60735

[Patent Document 7] Japanese Unexamined Patent Application Publication No. 2004-349572

[Patent Document 8] Japanese Patent Application Laid-Open No. 2005-15779

[Patent Document 9] Japanese Unexamined Patent Publication No. 2004-157469

[Patent Document 10] Japanese Unexamined Patent Publication No. 2004-191386

[Non-Patent Document 1] J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)

[Non-Patent Document 2] C. J. Brinker and G. W. Scherer, "Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)

An object of the present invention is to (1) form a photoresist film on a silicon-containing film formed on an organic film, and when the resist pattern is subsequently formed, the silicon-containing film has light absorption performance, so that a good pattern is formed even under high NA exposure conditions. (2) A silicon-containing film for dry etching masks can be formed between the photoresist film as the upper layer of the silicon-containing film and the organic film as the lower layer, and (3) the silicon-containing film-forming composition having good storage stability, and It is providing the silicon containing film obtained from a composition, the board | substrate with which this silicon containing film was formed, and the pattern formation method further.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined the lithographic characteristic and stability of the composition for silicon-containing interlayer formation, The following (B) component, (C) is carried out to the silicon-containing compound obtained by hydrolytically condensing a hydrolyzable silicon compound using an acid as a catalyst. By adding a component, (D) component, and (E) component,

(1) a silicon-containing film capable of suppressing reflection even under high NA exposure conditions of either dry or immersion by introducing a light absorbing substituent described later;

(2) a silicon-containing film from which a sufficient etching selectivity is obtained as a dry etching mask;

(3) It discovered that the composition for silicon-containing film formation which does not have the performance change which maintained lithographic performance for a long time was obtained, and came to complete this invention.

That is, this invention is the silicon containing compound obtained by hydrolytically condensing a hydrolyzable silicon compound using (A) acid as a catalyst,

(B) one or two or more of the compounds represented by the following general formula (1) or (2),

L _a H _b X

(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, b is 0 or an integer of 1 or more) A + b is a valence of hydroxyl or organic acid)

M _a H _b A

(Wherein M is sulfonium, iodonium or ammonium, A is X or a nonnucleophilic counter ion, a, b are the same as above, and a + b is a hydroxyl, organic acid or non-nucleophilic counter ion Singer)

(C) a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms,

(D) monovalent or divalent or higher alcohol having a cyclic ether as a substituent,

(E) Organic solvents

It provides a composition for forming a thermosetting silicon-containing film comprising a (claim 1).

In general, when water is reacted with a hydrolyzable silicon compound (hereinafter referred to as a monomer) under an acid catalyst, a hydrolyzable substituent bound to the silicon atom is hydrolyzed to form a silanol group. This silanol group is condensed with another silanol group or an unreacted hydrolyzable group to form a siloxane bond. And this reaction is repeated in order, and forms the so-called oligomer, a polymer, and the silicon containing compound called a sol in some cases. At this time, among the silanol groups derived from monomers, oligomers, and polymers produced by hydrolysis reaction in the system, the condensation reaction proceeds in order from the most reactive one, and the sila belongs to the monomer, oligomer, polymer, or the like. Play is consumed to form silicon-containing compounds. And this condensation reaction may advance without restriction and may advance until finally the silicon-containing compound solution gelatinizes.

However, this condensation reaction is known to be suppressed to a specific pH in Non-Patent Document 2 (CJ Brinker and GW Scherer, "Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)). In particular, Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)) describes that the pH is stabilized to about 1.5 (hereinafter referred to as stable pH).

In this invention, when controlling to stable pH using (C) component, it discovered that storage stability improves.

In order to suppress condensation of the remaining silanol groups contained in the silicon-containing compound at about room temperature, intensive studies have been conducted. When monovalent or divalent or higher alcohol having a cyclic ether as a substituent is added as a stabilizer, It has been found that condensation is suppressed and the storage stability of the composition is dramatically improved.

Conventionally, the silicon containing compound was hardened by the high temperature of 300 degreeC or more and the acid catalyst by a thermal acid generator. In the present invention, the pH region around the silanol group becomes unstable at a stable pH due to the action of the added component (B) when the composition is applied and cured under heat (Non-Patent Document 2: CJ Brinker and GW). Scherer, "So1-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)), allows for efficient curing of the film. That is, when heat-hardened on the conditions similar to the conventional temperature conditions, the film | membrane which crosslinked very much compared with the conventional cured film can be provided. For this reason, the movement of the active ingredient to the silicon-containing film in the resist film is suppressed, and the lithography characteristics on the same level as those of the normal organic antireflection film can be obtained.

Thus, a combination of techniques such as pH control, stabilizer addition, and crosslinking catalyst addition finds a composition that is stable at room temperature and can be cured efficiently at the time of curing, and thus silicon having stability equivalent to that of a conventional organic antireflection film. A containing antireflection film composition can be obtained.

In the present invention, the acid catalyst is substantially obtained from a reaction mixture obtained by hydrolytically condensing a hydrolyzable silicon compound using at least one compound selected from inorganic acids and sulfonic acid derivatives as acid-containing compounds as silicon-containing compounds. It provides the composition for thermosetting silicon-containing film formation characterized by including the silicon-containing compound obtained by the process of removing (claim 2).

The silicon-containing compound produced in the prior art was used in the composition for forming a coating film without substantially removing the acid catalyst used in the hydrolysis condensation. For this reason, since a condensation reaction catalyst remains in a composition, even the composition controlled by stable pH could not suppress condensation of silanol, and only the composition with poor storage stability was obtained.

Moreover, since the condensation reaction of a silanol group does not fully advance in the composition for coating film formation obtained using the acidic substance which becomes a silanol stable pH from the beginning as a hydrolysis condensation catalyst, there exist many silanol groups. For this reason, even if the composition is kept at a stable pH, for example, since the amount of silanol groups is too large, only a composition having low storage stability could be obtained.

In this invention, after removing an acid catalyst substantially from the silicon-containing compound obtained using the acid catalyst which is optimal for hydrolysis condensation, it became possible to improve storage stability using (C) and (D) component.

In the present invention, the composition for forming a thermosetting silicon-containing film according to claim 1 or 2, wherein M in the formula (2) is tertiary sulfonium, secondary iodonium, or quaternary ammonium (claim 3).

As a component (B), when a cured film is formed using the composition using the compound represented by General formula (2), the dense film which crosslinked advanced can be provided. For this reason, the movement of the active ingredient to the silicon-containing film in the resist film is suppressed, and the lithography characteristics on the same level as those of the normal organic antireflection film can be obtained.

The present invention provides a composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 3, wherein M in formula (2) is photodegradable (claim 4).

When component (B) does not volatilize at the time of heat-hardening, component (B) may remain in a silicon containing film. This component may deteriorate the shape of the resist pattern. On the other hand, when the compound which the cationic part of (B) component decomposes at the time of exposure is used, it becomes possible to prevent deterioration of the resist pattern shape at the time of exposure. That is, it discovered that the hardening performance of a silicon-containing compound can improve remarkably and can provide the silicon-containing cured film with a favorable lithographic shape.

The present invention provides a composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 4, comprising water (claim 5).

By adding water, the silanol group in the silicon-containing compound is activated, and a denser film can be obtained in the thermosetting reaction. When such a dense film is used, the lithography performance of the upper photoresist layer can be made to be equal to or more than that of a general organic antireflection film.

The present invention provides a composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 5, further comprising a photoacid generator (claim 6).

When (B) component does not volatilize at the time of heat-hardening or exposure, the (B) component which remain | survives in a silicon containing film may affect a pattern shape. In order to prevent this, it is possible to prevent deterioration of the resist pattern shape by generating acid in the silicon-containing film at the time of forming the resist pattern.

The present invention further provides the following silicon-containing film, substrate, and pattern forming method.

After forming an organic film on a to-be-processed board | substrate, forming a silicon containing film on it, and using the chemically amplified resist composition which does not contain silicon on it further, forming a resist film, pattern-processing this resist film, and then making this resist The silicon-containing film is pattern-processed using the film pattern, the processed silicon-containing film pattern is pattern-processed on the underlying organic film as an etching mask, and the processed organic film is used in a multilayer resist method for etching the substrate to be processed as an etching mask. Silicon-containing film (claim 7) formed from the composition of any one of Claims 1-6 which is a silicon-containing film.

In the process of the multilayer resist method of Claim 7, it is a silicon-containing film used by the multilayer resist method which interposed the organic antireflective film between the resist film obtained from a chemically amplified resist composition, and a silicon containing film, The process of Claims 1-6. A silicon-containing film (claim 8) formed from the composition according to any one of claims.

An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6 on this organic film, and a photoresist film are sequentially formed thereon, the substrate (claim 9).

An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6 on the organic film, an organic antireflection film, and a photoresist film formed thereon, the substrate (claim 10) .

The substrate (claim 11) according to claim 9 or 10, wherein the organic film is a film having an aromatic skeleton.

A method of forming a pattern on a substrate, wherein the substrate according to claim 9 is prepared, the pattern circuit region of the photoresist film of the substrate is exposed, and then developed with a developer to form a resist pattern on the photoresist film. Dry etching the silicon-containing film using the formed photoresist film as an etching mask, etching the organic film using the silicon-containing film having the pattern as an etching mask, and etching the substrate using the organic film having the pattern as a mask to form a pattern on the substrate. The pattern formation method characterized by the claim (claim 12).

A method of forming a pattern on a substrate, wherein the substrate according to claim 10 is prepared, the pattern circuit region of the photoresist film of the substrate is exposed, and then developed with a developer to form a resist pattern on the photoresist film. The organic anti-reflection film and the silicon-containing film are dry-etched using the formed photoresist film as an etching mask, the organic film is etched using the silicon-containing film with the pattern as an etching mask, the substrate is etched with the organic film with the pattern as a mask, and the pattern is applied to the substrate. Pattern formation method characterized by forming (claim 13).

The pattern forming method according to claim 12 or 13, wherein the organic film is a film having an aromatic skeleton (claim 14).

The pattern formation method according to any one of claims 12 to 14, wherein in forming the photoresist pattern, a photolithography method using light having a wavelength of 300 nm or less is used (claim 15).

When the pattern is formed on the substrate by lithography using the intermediate film or the substrate of the present invention, a fine pattern can be formed on the substrate with high accuracy.

In this case, the use of an organic film having an aromatic skeleton not only has an antireflection effect in the lithography step, but also an organic film having sufficient etching resistance when etching the substrate, thereby enabling etching.

In the present invention, when the pattern is formed by lithography using a light having a wavelength of 300 nm or less, especially an ArF excimer laser, a fine pattern can be formed with high accuracy.

By using the silicon containing intermediate film formed using the composition for thermosetting silicon-containing film formation of this invention, favorable pattern formation of the photoresist film formed on it is possible. In addition, since high etching selectivity is obtained between the organic materials, the formed photoresist pattern can be transferred using a dry etching process in order with the silicon-containing intermediate film and the organic underlayer film. Finally, the substrate can be processed with high precision using the organic underlayer film as an etching mask. In addition, it is possible to suppress the occurrence of pattern defects after lithography and to provide a material having excellent storage stability.

In the composition for forming a thermosetting silicon-containing film of the present invention, the silicon-containing compound used in the present invention is obtained by hydrolytic condensation of a monomer (hydrolyzable silicon compound) with an acid catalyst. Although the following method can be illustrated as a manufacturing method of a preferable silicon containing compound, It is not limited to this method.

The monomer which becomes a starting material can be represented by following formula (3).

R ¹ _m1 R ² _m2 R ³ _m3 Si (OR) _(4-m1-m2-m3)

(R is an alkyl group having 1 to 3 carbon atoms, R ¹ , R ² , R ³ may be the same or different from each other, a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, m 1, m 2, m 3 are 0 or 1, m1 + m2 + m3 is 0 to 3, in particular 0 or 1 is preferred)

Hydrolytically condensed 1 type, or 2 or more types of mixtures chosen from the monomer represented by this General formula (3).

Here, the organic group means a group containing carbon, and further contains hydrogen, and may also include nitrogen, oxygen, sulfur, silicon, and the like. As an organic group of R <^1> , R <^2> , R <^3> , Unsubstituted monovalent hydrocarbon groups, such as a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and the hydrogen atom of these groups are 1 Groups represented by the following formula (4), such as groups in which one or more are substituted with an epoxy group, an alkoxy group, a hydroxy group, or the like, or a group having -O-, -CO-, -OCO-, -COO-, or -OCOO- And organic groups containing silicon-silicon bonds.

Preferred as R ¹ , R ² , R ³ of the monomer represented by the formula (3) are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t- Alkyl groups, such as a butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-diethylpropyl group, a cyclopentyl group, n-hexyl group, and a cyclohexyl group, a vinyl group, and an allyl group Alkynyl groups, such as alkenyl groups, an ethynyl group, etc., Aralkyl groups, such as an aryl group, such as a phenyl group and a tolyl group, benzyl group, and a phenethyl group, are mentioned as a light absorbing group further.

For example, as tetraalkoxysilanes of m1 = 0, m2 = 0, and m3 = 0, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetra-isopropoxysilane can be illustrated as monomers. Can be. Preferably, they are tetramethoxysilane and tetraethoxysilane.

For example, as a trialkoxysilane of m1 = 1, m2 = 0, and m3 = 0, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-isopropoxysilane, and methyltrimethoxy Silane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso Propoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-isopropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n -Propyltri-n-propoxysilane, n-propyltri-isopropoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyl Tri-isopropoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso Foxysilane, sec-butyltrimethoxysilane, sec-butyl-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-isopropoxysilane, t-butyltrimethoxysilane , t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-isopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyl-tri-n -Propoxysilane, cyclopropyl-tri-isopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyl-tri-n-propoxysilane, cyclobutyl-tri-isopropoxysilane, Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl-tri-n-propoxysilane, cyclopentyl-tri-isopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclo Hexyl-tri-n-propoxysilane, cyclohexyl-tri-isopropoxysilane, Clohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyl-tri-n-propoxysilane, cyclohexenyl-tri-isopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexen Senylethyltriethoxysilane, cyclohexenylethyl-tri-n-propoxysilane, cyclohexenylethyltri-isopropoxysilane, cyclooctanyltrimethoxysilane, cyclooctanyltriethoxysilane, cyclooctanyl -Tri-n-propoxysilane, cyclooctanyl-tri-isopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyl-tri-n- Propoxysilane, cyclopentadienylpropyl-tri-isopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyl-tri-n-propoxysilane, bicyclo Heptenyl-tri-isopropoxyl , Bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyl-tri-n-propoxysilane, bicycloheptyl-tri-isopropoxysilane, adamantyltrimethoxysilane, adamantylt Liethoxysilane, adamantyl- tri-n-propoxysilane, adamantyl-tri-isopropoxysilane, etc. can be illustrated. Moreover, as a light absorbing monomer, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltri-n-propoxysilane, Phenyl tri-isopropoxysilane, Benzyl trimethoxysilane, Benzyl triethoxysilane, Benzyl tri- n-propoxysilane, benzyltri-isopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltri-n-propoxysilane, tolyltri-isopropoxysilane, phenethyltrimethoxysilane, phenene Butyltriethoxysilane, phenethyltri-n-propoxysilane, phenethyltri-isopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltri-n-propoxysilane, naphthyltri- Isopropoxysilane, etc. can be illustrated.

Preferably methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n-propyl Triethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyl tri Methoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltri Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, and phenethyltriethoxysilane.

For example, as a dialkoxysilane of m1 = 1, m2 = 1, m3 = 0, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyl-di-n-pro Foxysilane, dimethyl-di-isopropoxysilane, diethyldimethoxysilane, diethyldiethoxy silane, diethyl-di-n-propoxysilane, diethyl-di-isopropoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-isopropoxysilane, di-isopropyldimethoxysilane, di- Isopropyl diethoxysilane, di-isopropyl-di-n-propoxysilane, di-isopropyl-di-isopropoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di -n-butyl-di-n-propoxysilane, di-n-butyl-di-isopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl- Di-n-propoxysilane, di-sec-butyl- Isopropoxysilane, di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyl-di-n-propoxysilane, di-t-butyl-di-isopropoxysilane Di-cyclopropyldimethoxysilane, di-cyclopropyldiethoxysilane, di-cyclopropyl-di-n-propoxysilane, di-cyclopropyl-di-isopropoxysilane, di-cyclobutyldimethoxysilane, Di-cyclobutyldiethoxysilane, di-cyclobutyl-di-n-propoxysilane, di-cyclobutyl-di-isopropoxysilane, di-cyclopentyldimethoxysilane, di-cyclopentyldiethoxysilane, di -Cyclopentyl-di-n-propoxysilane, di-cyclopentyl-di-isopropoxysilane, di-cyclohexyldimethoxysilane, di-cyclohexyl diethoxysilane, di-cyclohexyl-di-n-prop Foxysilane, Di-cyclohexyl-di-isopropoxysilane, Di-cyclohexenyldimethoxysilane, Di-cyclohexenyl diethoxysilane, Dicyclohexenyl-di-n-prop Foxysilane, Di-cyclohexenyl-di-isopropoxysilane, Di-cyclohexenylethyldimethoxysilane, Di-cyclohexenylethyl diethoxysilane, Di-cyclohexenylethyl-di-n-propoxysilane , Di-cyclohexenylethyl-di-isopropoxysilane, di-cyclooctanyldimethoxysilane, di-cyclooctanyl diethoxysilane, di-cyclooctanyl-di-n-propoxysilane, di-cyclo Octanyl-di-isopropoxysilane, di-cyclopentadienylpropyldimethoxysilane, di-cyclopentadienylpropyl diethoxysilane, di-cyclopentadienylpropyl-di-n-propoxysilane, di -Cyclopentadienylpropyl-di-isopropoxysilane, bis-bicycloheptenyldimethoxysilane, bis-bicycloheptenyldiethoxysilane, bis-bicycloheptenyl-di-n-propoxysilane, bis -Bicycloheptenyl-di-isopropoxysilane, bis-bicycloheptyldimethoxysilane, bis-bicycloheptyldiethoxy Cysilane, bis-bicycloheptyl-di-n-propoxysilane, bis-bicycloheptyl-di-isopropoxysilane, bis-adamantyldimethoxysilane, bis-adamantyl diethoxysilane, bis-a Danmanyl-di-n-propoxysilane, bis-adamantyl-di-isopropoxysilane and the like can be exemplified. Moreover, as a light absorbing monomer, diphenyl dimethoxysilane, diphenyl-di-ethoxysilane, methylphenyldimethoxysilane, methylphenyl diethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-isopro Foxysilane etc. can be illustrated.

Preferably dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, di-n-propyl-di-methoxysilane, di -n-butyldi-methoxysilane, methylphenyldimethoxysilane, methylphenyl diethoxysilane, etc. can be illustrated.

For example, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, etc. can be illustrated as monoalkoxysilane whose m1 = 1, m2 = 1, m3 = 1. Moreover, dimethylphenyl methoxysilane, dimethylphenylethoxysilane, dimethylbenzyl methoxysilane, dimethylbenzyl ethoxysilane, dimethyl phenethyl methoxysilane, dimethyl phenethyl ethoxysilane etc. can be illustrated as a light absorbing monomer.

Preferably, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc. can be illustrated.

As another example of the organic group represented by said R <^1> , R <^2> , R <^3> , the organic group which has one or more carbon-oxygen single bond or carbon-oxygen double bond is mentioned. Specifically, it is an organic group which has 1 or more groups chosen from the group which consists of an epoxy group, an ester group, an alkoxy group, and a hydroxyl group. Examples of the organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond in the formula (3) include those represented by the following formula (4).

(PQ _1- (S ₁ ) _v1 -Q _2- ) _u- (T) _v2 -Q _3- (S ₂ ) _v3 -Q _4-

, 탄소수 1 내지 4의 알콕시기, 탄소수 1 내지 6의 알킬카르보닐옥시기, 또는 탄소수 1 내지 6의 알킬카르보닐기이고, Q₁과 Q₂와 Q₃과 Q₄는 각각 독립적으로 -C_qH_{(2 q-p)}P_p-(식 중, P는 상기와 동일하고, p는 0 내지 3의 정수이며, q는 0 내지 10의 정수(단, q=0은 단결합인 것을 나타냄)임), u는 0 내지 3의 정수이고, S₁과 S₂는 각각 독립적으로 -O-, -CO-, -OCO-, -COO- 또는 -OCOO-를 나타낸다. v1, v2, v3은 각각 독립적으로 0 또는 1을 나타낸다. 이들과 함께, T는 헤테로 원자를 포함할 수도 있는 지환 또는 방향환을 포함하는 2가의 기이며, T의 산소 원자 등의 헤테로 원자를 포함할 수도 있는 지환 또는 방향환의 예를 이하에 나타낸다. T에서 Q₂와 Q₃과 결합하는 위 치는 특별히 한정되지 않지만, 입체적인 요인에 의한 반응성이나 반응에 이용하는 시판 시약의 입수성 등을 고려하여 적절하게 선택할 수 있다.)(In the above formula, P is a hydrogen atom, a hydroxyl group,

, An alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms, and Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently -C _q H _{( 2 qp)} P _p- (wherein P is the same as above, p is an integer from 0 to 3, q is an integer from 0 to 10 (where q = 0 represents a single bond), u Is an integer of 0 to 3, and S ₁ and S ₂ each independently represent -O-, -CO-, -OCO-, -COO-, or -OCOO-. v1, v2, and v3 each independently represent 0 or 1. Together with these, T is a divalent group containing an alicyclic or aromatic ring which may contain a hetero atom, and examples of the alicyclic or aromatic ring which may contain a hetero atom such as an oxygen atom of T are shown below. The position at which T binds to Q ₂ and Q ₃ is not particularly limited but may be appropriately selected in consideration of reactivity due to steric factors and availability of commercially available reagents used for the reaction.)

Examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) include the following ones. In addition, in the following chemical formula, (Si) was described in order to show the bonding site with Si.

Moreover, as an example of the organic group of R <^1> , R <^2> , R <^3> , the organic group containing a silicon-silicon bond can also be used. Specifically, the following are mentioned.

It can be set as the reaction raw material which selects 1 type (s) or 2 or more types from these monomers, mixes before or during reaction, and forms a silicon-containing compound.

The silicon-containing compound can be produced by subjecting the monomer to hydrolysis condensation using at least one compound selected from inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids as acid catalysts.

The acid catalyst used at this time includes hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid. The amount of the catalyst is from 10 ^-6 mol to 10 mol, preferably 10 ^-5 to 5 moles to moles, more preferably from 10 ^-4 mol to 1 mol per 1 mol of the silicon monomer.

The amount of water when obtaining a silicon-containing compound by hydrolysis condensation from these monomers is 0.01 to 100 moles, more preferably 0.05 to 50 moles, more preferably 0.1 to 30 moles per mole of hydrolyzable substituents bound to the monomers. Preference is given to adding. Additions in excess of 100 moles are not economical only because the apparatus used for the reaction is excessive.

As an operation method, a monomer is added to the aqueous catalyst solution to initiate a hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, the monomer may be diluted with an organic solvent, or both. The reaction temperature is 0 to 100 ° C, preferably 5 to 80 ° C. Preferred is a method of maintaining the temperature at 5 to 80 ° C. under the dropwise addition of the monomer and then aging at 20 to 80 ° C.

Organic solvents that can be added to the aqueous catalyst solution or can dilute the monomers include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile , Tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol mono Ethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, 3-methoxypropionate, 3-ether Ethyl oxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Acetates, such as γ- butyrolactone, and mixtures thereof are preferred.

Preferred among these solvents is water soluble. For example, alcohols, such as methanol, ethanol, 1-propanol, and 2-propanol, polyhydric alcohols, such as ethylene glycol and propylene glycol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl Polyhydric alcohol condensate derivatives such as ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran and the like. have.

Especially preferable thing in this is a boiling point of 100 degrees C or less.

Moreover, the usage-amount of the organic solvent is 0-1,000 ml with respect to 1 mol of monomers, Especially 0-500 ml is preferable. If the amount of organic solvent used is large, the reaction vessel becomes excessive and it is not economical.

Thereafter, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol produced in the hydrolysis condensation reaction is removed under reduced pressure to obtain a reaction mixture aqueous solution. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents based on the acid used as the catalyst. This alkaline substance may be any substance as long as it shows alkalinity in water.

Subsequently, the alcohol produced in the hydrolytic condensation reaction must be removed from the reaction mixture. The temperature at which the reaction mixture is heated at this time depends on the organic solvent added and the type of alcohol generated in the reaction, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C and even more preferably 15 to 80 ° C. . The degree of decompression at this time depends on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device and the heating temperature, but is preferably at most atmospheric pressure, more preferably at most 80 kPa, more preferably at absolute pressure. 50 kPa or less. Although it is difficult to know the quantity of alcohol removed at this time, it is preferable that 80 mass% or more of the produced | generated alcohol is generally removed.

Subsequently, the acid catalyst used for hydrolysis condensation can be removed from the reaction mixture. As a method of removing an acid catalyst, water and a silicon containing compound are mixed, and a silicon containing compound is extracted with the organic solvent. As an organic solvent used at this time, a silicon-containing compound can be dissolved, and when mixed with water, it is preferable to separate two layers. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl- 2-n-amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl Ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, (gamma) -butyl lactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc., and mixtures thereof are mentioned.

It is also possible to use mixtures of water-soluble organic solvents and poorly water-soluble organic solvents. For example, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol monomethyl ether, Butanediol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + acetic acid Ethyl, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobutyl ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether Propylene glycol monoethyl ether + methyl isobutyl ketone, Tylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + Cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + cyclopentyl methyl ether, ethylene glycol monomethyl ether + cyclopentyl methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol Monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl ether + cyclopentyl methyl ether, methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + Propylene glycol methyl Teracetate, 2-propanol + propylene glycol methyl ether acetate, propylene glycol monomethyl ether + propylene glycol methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, Combinations of ethylene glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate are preferred, but the combination is not limited to these. .

In addition, although the mixing ratio of a water-soluble organic solvent and a poorly water-soluble organic solvent is suitably selected, 0.1-1,000 mass parts of water-soluble organic solvents, Preferably 1-500 mass parts, More preferably, with respect to 100 mass parts of poorly water-soluble organic solvents. Preferably from 2 to 100 parts by mass.

Subsequently, it is washed with neutral water. This water can use what is normally called deionized water or ultrapure water. The amount of this water is 0.01 to 100 L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L with respect to 1 L of the silicon-containing compound solution. In this method of washing, both sides are put in the same container, mixed, and then left still to separate the aqueous layer. Although the frequency | count of washing | cleaning should just be one or more times, since the effect as much as the washing | cleaning is not acquired even if it wash | cleans 10 times or more, it is preferably about 1 to 5 times.

In addition, as a method of removing an acid catalyst, the method by ion-exchange resin, the method of neutralizing with epoxy compounds, such as ethylene oxide and a propylene oxide, and removing is mentioned. These methods can be appropriately selected for the acid catalyst used in the reaction.

In addition, in the above catalyst removal operation, the fact that the acid catalyst was substantially removed means that the acid catalyst used in the reaction is 10 mass% or less, preferably about 5 mass% or less, based on the amount added at the start of the reaction in the silicon-containing compound. To remain means to be allowed.

The washing operation at this time may cause a part of the silicon-containing compound to fall out of the water layer and obtain an effect substantially equivalent to that of the fractionation operation. Therefore, the number of washing times and the amount of washing water are appropriately taken in consideration of the catalyst removal effect and the fractionation effect. You can choose.

In either case of the silicon-containing compound in which the acid catalyst remains or the silicon-containing compound solution from which the acid catalyst has been removed, the silicon-containing compound solution is obtained by adding the final solvent and performing solvent exchange under reduced pressure. Although the temperature of the solvent exchange at this time changes with kinds of reaction solvent or extraction solvent to remove, Preferably it is 0-100 degreeC, More preferably, it is 10-90 degreeC, More preferably, it is 15-80 degreeC. The degree of decompression at this time depends on the type of extraction solvent to be removed, the exhaust device, the condenser and the heating temperature, but is preferably at most atmospheric pressure, more preferably at most 80 kPa or less, even more preferably at 50 absolute pressure. kPa or less.

Under the present circumstances, a silicon-containing compound may become unstable by changing a solvent. This occurs due to the compatibility between the final solvent and the silicon-containing compound, but in order to prevent this, the component (C) described later may be added as a stabilizer. The amount to be added is 0 to 25 parts by mass, preferably 0 to 15 parts by mass, and more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the silicon-containing compound in the solution before solvent exchange, but 0.5 mass is added when added. More than a part is preferable. If necessary to the solution before solvent exchange, (C) component can be added and a solvent exchange operation can be performed.

When the silicon-containing compound is concentrated to a specific concentration or more, the condensation reaction proceeds, and the silicon-containing compound changes to a state that cannot be re-dissolved in an organic solvent. For this reason, it is preferable to set it as the solution state of a suitable density | concentration. As concentration at this time, it is 50 mass% or less, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less.

The final solvent added to the silicon-containing compound solution is preferably an alcohol solvent, and particularly preferably monoalkyl ethers such as ethylene glycol, diethylene glycol and triethylene glycol, and monoalkyl ethers such as propylene glycol and dipropylene glycol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene Glycol monopropyl ether etc. are preferable.

In addition, in another reaction operation, water or a hydrous organic solvent is added to the monomer or the organic solution of the monomer, and the hydrolysis reaction is started. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. Reaction temperature is 0-100 degreeC, Preferably it is 10-80 degreeC. The method of heating to 10-50 degreeC under dripping of water, heating it to 20-80 degreeC, and then ripening is preferable.

When using an organic solvent, water-soluble thing is preferable, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, Butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether And polyhydric alcohol condensate derivatives such as propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, and mixtures thereof.

The amount of the organic solvent used may be the same as the above amount. Post-treatment of the obtained reaction mixture is carried out in the same manner as in the above method to obtain a silicon-containing compound.

Although the molecular weight of the silicon-containing compound obtained can be adjusted not only by the selection of the monomer but also by the reaction condition control at the time of polymerization, when a weight average molecular weight exceeds 100,000, in some cases generation of foreign matters or coating unevenness occurs. It is preferred to use 100,000 or less, more preferably 200 to 50,000, still more preferably 300 to 30,000. In addition, the said data concerning the weight average molecular weight show the molecular weight in polystyrene conversion using polystyrene as a reference material by gel permeation chromatography (GPC) using RI as a detector.

The composition for forming a silicon-containing film of the present invention may contain two or more kinds of silicon-containing compounds having different compositions and / or reaction conditions as long as they are produced under acidic conditions.

A thermal crosslinking accelerator (B), an acid (C), a stabilizer (D) and an organic solvent (E) can be further blended with the silicon-containing compound to form a composition for forming a silicon-containing film.

In this invention, since the crosslinking reaction at the time of silicon-containing film formation is further accelerated | stimulated, you must contain a thermal crosslinking promoter as (B) component. As such a compound, the compound represented by General formula (1) and (2) is mentioned.

&Lt; Formula 1 >

L _a H _b X

(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, b is 0 or an integer of 1 or more) A + b is a valence of hydroxyl or organic acid)

(2)

M _a H _b A

Wherein M is sulfonium, iodonium or ammonium, preferably tertiary sulfonium, secondary iodonium or quaternary ammonium, in particular photodegradable, ie triphenylsulfonium compounds, diphenyl Iodonium compounds are preferred, where A is X or a non-nucleophilic counter ion, a, b are the same as above, and a + b is a valence of a hydroxyl group, an organic acid group or a non-nucleophilic counter ion)

As a compound represented by General formula (1), an alkali metal organic acid salt can be illustrated. For example, lithium, sodium, potassium, rubidium, cesium oxalate, formate, acetate, propionate, butanate, pentanate, hexanoate, heptanate, octanoate, nonanate, decanate, oleate, stearic acid Monovalent salts such as acid salt, linoleate salt, linoleate salt, benzoate salt, phthalate salt, isophthalate salt, terephthalate salt, salicylate salt, trifluoroacetic acid salt, monochloroacetic acid salt, dichloroacetic acid salt and trichloroacetic acid salt, 1 Divalent or divalent oxalate, malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonate, succinate, methylsuccinate, glutarate, adipicate, Itaconic acid salt, maleate, fumarate, citraconate, citrate, carbonate, etc. are mentioned.

Specifically, lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium pentanate, lithium hexanoate, lithium heptanoate, lithium octanoate, lithium nonanoate, lithium decanoate, lithium oleate, lithium stearate, lithium linoleate Lithium linoleate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, Lithium oxalate, lithium malonate, lithium methyl malonate, lithium ethyl malonate, lithium propyl malonate, lithium butyl malonate, lithium dimethylmalonate, lithium diethylmalonate, lithium succinate, methyl succinate lithium, glutaric acid Lithium Oxygen, Lithium Adipic Acid, Lithium Itaconic Acid, Lithium Maleic Acid, Lithium Fumaric Acid, Sitracon Lithium Oxide, Lithium Citrate, Lithium Carbonate, Lithium Oxalate, Lithium Malonate, Lithium Methyl Malonate, Lithium Ethyl Malonate, Lithium Propyl Malonate, Lithium Malonate, Lithium Dimethyl Malonate, Lithium Diethyl Malonate, Succinic Acid Lithium, lithium methyl succinate, lithium glutarate, lithium adipic acid, lithium itaconate, lithium maleate, lithium fumarate, lithium citrate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate Sodium, sodium pentanate, sodium hexanoate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium oleate, sodium stearate, sodium linoleate, sodium linoleate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, salicylic acid Sodium, Sodium Trifluoromethanesulfonate, Sodium Trifluoroacetic Acid, Sodium Monochloroacetic Acid, Dichloroacetic Acid Sodium acid, sodium trichloroacetate, sodium hydroxide, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen methyl malate, sodium hydrogen malonate, sodium hydrogen propyl malonate, sodium hydrogen butyl malonate, sodium hydrogen dimethyl malonate, sodium diethyl malonate, Sodium hydrogen succinate, sodium hydrogen succinate, sodium hydrogen glutate, sodium adipic acid, sodium hydrogen itaconate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citrate, sodium hydrogen citrate, sodium hydrogen carbonate, sodium oxalate, malonic acid Sodium, sodium methyl malate, sodium ethyl malonate, sodium propyl malonate, sodium butyl malonate, sodium dimethyl malonate, sodium diethyl malonate, sodium succinate, sodium methyl succinate, sodium glutarate, sodium adipic acid, Sodium itacate, sodium maleate, sodium fumarate, citraconic acid na Cerium, Sodium Citrate, Sodium Carbonate, Potassium Formate, Potassium Acetate, Potassium Propionate, Potassium Butane, Potassium Pentanate, Potassium Hexate, Potassium Heptanate, Potassium Octanate, Potassium Nonanoate, Potassium Decanoate, Potassium Oleate, Potassium Stearate , Potassium linoleate, potassium linoleate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, Potassium Hydroxide, Potassium Hydrogen Oxalate, Potassium Hydrogen Malon, Potassium Hydrogen Methyl Malonate, Potassium Hydrogen Malonate, Potassium Hydrogen Hydrogen, Potassium Hydrogen Hydrogen Butyl, Potassium Hydrogen Malonate, Potassium Hydrogen Dimethyl Malonate, Potassium Hydrogen Dimethyl Malonate, Potassium Hydrogen Succinate, Methyl Succinate Potassium, Potassium Hydrogen Glutarate, Potassium Hydrogen Adipate, Potassium Hydrogen Itaconate, Potassium Hydrogen Maleate, Fumar Potassium Hydrogen, Potassium Hydrogen Citrate, Potassium Hydrogen Citrate, Potassium Hydrogen Carbonate, Potassium Oxalate, Potassium Malonate, Potassium Methyl Malate, Potassium Malonate, Potassium Propyl Malate, Potassium Butylonate, Potassium Dimethyl Malonate, Diethyl Potassium malonate, potassium succinate, potassium methyl succinate, potassium glutarate, potassium adipic acid, potassium itaconic acid, potassium maleate, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate and the like can be exemplified.

As a compound represented by General formula (2), the sulfonium compound, iodonium compound, and ammonium compound represented by (Q-1), (Q-2), and (Q-3) is mentioned.

^Wherein R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ²⁰⁵ and R ²⁰⁶ may form a ring or a ring In the case of forming R ²⁰⁵ and R ²⁰⁶ , each represents an alkylene group having 1 to 6 carbon atoms, A ⁻ represents a non-nucleophilic counter ion, and R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ , and R ²¹⁰ represent R ²⁰⁴ , R ²⁰⁵ , The same as R ²⁰⁶ but may be a hydrogen atom R ²⁰⁷ and R ²⁰⁸ , R ²⁰⁷ and R ²⁰⁸ and R ²⁰⁹ may form a ring, and in the case of forming a ring, R ²⁰⁷ and R ²⁰⁸ and R ²⁰⁷ and R ²⁰⁸ and R ²⁰⁹ represent alkylene groups having 3 to 10 carbon atoms.)

R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ , R ²¹⁰ may be the same or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group , Norbornyl group, adamantyl group, etc. are mentioned. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like. Examples of the oxoalkyl group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group. Examples of the oxoalkyl group include a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl- - (4-methylcyclohexyl) -2-oxoethyl group and the like. As an aryl group, alkoxy, such as a phenyl group, a naphthyl group, and p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, an ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, etc. Alkyl naph, such as alkylphenyl groups, such as a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, methylnaphthyl group, and ethyl naphthyl group, etc. Dialkoxy naphthyl groups, such as an alkoxy naphthyl group, such as a methyl group, a methoxy naphthyl group, and an ethoxy naphthyl group, a dimethyl naphthyl group, a diethyl naphthyl group, dialkoxy naphthyl groups, such as a dialkyl naphthyl group, a dimethoxy naphthyl group, and a diethoxy naphthyl group, etc. are mentioned. Can be. Examples of the aralkyl group include benzyl group, phenylethyl group and phenethyl group. As the aryl oxoalkyl group, 2-aryl-2-oxo such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group Ethyl group etc. are mentioned.

A ^- furnace is hydroxy ions, formic ions, acetate ions, propionic ions, butanoic ions, pentanic acid ions, hexanoic acid ions, heptanoic acid ions, octanoic acid ions, nonanoic acid ions, decanoic acid ions, oleic acid ions, stearic acid ions, Linoleic acid ion, linolenic acid ion, benzoic acid ion, p-methylbenzoic acid ion, pt-butylbenzoic acid ion, phthalate ion, isophthalic acid ion, terephthalic acid ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloro Roacetic acid ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, chlorate ion, perchlorate ion, bromate ion, iodide ion, oxalate ion, malonic acid ion, methylmalonic acid ion, ethyl malonic acid Ions, propyl malonic acid ions, butyl malonic acid ions, dimethyl malonic acid ions, diethyl malonic acid ions, succinic acid ions, methyl succinic acid On, glutaric acid ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, carbonate ion, and the like.

Specific examples of the sulfonium compound include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butane, triphenylsulfonium butane, triphenylsulfonium hexanoate, and heptanoic acid. Triphenylsulfonium, triphenylsulfonium octanoate, triphenylsulfonium nonanoate, triphenylsulfonium decanoate, triphenylsulfonium oleate, triphenylsulfonium stearate, triphenylsulfonium linoleate, triphenylsulfonium linolenic acid Triphenylsulfonium benzoate, triphenylsulfonium p-methylbenzoate, triphenylsulfonium pt-butylbenzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, Trifluoromethanesulfonic acid triphenylsulfonium, trifluoroacetic acid triphenylsulfonium, monochloroacetic acid triphenylsulfonium, dichloroacetic acid triphenylsulfonium, trichloroa Triphenylsulfonium oxalate, triphenylsulfonium hydroxide, triphenylsulfonium oxalate, triphenylsulfonium malonic acid, triphenylsulfonium methyl malonic acid, triphenylsulfonium methyl ethyl acid, triphenylsulfonium propyl malonic acid, butyl Triphenylsulfonium malonate, triphenylsulfonium dimethyl malonic acid, triphenylsulfonium diethylmalonic acid, triphenylsulfonium succinate, triphenylsulfonium methyl succinate, triphenylsulfonium glutarate, triphenyl adipic acid Sulfonium, triphenylsulfonium itaconic acid, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconate, triphenylsulfonium citrate, triphenylsulfonium carbonate, triphenylsulfonium chloride, brominated Triphenylsulfonium, triphenylsulfonium iodide, triphenylsulfonium nitrate, triphenylsulfonium chlorate, triphenylsulfonium perchlorate, triphenylsulfonium bromide, triphenylsulfonium iodide, bisulfitephenylsulfonate Bismuthylphenyl sulfonium, methyl malonic acid bistriphenylsulfonium, methyl malonic acid bistriphenylsulfonium, propyl malonic bistriphenylsulfonium, butyl malonic acid bistriphenylsulfonium, dimethyl malonic acid bistriphenylsulfonium, di Ethyl malonic acid bistriphenylsulfonium, succinic acid bistriphenylsulfonium, methyl succinic acid bistriphenylsulfonium, glutaric acid bistriphenylsulfonium, adipic bistriphenylsulfonium, itaconic acid bistriphenylsulfonium, maleic acid bistri Phenylsulfonium, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconate, bistriphenylsulfonium citrate, bistriphenylsulfonium carbonate and the like.

Specific examples of the iodonium compound include diphenyl iodonium formate, diphenyl iodonium acetate, diphenyl iodonium propionate, diphenyl iodonium butane, diphenyl iodonium pentanate, and diphenyl iodohexanoate. Diphenyl iodonium heptane, diphenyl iodonium octanoate, diphenyl iodonium nonanoate, diphenyl iodonium decanoate, diphenyl iodonium oleate, diphenyl iodonium stearate, diphenyl iodonium linoleate Diphenyl iodonium linolenic acid, diphenyl iodonium benzoate, diphenyl iodonium p-methylbenzoate, diphenyl iodonium pt-butylbenzoate, diphenyl iodonium phthalate, diphenyl iodonium phthalate, Diphenyl iodonium terephthalate, diphenyl iodonium salicylate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium trifluoroacetic acid, diphenyl iodonium monochloroacetate, dichloro acetate diphenyl iodo Ium, triclo Diphenyl iodonium rotate, diphenyl iodonium hydroxide, diphenyl iodonium oxalate, diphenyl iodonium malonic acid, diphenyl iodonium methyl malonate, diphenyl iodonium ethyl malonic acid, diphenyl iodonium propyl malonic acid diphenyl iodo Dinium iodonium, butyl malonate, diphenyl iodonium dimethyl malonate, diphenyl iodonium dimethyl malonate, diphenyl iodonium succinate, diphenyl iodonium succinate, diphenyl iodonium glutarate , Diphenyl iodonium adipic acid, diphenyl iodonium itaconic acid, diphenyl iodonium maleate, diphenyl iodonium fumarate, diphenyl iodonium citrate, diphenyl iodonium citrate, diphenyl iodonium citrate Donium, diphenyl iodonium chloride, diphenyl iodonium bromide, diphenyl iodonium iodide, diphenyl iodonium nitrate, diphenyl iodonium chlorate, diphenyl iodonium perchlorate, diphenyl iodo bromide Ium, diphenyl iodonium iodide, oxalic acid bisdipe Iodonium, bis diphenyl iodonium malonate, bis diphenyl iodonium methyl malonate, bis diphenyl iodonium ethyl malonic acid, bis diphenyl iodonium propyl malonic acid bis diphenyl iodonium butyl malonic acid Donium, bis diphenyl iodonium dimethyl malonic acid, bis diphenyl iodonium diethyl malonic acid, bis diphenyl iodonium succinate, bis diphenyl iodonium methyl succinate, bis diphenyl iodonium glutarate , Bis diphenyl iodonium adipic acid bis diphenyl iodonium itaconate bis diphenyl iodonium maleic acid bis diphenyl iodonium fumarate bis diphenyl iodonium citrate Phenyl iodonium, bis diphenyl iodonium, etc. are mentioned.

On the other hand, specifically, as an ammonium compound, tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium pentanate, tetramethylammonium hexanoate, tetramethylammonium heptane, tetraoctamethane octanoate Methyl ammonium, tetramethylammonium nonanoate, tetramethylammonium decanoate, tetramethylammonium oleate, tetramethylammonium stearate, tetramethylammonium linoleate, tetramethylammonium linoleate, tetramethylammonium benzoate, tetramethylammonium benzoate, tetramethylammonium benzoate, pt -Butyl benzoate tetramethylammonium, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonic acid tetramethylammonium, trifluoroacetic acid tetramethylammonium, monochloroacetic acid tetramethyl Monium, dichloroacetic acid tetramethylammonium, trichloroacetic acid tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium oxalate, tetramethylammonium malonate, methylmalonic acid tetramethylammonium, ethylmalonic acid tetramethylammonium, propylmalonic acid tetramethyl Ammonium, butylmalonic acid tetramethylammonium, dimethylmalonic acid tetramethylammonium, diethylmalonic acid tetramethylammonium, succinate tetramethylammonium, methylsuccinate tetramethylammonium, glutaric acid tetramethylammonium, adipic acid tetramethylammonium, ita Tetramethylammonium Contralate, Tetramethylammonium Maleate, Tetramethylammonium Fumarate, Tetramethylammonium Citrate, Tetramethylammonium Citrate, Tetramethylammonium Carbonate, Tetramethylammonium Chloride, Tetramethylammonium Iodide, Tetramethylammonium Iodide, Tetra Nitrate Methyl Ammonium Chlorate Tramethylammonium, tetramethylammonium perchlorate, tetramethylammonium bromide, tetramethylammonium iodide, bistetramethylammonium oxalate, bistetramethylammonium malonic acid, bistetramethylammonium methylmalonic acid, bistetramethylammonium ethylmalonic acid, Bismethyl methyl bisulfate, butyl malonic acid bistetramethylammonium, dimethyl malonic acid bistetramethylammonium, diethylmalonic acid bistetramethylammonium, succinic acid bistetramethylammonium, methyl succinate bistetramethylammonium, bis glutaric acid bis Tetramethylammonium, adipic acid bistetramethylammonium, itaconic acid bistetramethylammonium, maleic acid bistetramethylammonium, fumaric acid bistetramethylammonium, citraconic acid bistetramethylammonium, citrate bistetramethylammonium, bistetramethyl carbonate Ammonium, tetrapropyl ammonium formate, acetate Lapropyl ammonium, tetrapropyl ammonium propionate, tetrapropyl ammonium butyrate, tetrapropyl ammonium pentanate, tetrapropyl ammonium hexanoate, tetrapropyl ammonium heptanoate, tetrapropyl ammonium octanoate, tetrapropyl ammonium nonanoate, tetrapropyl ammonium decanoate , Tetrapropylammonium oleate, tetrapropylammonium stearate, tetrapropylammonium linoleate, tetrapropylammonium linoleate, tetrapropylammonium benzoate, tetrapropylammonium benzoate, pt-butylbenzoate tetrapropylammonium, tetrapropylammonium phthalate, isophthalic acid Tetrapropylammonium, terephthalate tetrapropylammonium, salicylic acid tetrapropammonium, trifluoromethanesulfonic acid tetrapropylammonium, trifluoroacetic acid tetrapropylammonium, monochloroacetic acid tetrapropylammonium, dichloroacetic acid Tetrapropylammonium, trichloroacetic acid tetrapropylammonium hydroxide, tetrapropylammonium hydroxide, tetrapropylammonium oxalate, tetrapropylammonium malonic acid, tetrapropylammonium methyl malonate, tetrapropylammonium ethyl malonate, tetrapropylammonium propyl malonic acid, butyl mala Tetrapropylammonium lonate, tetrapropylammonium dimethylmalonate, tetrapropylammonium diethylmalonic acid, tetrapropylammonium succinate, tetrapropylammonium succinate, tetrapropylammonium succinate, tetrapropylammonium glutarate, tetrapropylammonium adipic acid, tetrapropylammonium itaconate Tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium carbonate, tetrapropylammonium chloride, tetrapropylammonium iodide, tetrapropylammonium iodide, tetranitrate Trapropylammonium, tetrapropylammonium chlorate, tetrapropylammonium perchlorate, tetrapropylammonium bromide, tetrapropylammonium iodide, bistetrapropylammonium oxalate, bistetrapropylammonium, methylmalonic acid bistetrapropylammonium, ethylmalonic acid Bistetrapropylammonium, propylmalonic acid bistetrapropylammonium, butylmalonic acid bistetrapropylammonium, dimethylmalonic acid bistetrapropylammonium, diethylmalonic acid bistetrapropylammonium, succinic acid bistetrapropylammonium, methylsuccinate bistetrapropylammonium , Bistetrapropylammonium glutarate, bistetrapropylammonium adipic acid, bistetrapropylammonium itaconic acid, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citrate, bistetrapropylammonium citrate Potassium bistrapropylammonium, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium pentate, tetrabutylammonium hexanoate, tetrabutylammonium hexanoate, octanoic acid Tetrabutylammonium, tetrabutylammonium nonanoate, tetrabutylammonium decanoate, tetrabutylammonium oleate, tetrabutylammonium stearate, linoleic acid tetrabutylammonium, linoleate tetrabutylammonium, benzoate tetrabutylammonium, p-methylbenzoate tetrabutylammonium, pt-butylbenzoate tetrabutylammonium, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonic acid tetrabutylammonium, trifluoroacetic acid tetrabutylammonium, monochloroacetic acid tetra Butyl Arm Tetrabutylammonium, trichloroacetic acid tetrabutylammonium hydroxide, tetrabutylammonium hydroxide, oxalate tetrabutylammonium, malonate tetrabutylammonium, methylmalonic acid tetrabutylammonium, ethylmalonic acid tetrabutylammonium, propylmalonic acid tetrabutyl Ammonium, butylmalonic acid tetrabutylammonium, dimethylmalonic acid tetrabutylammonium, diethylmalonic acid tetrabutylammonium, succinate tetrabutylammonium, methyl succinate tetrabutylammonium, glutaric acid tetrabutylammonium, adipic acid tetrabutylammonium, ita Tetrabutylammonium, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium carbonate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetranitrate nitrate Butyl Ammonium Chlorate Butyl ammonium, tetrabutylammonium perchlorate, tetrabutylammonium bromide, tetrabutylammonium iodide, bistetrabutylammonium oxalate, bistrabutylammonium malonic acid, bis tetrabutylammonium, ethylmalonic acid bistetrabutylammonium, propyl Bistetrabutylammonium malonate, bistetrabutylammonium butyl malonic acid, bistetrabutylammonium dimethyl malonic acid, bistetrabutylammonium diethylmalonic acid, bistetrabutylammonium succinate, bistetrabutylammonium succinate bistrabutylammonium glutamate Butyl ammonium, adipic acid bistetrabutylammonium, itaconic acid bistetrabutylammonium, maleic acid bistetrabutylammonium, fumaric acid bistetrabutylammonium, citraconic acid bistetrabutylammonium, citrate bistetrabutylammonium, bistetrabutylammonium carbonate Etc. can be illustrated.

In addition, the said thermal crosslinking promoter can be used individually by 1 type or in combination of 2 or more types. The amount of the thermal crosslinking accelerator added is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained in the above method).

In order to ensure the stability of the composition for thermosetting silicon-containing film of this invention, you should add C1-C30 monovalent or divalent or more organic acid as (C) component. At this time, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, Terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, Succinic acid, methyl succinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid, etc. can be illustrated. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are particularly preferable. Moreover, in order to maintain stability, you may mix and use 2 or more types of acid. The addition amount is 0.001-25 mass parts, Preferably it is 0.01-15 mass parts, More preferably, it is 0.1-5 mass parts with respect to 100 mass parts of silicon containing compounds contained in a composition.

Alternatively, the organic acid may be converted to the pH of the composition, and preferably blended so as to be 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5 and even more preferably 0.5 ≦ pH ≦ 6.

In addition, when the monohydric or divalent or higher alcohol having a cyclic ether as a substituent as a stabilizer (D), especially an ether compound represented by the following structure, is added, the stability of the silicon-containing film-forming composition can be improved. As such a compound, the compound shown below is mentioned.

Wherein R ^90a is a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁹¹ O— (CH ₂ CH ₂ O) _n 1-(CH ₂ ) _{n 2-} (where 0 ≦ n1 ≦ 5, 0 ≦ n2 ≦ 3, R ⁹¹ is a hydrogen atom or a methyl group), or R ⁹² O— [CH (CH ₃ ) CH ₂ O] _n3 — (CH ₂ ) _n4 —, where 0 ≦ _n3 ≦ 5 , 0 ≦ n4 ≦ 3, R ⁹² is a hydrogen atom or a methyl group), R ^90b is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group, one or two or more hydroxyl groups, HO _{- (CH 2 CH 2 O)} n5 - (CH 2) n6 - ( wherein, 1≤n5≤5, 1≤n6≤3), or HO- [CH (CH ₃₎ CH ₂ O] _n7 - (CH ₂ ) _n8 - (wherein a 1≤n7≤5, 1≤n8≤3).

In addition, the said stabilizer can be used individually by 1 type or in combination of 2 or more type. The amount of the stabilizer added is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained in the above method). In addition, these stabilizers can be used individually by 1 type or in mixture of 2 or more types. Among them, preferred structures are compounds having a crown ether derivative and a bicyclo ring in which the bridge position is an oxygen atom as a substituent.

The addition of such stabilizers further stabilizes the charge of the acid and contributes to the stabilization of the silicon-containing compounds in the composition.

The composition containing the silicon-containing compound of the present invention contains the same organic solvent as that used for the production of the silicon-containing compound as the component (E), preferably a water-soluble organic solvent, in particular ethylene glycol, diethylene glycol, triethylene glycol, or the like. Monoalkyl ethers such as monoalkyl ether, propylene glycol, dipropylene glycol, butanediol and pentanediol are used. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene An organic solvent selected from glycol monopropyl ether and the like is used.

 In the present invention, water may be added to the composition. When water is added, the silicon-containing compound is hydrated, thereby improving the lithographic performance. The content rate of water in the solvent component of a composition is more than 0 mass% and less than 50 mass%, Especially preferably, it is 0.3-30 mass%, More preferably, it is 0.5-20 mass%. If the amount of each component is too large, the uniformity of the coating film is deteriorated, and in the worst case, the cratering occurs. On the other hand, when the addition amount is small, lithography performance is lowered, which is not preferable.

As for the usage-amount of the whole solvent containing water, 500-100,000 mass parts, especially 400-50,000 mass parts are preferable with respect to 100 mass parts of base polymers.

In this invention, a photoacid generator can also be used. As the photoacid generator used in the present invention,

(A-I) an onium salt of formula (P1a-1), (P1a-2) or (P1b),

(A-II) diazomethane derivatives of the general formula (P2)

(A-III) glyoxime derivative of formula (P3),

(A-IV) bissulfon derivatives of the general formula (P4),

(A-V) sulfonic acid esters of N-hydroxyimide compounds of formula (P5),

(A-VI) β-ketosulfonic acid derivatives,

(A-VII) disulfone derivatives,

(A-VIII) nitrobenzylsulfonate derivatives,

(A-IX) sulfonic acid ester derivative

And the like.

^Wherein R ^101a , R ^101b and R ^101c each represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Or an aralkyl group or an aryl oxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted by an alkoxy group, etc. R ^101b and R ^101c may form a ring or a ring In the case of forming R, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms. K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b , and R ^101c may be the same as or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl have. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like. Examples of the oxoalkyl group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group. Examples of the oxoalkyl group include a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl- - (4-methylcyclohexyl) -2-oxoethyl group and the like. As an aryl group, alkoxy, such as a phenyl group, a naphthyl group, and p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, an ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, etc. Alkyl naph, such as alkylphenyl groups, such as a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, methylnaphthyl group, and ethyl naphthyl group, etc. Dialkoxy naphthyl groups, such as an alkoxy naphthyl group, such as a methyl group, a methoxy naphthyl group, and an ethoxy naphthyl group, a dimethyl naphthyl group, a diethyl naphthyl group, dialkoxy naphthyl groups, such as a dialkyl naphthyl group, a dimethoxy naphthyl group, and a diethoxy naphthyl group, etc. are mentioned. Can be. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryl oxoalkyl group, 2-aryl-2-oxo such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group Ethyl group etc. are mentioned. Non ^- nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, Alkyl sulfonates, such as aryl sulfonate, such as tosylate, benzene sulfonate, 4-fluorobenzene sulfonate, and 1,2,3,4,5-pentafluorobenzene sulfonate, mesylate, butane sulfonate, etc. are mentioned. Can be.

( ^Wherein , R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ represents a straight, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ^104a , R ^104b each represents a 2-oxoalkyl group having 3 to 7 carbon atoms. K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of the R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and cyclophene A methyl group, a cyclohexyl group, a cyclopropylmethyl group, 4-methylcyclohexyl group, a cyclohexylmethyl group, etc. are mentioned. R ¹⁰³ is a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a 1,4-cyclopentylene group, a 1,2-cyclohexylene group, 1 A, 3-cyclopentylene group, a 1, 4- cyclooctylene group, a 1, 4- cyclohexane dimethylene group, etc. are mentioned. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxocycloheptyl group, and the like. K <^-> can mention the same thing as what was demonstrated by general formula (P1a-1), (P1a-2), and (P1a-3).

(Wherein R ¹⁰⁵ and R ¹⁰⁶ are a linear, branched or cyclic alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or an aral having 7 to 12 carbon atoms) Kills.)

^Examples of the alkyl group represented by R ¹⁰⁵ and R ¹⁰⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert- butyl group, a pentyl group, a hexyl group, a heptyl group, A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group. Examples of the aryl group include alkoxyphenyl groups such as phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group and m-tert-butoxyphenyl group. And alkylphenyl groups such as methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

^Wherein R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ is a linear, branched or cyclic alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl having 7 to 12 carbon atoms. R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene groups represented by R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group.

(In formula, ^R101a and ^R101b are the same as the above.)

(Wherein, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms contained in these groups further have 1 to 4 carbon atoms. May be substituted with a linear or branched alkyl group or an alkoxy group, a nitro group, an acetyl group, or a phenyl group of R ¹¹¹ is a linear, branched or substituted alkyl, alkenyl or alkoxyalkyl group having 1 to 8 carbon atoms, A phenyl group or a naphthyl group, a part or all of the hydrogen atoms of these groups further being an alkyl or alkoxy group having 1 to 4 carbon atoms, a phenyl group which may be substituted with an alkyl, alkoxy, nitro or acetyl group having 1 to 4 carbon atoms; A heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom.)

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, and the like are used as alkylene groups, such as methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group and norbor Examples of the alkenylene group such as an egg-2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, and 5-norbornene-2,3-diyl group. . ^Examples of the alkyl group of R ¹¹¹ are the same as those of R ^101a to R ^101c, and examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl, 7-octene Examples of the alkoxyalkyl group include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group and butoxy Ethyl group, pentyloxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, Ethoxy pentyl group, a methoxyhexyl group, a methoxyheptyl group, etc. are mentioned.

In addition, examples of the alkyl group having 1 to 4 carbon atoms which may be further substituted include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. A methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like may be substituted with an alkyl, alkoxy, nitro or acetyl group having 1 to 4 carbon atoms. Examples of the phenyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group and a p-nitrophenyl group. Examples of the hetero aromatic group having 3 to 5 carbon atoms include a pyridyl group and a furyl group.

Specifically, the following photoacid generators are mentioned, for example. Trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-part Methoxyphenyl) phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butoxy Phenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium , p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid triphenyl Sulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluenesulfonic acid trimethylsulfonium, trifluoromethanesulfonic acid Lohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid dimethylphenylsulfonium, p-toluenesulfonic acid dimethylphenylsulfonium, tri Fluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, Trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthyl Onium salts, such as carbonyl methyl tetrahydrothiophenium triplate.

Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane , Bis (isopropyl sulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec Amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- diazomethane derivatives such as (tert-amylsulfonyl) diazomethane and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane.

Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α -Dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione Glyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl ) -α-dicyclohexylglyoxime, bis-O- (n-butanesulfonyl) -2,3-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4 -Pentanedioneglyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,1, 1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethyl Glyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylgly Shim, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesul Glyoxime derivatives, such as a fonyl) -alpha-dimethylglyoxime, bis-O- (xylenesulfonyl) -alpha-dimethylglyoxime, and bis-O- (campasulfonyl) -alpha-dimethylglyoxime.

Bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bis Bissulfon derivatives such as benzenesulfonylmethane.

? -Ketosulfonic acid derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

Disulfone derivatives, such as diphenyl disulfone and dicyclohexyl disulfone.

nitrobenzylsulfonate derivatives such as p-toluenesulfonic acid 2,6-dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl.

1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, etc. Sulfonic acid ester derivatives.

N-hydroxysuccinimidemethanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N -Hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octane sulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester , N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimidebenzenesulfonic acid ester, N-hydroxysuccinimide-2 , 4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimidemethanesulfonic acid ester , N-hydroxy Imide methanesulfonic acid ester, N-hydroxy maleimide ethane sulfonic acid ester, N-hydroxy-2-phenyl maleimide methane sulfonic acid ester, N-hydroxy glutarimide methane sulfonic acid ester, N-hydroxy glutarimide benzene sulfonic acid Ester, N-hydroxy phthalimide methanesulfonic acid ester, N-hydroxyphthalimide benzene sulfonic acid ester, N-hydroxy phthalimide trifluoromethane sulfonic acid ester, N-hydroxy phthalimide p-toluene sulfonic acid Ester, N-hydroxy naphthalimide methane sulfonic acid ester, N-hydroxy naphthalimide benzene sulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimide methane sulfonic acid ester, N- N- such as hydroxy-5-norbornene-2,3-dicarboxyimidetrifluoromethanesulfonic acid ester and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonic acid ester Hydroxyimide Sulfonic acid ester derivatives such as water.

Among them, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, and trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium , p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid Trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, 1,2'- Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triplate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, Bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) dia Diazomethane derivatives, such as bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert- butylsulfonyl) diazomethane, bis-O- (p Glyoxime derivatives such as -toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bissulphone derivatives such as bisnaphthylsulfonylmethane, and N-hydride Oxysuccinimidemethanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N- N such as hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxy naphthalimide methane sulfonic acid ester, N-hydroxy naphthalimide benzene sulfonic acid ester Sulfonic acid ester derivatives of hydroxyimide compounds are preferably used. The.

In addition, the said photoacid generator can be used individually by 1 type or in combination of 2 or more types. The addition amount of a photo acid generator becomes like this. Preferably it is 0.01-50 mass parts, More preferably, it is 0.05-40 mass parts with respect to 100 mass parts of base polymers (silicon containing compound obtained by the said method).

Further, in the present invention, it is possible to formulate a surfactant if necessary. Here, as surfactant, a nonionic thing is preferable, and a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl ethylene oxide adduct, and a fluorine-containing organosiloxane type | system | group The compound can be mentioned. For example, Florade "FC-430", "FC-431", "FC-4430" (all manufactured by Sumitomo 3M Co., Ltd.), Suplon "S-141", "S-145", "KH-10" "," KH-20 "," KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), United" DS-401 "," DS-403 "," DS-451 "(all Daikin Kogyo Co., Ltd., Mega Pack "F-8151" (Dai Nippon Ing. Co., Ltd.), "X-70-092", "X-70-093" (All Shin-Etsu Kagaku High School) Note) production). Preferably, the flora "FC-4430", "KH-20", "KH-30", and "X-70-093" are mentioned.

In addition, the addition amount of surfactant can be made a normal amount in the range which does not prevent the effect of this invention, and it is preferable to set it as 0-10 mass parts with respect to 100 mass parts of base polymers especially 0-5 mass parts.

A silicon-containing film effective for the etching mask of the present invention can be produced from a silicon-containing film-forming composition on a substrate by spin coating or the like similarly to a photoresist film. After spin coating, it is preferable to bake the solvent in order to evaporate the solvent and to prevent mixing with the upper resist film to promote the crosslinking reaction. The baking temperature is preferably used within the range of 10 to 300 seconds within the range of 50 to 500 ° C. The particularly preferred temperature range also depends on the structure of the device being manufactured, but 400 ° C. or less is preferred in order to reduce heat loss to the device.

Here, in the present invention, the silicon-containing film is formed on the portion of the substrate to be processed through an underlayer film, and a photoresist film is formed thereon, whereby pattern formation can be performed.

In this case, as the to-be-processed part of a to-be-processed board | substrate, the low dielectric constant insulating film whose k-value is three or less, the primary low dielectric constant insulating film processed, the nitrogen and / or oxygen containing inorganic film, a metal film, etc. are mentioned.

In more detail, a to-be-processed substrate can be what formed the to-be-processed layer (processing part) on a base substrate. The base substrate is not particularly limited and may be a material different from the layer to be processed using Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, or the like. have. As the layer to be processed, Si, SiO ₂ , SiN, SiON, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and various low dielectric films and their etching stopper films are used. It may be formed to a thickness of 50 to 10,000 nm, in particular 100 to 5,000 nm.

In the present invention, a commercially available organic antireflection film may be formed between the silicon-containing film and the upper resist film. At this time, the structure of the antireflection film is a compound having an aromatic substituent. The anti-reflection film should not be subjected to an etching load on the upper resist film when the pattern of the upper resist film is transferred by dry etching. For example, with respect to the upper layer resist film, if the film thickness is 80% or less, preferably 50% or less, the load at the time of dry etching becomes very small.

In this case, it is preferable that the antireflection film is adjusted so that the minimum reflection is 2% or less, preferably 1% or less, more preferably 0.5% or less.

When the silicon containing film of this invention is used for the exposure process by ArF excimer laser beam, all the normal resist compositions for ArF excimer laser beam can be used as an upper resist film. Resist composition for ArF excimer laser light is a number of candidates are already known, if the positive type is an acid labile group is decomposed by the action of an acid, solubility in alkali aqueous solution, a basic material for controlling the diffusion of acid and photoacid generator and acid In the case of the negative type, the main component is a resin which reacts with the crosslinking agent by the action of an acid and is insoluble in an aqueous alkali solution, and a basic acid for controlling the diffusion of the photoacid generator, the crosslinking agent, and the acid. There is a difference in character. The known resins can be broadly classified into poly (meth) acrylic, COMA (cycloolefin maleic anhydride), COMA- (meth) acrylic hybrid, ROMP (ring-opening metathesis polymerization) and polynorbornene. Among them, the resist composition using a poly (meth) acrylic resin has an etching resistance by securing an alicyclic skeleton in the side chain, so that the resolution performance is superior to other resin systems.

A large number of resist compositions for ArF excimer lasers using poly (meth) acrylic resins are known, but all of them are used as positive functions for the positive type, which are decomposed by the action of an acid and an acid to ensure etching resistance. A polymer is comprised by the combination of a unit, a unit for ensuring adhesiveness, etc., or the combination which contains the unit which the one unit has two or more of the above functions, as the case may be. Among these, as a unit whose alkali solubility changes with an acid, (meth) acrylic acid ester (JP-A-9-73173) which has an acid labile group which has an adamantane skeleton, norbornane, or tetracyclo (Meth) acrylic acid esters having an acid labile group having a dodecane skeleton (JP-A-2003-84438) provide high resolution and etching resistance and are particularly preferably used. Moreover, as a unit for ensuring adhesiveness, the (meth) acrylic acid ester which has a norbornane side chain which has a lactone ring (international publication No. 00/01684), and the (meth) acrylic acid ester which has an oxanorbornane side chain (Japan Japanese Patent Application Laid-Open No. 2000-159758) or (meth) acrylic acid ester having a hydroxyadamantyl side chain (Japanese Patent Application Laid-open No. Hei 8-12626) provides good etching resistance and high resolution. Especially preferably, it can be used. In addition, the polymer containing a unit having an alcohol having an acidic property as a functional group (for example, Polym. Mater. Sci. Eng. 1997. 77. pp449) in which the adjacent position is fluorine-substituted is used to inhibit swelling in the polymer. In order to provide physical properties and provide high resolution, the film has attracted attention as a resist polymer corresponding to the imazone method, which has recently attracted attention in recent years. However, fluorine is contained in the polymer, causing a problem of lowering etching resistance. The silicon-containing film for etching masks of the present invention can be particularly effectively used for organic resist materials that are difficult to secure such etching resistance.

Although the acid generator, a basic compound, etc. are contained in the resist composition for ArF excimer laser containing the said polymer, the acid generator can use about the same thing that can be added to the composition for silicon-containing film formation of this invention, Onium salts are particularly advantageous in terms of sensitivity and resolution. In addition, a large number of basic substances are known, and are exemplified in Japanese Unexamined Patent Publication No. 2005-146252, which has been recently published, and can be advantageously selected from them.

After the silicon-containing film layer for etching mask is produced, a photoresist layer is produced using the photoresist composition solution thereon, but the spin coating method is preferably used similarly to the silicon-containing film layer for etching mask. Although prebaking is performed after spin-coating a resist composition, the range of 10 to 300 second is preferable at 80-180 degreeC. Then, exposure is performed, post-exposure baking (PEB) and image development are performed, and a resist pattern is obtained.

The etching of the silicon-containing film for etching masks is performed using a pron-based gas, nitrogen gas, carbon dioxide gas, or the like. The silicon-containing film for etching masks of the present invention is characterized by a high etching rate with respect to the gas and a small film reduction of the upper resist film.

In the multilayer resist method using the silicon-containing film of the present invention, an underlayer film is provided between the silicon-containing film and the substrate to be processed of the present invention. When the lower layer film is used as an etching mask of the substrate to be processed, it is preferable that the lower layer film is an organic film having an aromatic skeleton, but the lower layer film is not only an organic film but also a silicon-containing material if the silicon content is 15% by mass or less. It may be.

In addition, the organic film which has an aromatic skeleton is many well-known as an underlayer film specifically, The 4,4 '-(9H-fluorene-9-ylidene) bisphenol novolak resin described in Unexamined-Japanese-Patent No. 2005-128509. Besides (molecular weight 11,000), many resins including novolak resin are known as a resist underlayer film material of a two-layer resist method or a three-layer resist method, and both can be used. Moreover, in order to improve heat resistance more than normal novolak, polycyclic frame | skeleton like 4,4 '-(9H-fluorene-9-ylidene) bisphenol novolak resin can also be put, and a polyimide-type resin is further added. It is also possible to select (for example, Japanese Patent Laid-Open No. 2004-153125).

In the case of the multilayer resist method using an organic film that serves as an etching mask of a substrate to be processed, the organic film is a film which transfers the patterned resist pattern to the silicon-containing film and then transfers the pattern once more, and the silicon-containing film is high. In addition to having the property of being capable of etching under etching conditions exhibiting etching resistance, the characteristics of having high etching resistance are required for the conditions for etching the substrate to be processed.

Organic films as such underlayer films are already well known as underlayer films for the three-layer resist method or for the two-layer resist method using the silicon resist composition, and the 4,4 '-(9H-flu described in JP 2005-128509 A. In addition to oren-9-ylidene) bisphenol novolak resin (molecular weight 11,000), many resins, including a novolak resin, are known as a resist underlayer film material of a two-layer resist method or a three-layer resist method, and both can be used. Moreover, in order to improve heat resistance more than normal novolak, polycyclic frame | skeleton like 4,4 '-(9H-fluorene-9-ylidene) bisphenol novolak resin can also be put, and a polyimide-type resin is further added. It is also possible to select (for example, Japanese Patent Laid-Open No. 2004-153125).

The organic film can be formed on the substrate by a spin coating method or the like similarly to the photoresist composition using the composition solution. It is preferable to bake in order to evaporate the organic solvent after forming a resist underlayer film by a spin coating method or the like. The baking temperature is preferably in the range of 80 to 300 占 폚 and in the range of 10 to 300 seconds.

Although not particularly limited, the thickness of the underlayer film is 10 nm or more, in particular 50 nm or more, preferably 50,000 nm or less, and the thickness of the silicon-containing film according to the present invention is 1 nm or more and 200 nm or less, depending on the etching processing conditions. The thickness of the photoresist film is preferably 1 nm or more and 300 nm or less.

The three-layer resist method using the silicon containing film for etching masks of this invention is as follows. In this step, an organic film is first produced on the substrate to be processed by spin coating or the like. Since this organic film acts as a mask when etching a substrate, it is preferable that the etching resistance is high and that it is not required to mix with the silicon-containing film for etching mask of the upper layer. It is preferable to crosslink by. The silicon-containing film for etching mask and the photoresist film obtained from the composition of the present invention are formed thereon by the above method. The resist film is pattern-exposed using a light source according to the resist film, for example, a KrF excimer laser light, an ArF excimer laser light, or an F ₂ laser light in accordance with a conventional method, and after heat treatment according to a condition suitable for each resist film, A resist pattern can be obtained by performing a developing operation with a developing solution. Subsequently, using this resist pattern as an etching mask, etching is performed in dry etching conditions in which the silicon-containing film has a high etching rate with respect to the organic film, for example, fluorine-based gas plasma. When the antireflection film and the silicon-containing film are etched, a silicon-containing film pattern can be obtained without being substantially affected by the pattern change caused by side etching of the resist film. Subsequently, dry etching conditions in which the etching rate of the lower organic film is superior to the substrate having the silicon-containing film pattern to which the resist pattern obtained above is transferred, for example, reactive dry etching with a gas plasma containing oxygen, or hydrogen- Reactive dry etching with a gas plasma containing nitrogen is performed to etch the lower organic film. Although the pattern of an underlayer organic film is obtained by this etching process, the resist layer of an uppermost layer is normally lost at the same time. The substrate to be processed can be precisely etched by using dry etching of the substrate to be processed, for example, fluorine-based dry etching or chlorine-based dry etching, as the etching mask.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is concretely demonstrated using a synthesis example, an Example, and a comparative example, this invention is not limited by these description.

Synthesis Example 1

200 g of methanol, 200 g of ion-exchanged water, and 1 g of 35% hydrochloric acid were added to a 1,000 ml glass flask, and a mixture of 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane, and 10 g of phenyltrimethoxysilane was charged to room temperature. Was added. After hydrolysis condensation at room temperature for 8 hours as it was, 300 ml of propylene glycol monoethyl ether was added and concentrated under reduced pressure to obtain 300 g of a propylene glycol monoethyl ether solution of silicon-containing compound 1 (polymer concentration 21%). It was Mw = 2,000 when this polystyrene conversion molecular weight was measured.

[Synthesis Example 2]

Except for changing the mixture of 50 g of tetraethoxysilane of Synthesis Example 1, 100 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane to 100 g of methyltrimethoxysilane and 20 g of phenyltrimethoxysilane, the same 300 g (polymer concentration 19%) of the propylene glycol monoethyl ether solutions of the silicon-containing compound 2 were obtained by operation. It was Mw = 3,000 when this polystyrene conversion molecular weight was measured.

[Synthesis Example 3]

60 g of methanol of Synthesis Example 1, 200 g of ion-exchanged water, 1 g of 35% hydrochloric acid, 50 g of tetraethoxy silane, 100 g of methyltrimethoxysilane, 10 g of phenyltrimethoxysilane and propylene glycol monoethyl ether Silicon-containing compound 3 in the same operation, except that 260 g of exchanged water, 5 g of 65% nitric acid, 70 g of tetramethoxysilane, 70 g of methyltrimethoxysilane, 10 g of phenyltrimethoxysilane, and butanediol monomethyl ether were changed. 300 g of a butanediol monomethyl ether solution (polymer concentration 20%) was obtained. It was Mw = 2,500 when this polystyrene conversion molecular weight was measured.

[Synthesis Example 4]

260 g of ion-exchanged water and 1 g of 35% hydrochloric acid were charged into a 1,000 ml glass flask, followed by 70 g of tetramethoxysilane, 25 g of methyltrimethoxysilane, 25 g of a silane compound of the formula [i], and phenyltrimethoxy A mixture of 10 g of silane was added at room temperature. After hydrolysis condensation at room temperature for 8 hours as it is, by-product methanol was distilled off under reduced pressure. 800 ml of ethyl acetate and 300 ml of propylene glycol monopropyl ether were added thereto, and the aqueous layer was separated. 100 ml of ion-exchanged water was added to the remaining organic layer, followed by stirring, standing, and liquid separation. This was repeated three times. 200 ml of propylene glycol monopropyl ether was added to the remaining organic layer, and it concentrated under reduced pressure to obtain 300 g (polymer concentration of 20%) of the propylene glycol monopropyl ether solution of the silicon-containing compound 4. The obtained solution was analyzed for chloro ions by ion chromatography, but was not detected. It was Mw = 1,800 when this polystyrene conversion molecular weight was measured.

Synthesis Example 5

200 g of ethanol, 100 g of ion-exchanged water, and 3 g of methanesulfonic acid were charged into a 1,000 ml glass flask, 40 g of tetramethoxysilane, 10 g of methyltrimethoxysilane, 50 g of a silane compound of the formula [ii] and phenyl A mixture of 10 g of trimethoxysilane was added at room temperature. After hydrolysis condensation at room temperature for 8 hours as it is, by-product methanol was distilled off under reduced pressure. 800 mL of ethyl acetate and 300 mL of ethylene glycol monopropyl ether were added thereto, and the aqueous layer was separated. 100 ml of ion-exchanged water was added to the remaining organic layer, followed by stirring, standing, and liquid separation. This was repeated three times. 200 ml of ethylene glycol monopropyl ether was added to the remaining organic layer, and it concentrated under reduced pressure, and obtained 300 g (polymer concentration 20%) of the ethylene glycol monopropyl ether solution of the silicon-containing compound 5. When the methanesulfonic acid ion was analyzed by the ion chromatograph of the obtained solution, it turned out that 99% of what was used for reaction was removed. It was Mw = 2,100 when this polystyrene conversion molecular weight was measured.

[Examples, Comparative Examples]

The silicon-containing film-forming composition solutions were prepared by mixing the silicon-containing compounds 1 to 5, the acid, the thermal crosslinking accelerator, the solvent, and the additives in the ratios shown in Table 1 below, followed by filtration with a 0.1 μm fluorine resin filter. And Sol. It was set to 1-10.

TPSOAc: triphenylsulfonium acetate (photodegradable thermal crosslinking accelerator)

TPSOH: triphenylsulfonium hydroxide (photodegradable thermal crosslinking accelerator)

TPSCl: triphenylsulfonium chloride (photodegradable thermal crosslinking accelerator)

TPSMA: mono maleic acid (triphenylsulfonium) (photodegradable thermal crosslinking accelerator)

TPSN: triphenylsulfonium nitrate (photodegradable thermal crosslinking accelerator)

TMAOAc: tetramethylammonium acetate (non-degradable thermal crosslinking accelerator)

TPSNf: triphenylsulfonium nonafluorobutanesulfonate (photoacid generator)

First, a 4,4 '-(9H-fluorene-9-ylidene) bisphenol novolak resin (molecular weight 11,000) (Japanese Patent Laid-Open No. 2005-128509) -containing composition (resin) was used as an underlayer film material on a Si wafer. 28 parts by mass and 100 parts by mass of a solvent) were spun on and then heated to film at 200 ° C. for 1 minute to form a lower organic film having a thickness of 300 nm. As this lower layer organic film material, many resins including a novolak resin are well-known as a lower layer film material of a multilayer resist method besides the above, and all can be used.

Then Sol. 1-10 were apply | coated rotationally, and it heated-deposited at 200 degreeC for 1 minute, and formed the silicon containing film | membrane with a film thickness of 100 nm.

In addition, PGMEA (propylene glycol monomethyl ether acetate) containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) as the following as a resist composition for ArF excimer laser light exposure to form an upper resist film: It melt | dissolved in the solution and manufactured by filtering by the filter of 0.1 micrometers fluororesins.

                                                             Mw = 6,800

(Me represents methyl group, Et represents ethyl group)

                                                             10 parts by mass

Photoacid generator: 0.2 parts by mass of triphenylsulfonium nonafluorobutanesulfonate

Basic compound: 0.02 mass part of triethanolamine

This composition was applied onto a silicon-containing intermediate layer and baked at 130 ° C. for 60 seconds to form a photoresist layer having a thickness of 200 nm.

Subsequently, it exposed with ArF exposure apparatus (made by Nikon Corporation; S305B, NA 0.68, (sigma) 0.85, 2/3 ring illumination, Cr mask), baked at 110 degreeC for 90 second (PEB), and 2.38 mass% tetramethylammonium. It developed with the hydroxide (TMAH) aqueous solution, and obtained the positive pattern. The result of having observed the pattern shape of 90 nmL / S of the obtained pattern is shown in following Table 2.

In any of the examples, a pattern without hamming, undercut, and intermixing was obtained in the vicinity of the substrate.

Subsequently, the dry etching resistance test was done. The composition Sol. 1-10 were spin-coated, and it heated-formed at 200 degreeC for 1 minute, and produced the silicon-containing film films 1-10 with a film thickness of 100 nm. These films, the underlayer film, and the photoresist film were subjected to an etching test under the following etching conditions (1). The results are shown in Table 3 below.

(1) Etching test in CHF ₃ / CF ₄ gas

Equipment: Tokyo Electron Co., Ltd. dry etching apparatus TE-8500P

Etching condition (1):

Chamber pressure 40.0 Pa

RF Power 1,300 W

9 mm gap

CHF ₃ gas flow rate 30 ml / min

CF ₄ gas flow rate 30 ml / min

Ar gas flow rate 100 ml / min

Processing time 10 seconds

Subsequently, as shown in Table 4 below, the rate of dry etching of the O ₂ -based gas was investigated under etching conditions (2) shown below. It is sufficiently slow compared to the lower layer film and the upper layer resist film, and it is possible to pattern-transfer the silicon-containing intermediate layer to the lower layer as an etching mask.

Etching condition (2):

Chamber pressure 60.0 Pa

RF power 600 W

Ar gas flow rate 40 ml / min

O ₂ gas flow rate 60 ml / min

Gap 9 mm

Processing time 20 seconds

Moreover, the storage stability test was done. After the silicon-containing film-forming composition (Sol. 1 to 10) obtained above was stored at 30 ° C. for 1 month, the coating by the above-described method was carried out again to test whether a change in film formability occurred. The results are shown in Table 5 below.

From the results of Table 5, it was confirmed that the composition of any example had a storage stability of at least 6 months when converted to room temperature for 3 months or longer at 30 ° C.

From the above, it was confirmed that the composition and the silicon-containing film of the present invention are excellent in stability and lithography characteristics. By using such a composition, it becomes possible to process a substrate by pattern formation and etching using the highest NA exposure machine of the highest stage.

Claims (16)

(A) Silicon-containing compound obtained by hydrolyzing and condensing 1 type, or 2 or more types of mixtures chosen from the hydrolyzable silicon compound represented by following formula using at least 1 type of compound chosen from an inorganic acid and a sulfonic acid derivative as an acid catalyst, R ¹ _m1 Si (OR) _(4-m1) (Wherein R is an alkyl group having 1 to 3 carbon atoms, R ¹ is a group selected from a methyl group, an ethyl group, a phenyl group, and a group represented by the following formula, and m1 is 0 or 1)

(In the above formula, (Si) represents a bonding position with Si)) (B) 1 or 2 or more types selected from sulfonium compounds and ammonium compounds represented by the following general formulas (Q-1) and (Q-3) as thermal crosslinking accelerators,

(Wherein, R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each represent a phenyl group, R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ each represent a methyl group, A ⁻ represents a hydroxyl ion, formic acid ion, acetic acid ion, propionic acid ion, Butanic acid ion, pentanic acid ion, hexanoic acid ion, heptanoic acid ion, octanoic acid ion, nonanoic acid ion, decanoic acid ion, oleic acid ion, stearic acid ion, linoleic acid ion, linolenic acid ion, benzoic acid ion, p-methylbenzoic acid ion, pt-butylbenzoic acid ion, phthalate ion, isophthalic acid ion, terephthalate ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion, nitrate ion, chlorate ion, perchlorate ion, bromic acid Ions, iodide ions, oxalic acid ions, malonic acid ions, methylmalonic acid ions, ethylmalonic acid ions, propylmalonic acid ions, butylmalonic acid ions, dimethylmalonic acid ions, diethyl Non-nucleophilic counter ion selected from malonic acid ion, succinate ion, methyl succinate ion, glutaric acid ion, adipic acid ion, itaconic acid ion, maleic acid ion, fumaric acid ion, citraconic acid ion, citric acid ion, and carbonate ion Indicates (C) formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, Trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid , Organic acids selected from glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid, (D) monovalent or divalent or higher alcohol having a cyclic ether as a substituent, (E) organic solvent (except monovalent or divalent or higher alcohol having cyclic ether as substituent) A composition for forming a thermosetting silicon-containing film comprising a. 2. The acid catalyst of claim 1, wherein the silicon-containing compound substantially removes the acid catalyst from the reaction mixture obtained by hydrolytically condensing the hydrolyzable silicon compound using at least one compound selected from inorganic acids and sulfonic acid derivatives as acid catalysts. A composition for forming a thermosetting silicon-containing film, comprising a silicon-containing compound obtained through a process to be performed. The hydrolyzable silicon-containing compound according to claim 1 or 2, wherein the hydrolyzable silicon-containing compound is selected from tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, and a silane compound represented by the following formula: The composition for thermosetting silicon containing film formation characterized by the above-mentioned.

The composition for forming a thermosetting silicon-containing film according to claim 1 or 2, wherein the component (C) is an organic acid selected from oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid. The method according to claim 1 or 2, wherein the component (E) is selected from monoalkyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, and pentanediol. A composition for forming a thermosetting silicon-containing film. The composition for forming a thermosetting silicon-containing film according to claim 1 or 2, further comprising water. The composition for forming a thermosetting silicon-containing film according to claim 1 or 2, further comprising a photo acid generator. After forming an organic film on a to-be-processed board | substrate, forming a silicon containing film on it, and using the chemically amplified resist composition which does not contain silicon on it further, forming a resist film, pattern-processing this resist film, and then making this resist The silicon-containing film is pattern-processed using the film pattern, the processed silicon-containing film pattern is pattern-processed on the underlying organic film as an etching mask, and the processed organic film is used in a multilayer resist method for etching the substrate to be processed as an etching mask. A silicon-containing film, which is a silicon-containing film and is formed from the composition according to claim 1 or 2. The silicon containing film of Claim 8 used by the multilayer resist method which interposed the organic antireflective film between the resist film obtained from a chemically amplified resist composition, and a silicon containing film. An organic film, a silicon-containing film formed from the composition according to claim 1 on the organic film, and a photoresist film are sequentially formed thereon. An organic film, a silicon containing film formed from the composition of Claim 1 on this organic film, an organic antireflection film, and a photoresist film formed thereon in turn. The substrate according to claim 10 or 11, wherein the organic film is a film having an aromatic skeleton. As a method of forming a pattern on a substrate, the substrate according to claim 10 is prepared, the pattern circuit region of the photoresist film of the substrate is exposed, and then developed with a developer to form a resist pattern on the photoresist film. Dry etching the silicon-containing film using the formed photoresist film as an etching mask, etching the organic film using the silicon-containing film having the pattern as an etching mask, and etching the substrate using the organic film having the pattern as a mask to form a pattern on the substrate. The pattern formation method characterized by the above-mentioned. As a method of forming a pattern on a substrate, the substrate according to claim 11 is prepared, the pattern circuit region of the photoresist film of the substrate is exposed, and then developed with a developer to form a resist pattern on the photoresist film. The organic antireflection film and the silicon-containing film are dry-etched using the formed photoresist film as an etching mask, the organic film is etched using the silicon-containing film with the pattern as an etching mask, the substrate is etched with the organic film with the pattern as a mask, and the pattern is formed on the substrate. Forming method, characterized in that to form a. The pattern forming method according to claim 13 or 14, wherein the organic film is a film having an aromatic skeleton. The pattern formation method of Claim 13 or 14 using the photolithographic method using the light whose wavelength is 300 nm or less in formation of a resist pattern.