WO2002039187A1 - Compositions for under-resist film and processes for producing the same, and under-resist films and processes for producing the same - Google Patents

Abstract

Under-resist compositions for forming an under-resist film which has satisfactory gas permeability, excellent adhesion to resist films, and excellent resistance to developing solutions. The first composition comprises: a film-forming ingredient comprising a product of the hydrolysis and/or condensation of a specific silane compound; and a heat-volatilizable substance which gasifies upon heating. The second composition comprises a film-forming ingredient comprising a product of the hydrolysis and/or condensation of a specific silane compound with other silane compound having a thermally decomposable organic group. Upon heating, the film-forming ingredient in each composition cures and simultaneously therewith, a gas generates due to the gasification of the heat-volatilizable substance or from the thermally decomposable organic groups. Thus, both compositions form porous silica films.

Description

 Specification

 Composition for resist underlayer film and method for producing the same, and

 Resist underlayer film and method of manufacturing the same

 The present invention relates to a composition for a resist underlayer film for forming a lower layer film serving as a base when a resist pattern is formed on a substrate to be processed, a method for producing the same, and a resist underlayer film and a method for producing the same. Background technology

 In pattern formation in the manufacture of semiconductor devices, etc., the required microfabrication of substrates to be processed made of organic and inorganic materials is performed by pattern transfer methods that apply lithography technology, resist development process, and etching technology. It is being done.

 However, as the degree of integration of semiconductor elements and the like on a circuit board increases, it becomes difficult to accurately transfer the pattern of an optical mask to a resist film in an exposure step. Errors (out of order) may occur in the pattern dimensions due to the effects of standing waves of light formed therein. It is known that an antireflection film is formed between the resist film and the surface of the substrate to be processed in order to reduce the influence of such a standing wave.

 On the other hand, a resist pattern is used as a mask in the process of processing a substrate to be processed on which a silicon oxide film or an inorganic interlayer insulating film has been formed. However, as the pattern becomes finer, the thickness of the resist film is reduced. Therefore, it is not possible to obtain sufficient mask performance on the gate film, and as a result, it becomes difficult to perform required fine processing without damaging the substrate to be processed.

Therefore, an oxide film / interlayer insulating film processing lower layer film is formed on an oxide film of a substrate to be processed, a resist pattern is transferred to the lower layer film, and the processing lower layer film is used as a mask to form an oxide film or an oxide film. A process of dry-etching the interlayer insulating film is performed. here The lower layer film for karoe is a film that also functions as a lower antireflection film or a film formed below the antireflection film.

 However, in this process, since the etching rates of the resist film and the processing lower layer film are close to each other, a mask for processing the processing lower layer film itself is provided between the resist film and the processing lower layer film. It has been proposed to form a layer. Specifically, for example, there has been proposed a method of forming a multilayer film structure in which a processing lower layer film, a lower layer film processing mask, and a resist film are laminated in this order on an oxide film.

 The process of forming a pattern on each layer in a multilayer film structure having such a configuration is generally an etching process using a developing solution for a surface resist film, and an etching gas for a layer below a lower layer for force processing. In order to selectively etch the lower layer processing mask and the processing lower layer film, the lower layer 11 is usually an alkyl fluorine-based gas in order to form the lower processing mask pattern. A seed is used, and in order to form a pattern of the processing lower layer film, ashing using oxygen gas is performed by changing an etching gas type.

 However, in the process of assembling the processing lower layer film, the lower film processing mask may be broken, and it is difficult to accurately form a fine pattern. When the cause was clarified, it was found that the reason was that the lower processing mask) had a high density and did not have sufficient gas permeability.

 In addition, for the mask for processing the lower layer film, other characteristics such as a good resist pattern without tailing, excellent adhesion with the resist, and It is required that the mask for processing has sufficient mask performance, and that the solution forming the mask for processing the underlayer film has excellent storage stability, but a material satisfying all of these is not known. Disclosure of the invention

The present invention has been made in view of the above circumstances, and has as its object to have good gas permeability, excellent adhesion to a resist film, An object of the present invention is to provide a composition for a resist underlayer film having excellent resistance to a developing solution used for development, and a method for producing the same.

 Another object of the present invention is to provide a resist underlayer film having good gas permeability, excellent adhesion to a resist film, and excellent resistance to a developing solution used for developing the resist film, and a method for producing the same. To provide.

 The first composition for a resist underlayer film of the present invention comprises a film-forming component comprising a hydrolyzate of a silane compound (A) represented by the following general formula (A) and / or a condensate thereof; It contains a heat-volatile substance that gasifies,

The film is characterized in that a film-forming component is hardened by heating, and a heat-volatile substance is gasified to form pores, thereby forming a porous silicon film. General formula (A) Ri _a S i (OR ² ) 4— _a

(R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 3.)

 In the first resist underlayer film composition, the silane compound (A) related to the film-forming component is preferably a silane compound in which a is 0 or 1 in the general formula (A).

 Further, the heating volatile substance is preferably a substance having a boiling point or a decomposition temperature of 200 to 450 ° C, and the heating volatile substance may be poly (meth) acrylate, having 2 to 1 carbon atoms. Preferably, the aliphatic polyether compound is a polyalkylene oxide having a repeating unit containing an aethenole group, and is at least one selected from compounds having a naphthoquinonediazide structure.

 The first resist underlayer film composition preferably further contains an acid-generating compound that generates an acid by at least one of irradiation with ultraviolet light and heating.

The first resist underlayer jj trillions of the present invention, a thin film formed by the resist underlayer film composition is formed by curing by heating, the density is 0.7 to 1. In 8 / cm ³ It is characterized by comprising a certain porous silica film. In the first method for producing a resist underlayer film, a thin film is formed from the composition for a resist underlayer film described above, and the thin film is heated to a temperature equal to or higher than the boiling point or the decomposition temperature of the heat-volatile substance contained in the composition. By heating, the film-forming component is cured, and the volatile material is gasified to form pores, thereby forming a porous silicon film.

 The first composition for a resist underlayer film is used for forming an underlayer of a resist film formed on a substrate to be processed, and the composition is a film formed by hydrolysis and partial condensation of a silane compound. Since the film-forming component contains a heating volatile component together with the forming component, when the film-forming component is hardened by heating, the heating volatile component gasifies and volatilizes, resulting in a relatively low density in which many or innumerable pores are formed. Thus, a porous silica film having the following characteristics is formed. As a result, a resist underlayer film having an appropriate gas permeability is formed. Therefore, the resist underlayer film can reliably and easily attain the required gas etching with respect to the lower processing lower layer film by sufficiently transmitting the etching gas.

 The second composition for a resist underlayer film of the present invention comprises a silane compound (A) represented by the following general formula (A) and a silane compound (B) having a thermally decomposable group represented by the following general formula (B). )) And / or a film-forming component comprising a condensate thereof.

The film-forming component is cured by heating, and the thermally decomposable group-containing silane compound (B) generates gas to form pores, whereby a porous silica film is formed. General formula (A) RS i (OR ² ) 4— a

CR ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group (however, excluding a thermally decomposable organic group defined as R ^{3 in the} general formula (B) below), and R ² represents a monovalent organic group. And a represents an integer of 0 to 3. ] General formula (B) R ³ _b S i (OR ⁴ ) 4- _b

(R ^a represents a monovalent thermally decomposable organic group decomposed at 200 to ⁴⁰⁰ ° (R ⁴ represents a monovalent organic group, and b represents an integer of 1 to 3.)

 In the above second resist underlayer film composition, the thermally decomposable group-containing silane compound

(B) are the compounds of formula (B), thermally decomposable containing a thermally decomposable organic group, linear or branched aliphatic group with carbon number 6-2 5 containing R ^'1 force cycloaliphatic radical A silane compound which is an organic group or a thermophilic organic group containing an aliphatic polyether chain having an ether bond-containing repeating unit having 2 to 12 carbon atoms is preferable.

 The second resist underlayer film composition preferably further contains an acid generating compound that generates an acid by at least one of irradiation with ultraviolet light and heating.

 The second method for producing a resist underlayer film composition comprises hydrolyzing the silane compound (A) and the thermally decomposable group-containing silane compound (B) in an organic solvent in the presence of water and a catalyst. And a step of partially condensing.

The second resist underlayer film of the present invention, a thin film formed by the resist underlayer film composition is formed by curing by heating, the density is 0.7 to 1. In 8 g / cm ³ It is characterized by comprising a certain porous silica film.

 In the second method for producing a resist underlayer film of the present invention, a thin film is formed from the above-described composition for a resist underlayer film, and the thin film is formed from the thermally decomposable group-containing silane compound (B) contained in the composition. Producing a porous silica film by heating to a temperature equal to or higher than the decomposition temperature of the thermally decomposable organic group, thereby forming film-forming components and generating gas to form pores. I do.

The second resist underlayer film composition of the present invention is used for forming an underlayer of a resist film formed on a substrate to be processed, and the composition is obtained by hydrolysis and partial condensation of a silane compound. When the film-forming component contains a silane compound (B) containing a thermally decomposable group as a part of the film-forming component, the film-forming component is hardened by heating. Gas is generated from the silane compound (B) As a result, a relatively low-density, porous silicon film having a large number or a large number of holes is formed, and eventually, a resist underlayer film having an appropriate gas permeability is formed. Therefore, this resist underlayer film can reliably and easily achieve the required gas etching on the lower processing lower layer film by sufficiently transmitting the etching gas.

 Further, in each of the first resist underlayer film composition and the second resist underlayer film composition, the film-forming component comprises a hydrolyzate and / or condensate of a specific silane compound. Because it is porous, it has high adhesion to resist despite being porous, and has sufficiently large resistance to resist developing solution and oxygen gas for ashes for removing resist, and has high reproducibility in resist film A resist underlayer film on which a resist pattern is formed can be formed, and excellent storage stability can be obtained. Industrial applicability

 The composition for a resist underlayer film of the present invention is used for forming a base layer of a resist film formed on a substrate to be processed. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described in detail.

 (First resist underlayer film composition)

 The first resist underlayer film composition of the present invention will be described.

 The first composition for a resist underlayer film of the present invention basically comprises a film-forming component composed of a specific substance, and a heat-volatile substance which is gasified and volatilized by heating.

 In the first resist underlayer film composition, a hydrolyzate of a silane compound (A) represented by the above general formula (A) and / or a condensate thereof is used as a film-forming component as a main component.

In the general formula (A) relating to the silane compound (A), R ′ is a hydrogen atom, fluorine Is an atom or a monovalent organic group, and R ² is a monovalent organic group. Examples of the monovalent organic group include aryl, alkyl and glycidyl groups. .

 Specific examples of the alkyl group include C1 to C5 alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group. These alkyl groups may be linear or branched, and may be a fluorinated alkyl group in which some or all of the hydrogen atoms have been replaced by fluorine atoms.

 Specific examples of the aryl group include a phenyl group, a naphthyl group, a tosyl group, an ethylphenyl group, a phenyl group, a bromophenyl group, and a fluorophenyl group.

 Examples of the silane compound (A) represented by the general formula (A) include the following silane compounds (1) to (5).

Silane compounds (1)

In the general formula (A), a force U, R ¹ is a hydrogen atom or a fluorine atom, and R ² is an alkyl group or a phenyl group having 1 to 5 carbon atoms.

 Specific examples thereof include, for example, trimethoxysilane, triethoxysilane, and triethoxysilane.

—N—propoxysilane, tree iso-propoxysilane, tree η-butoxysilane, tri-sec —butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n— Examples include propoxysilane, fluorotri-iso-propoxysilane, phenololorin n-butoxysilane, phenololorin sec-butoxysilane, fluororhyl tert-butoxysilane, and fluorotrifluorophenoxysilane.

Silane compounds (2)

A silane compound represented by the formula (A), wherein a is 0 and R ² is an alkyl group or a phenyl group having 1 to 5 carbon atoms;

Specific examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra- Examples thereof include n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and tetraphenoxysilane.

Silane compounds (3)

In the general formula (A), a force 1 and R ¹ are an alkyl group or substituted alkyl group having 1 to 5 carbon atoms, a butyl group or a phenyl group, and R ² is an alkyl group having 1 to 5 carbon atoms or a phenyl group. Silane compound

 Specific examples include methyltrimethoxysilane, methyltriethoxysilane, methyl_n-propoxysilane, methinoletri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, Methinoletriphenoxysilane, eth ^ / trimethyoxysilane, ethithriethoxysilane, ethinoletri- η-propoxysilane, ethynorietri iso-propoxysilane, ethynoletri-n-butoxysilane, ethinoletrie sec-butoxysilane, ethinoletri Butoxysilane, ethynoletriphenoxysilane, virtrimethoxysilane, bienotriethoxysilane, burtri-n-propoxysilane, burtri-iso Loxy silane, vinylinole n-butoxysilane, vinylin-sec—butoxysilane, vinyl ^^ tert-butoxysilane, vinylinoletriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n— Propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyl ^^ Enoxysilane, iso—propinoletrimethoxysilane, iso—propyltriethoxysilane, iso—propyltri-n-propoxysilane, iso_propinoletrione is 0—propoxysilane, iso—propynoletri-n—butoxysilane, iso—propylto Over s e c - butoxysilane, i s o- Puropinoretori t e r t - butoxysilane, i s 0- prop Norre triflate Enoki Sissi run,

n-butyl ^^ trimethoxysilane, n-butynoletriethoxysilane, n-butynoleto L-n-propoxysilane, n-butyl tree is 0-propoxy silane, n-butyl tree n-butoxy silane, n-butynoletri-sec-butoxy silane, n-buty ^^ tri-tert-butoxy silane, n-buty ^^ Triphenoxysilane, sec-butynoletrimethoxysilane, sec-butynole iso-triethoxysilane, sec-butyl-tree n-propoxysilane, sec-butyl-tri-is 0-propoxysilane, sec-butylinoletri-n-butoxysilane , Sec-butynole-sec-sec-butoxysilane, sec-butylintri-tert-butoxysilane, sec-butynole-triphenoxysilane, tert-butyltrimethoxysilane, tert-butynoletriethoxysilane, tert-butyltri-n —Propoxysilane, tert-butyltri-iso-propoxysilane, tert —Butyl tri-n-butoxysilane, tert-butyl tri-sec-butoxy silane, tert-butyl tri-tert-butoxy silane, tert-buty ^^ triphenoxy silane, pheny trimethyoxy silane, fueno tri tri toxic silane, phenole tri-n-propoxy silane, fuel tri — Iso-propoxysilane, phenyltri-n-butoxysilane, phenoltri-sec-butoxysilane, pheninoletri tert-butoxysilane, phenoletrifrenoxysilane, γ-aminopropinoletrimethoxysilane, γ-aminopropyl pills triethoxysilane, _gamma - glycidoxypropyltrimethoxysilane main Tokishishiran, gamma

—Glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, and γ-trifluoropropyltriethoxysilane.

Silane compound (4).

In the general formula (Α), a is 2, R ′ is an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group, a Bier group or a phenyl group, and R ² is an alkyl group having 1 to 5 carbon atoms or a phenyl group. Silane compound

Specific examples thereof include, for example, dimethyldimethoxysilane, dimethyljetoxysilane, dimethinoledi-n-propoxysilane, dimethylzie iso-propoxysilane, dimethinolezie n-butoxysilane, dimethylzie sec-butoxysilane. Xysilane, dimethyl tert-butoxy silane, dimethyl diphenoxy silane, methinoresimethoxy silane, getyl ethoxy silane, cetino rage 1 n-propoxy silane, cetino razy iso—propoxy silane, cetino les n-butoxy silane, cetino rage—sec_butoxy Getinole-di-tert-butoxysilane, di-Λ ^ diphenoxysilane, di-n-propyldimethyoxysilane, di-n-propyljetoxysilane, di-n-propynolage-n-propoxysilane, di-n-propyl Di-iso-propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propy ^ / —Geoff Nonoxysilane, di-iso-propyl methoxysilane, di-iso-propyl ethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl di-is 0—propoxysilane, di-iso-propynolage—n-butoxysilane , Di-iso-propyl-di-sec-butoxysilane, is-0-propynolase tert-butoxysilane, di-iso-propyl-di-phenoxysilane,

Di-n-butydimethoxysilane, di-η-butydiethoxysilane, di-η-buty-di-η-propoxysilane, di-η-butynorethy iso-propoxysilane, di-n-butynoriezy n-butoxysilane, zyn -Butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n-buty-diphenoxysilane, di-sec-buty ^^ dimethoxysilane, di-sec-butyl ethoxy Silane, g-sec-butyldi-n-propoxysilane, g-sec-butynolage-is 0-propoxysilane, di-sec-butyl-di-n-butoxysilane, g-sec-butynole-sec-butoxysilane, g-sec-butynole -G-tert-butoxysilane, G-sec-butynole-G-phenoxysilane, di-tert-petit dimethoxy Orchid, g-tert-butynolegetoxysilane, di-tert-butynolexy n-propoxysilane, g-tert-butylyl iso-propoxysilane, di-tert-butynolesy n-butoxysilane, di-tert-butynolage sec — butoxy Silane, di-tert-butynoledi-tert-butoxysilane, di-tert-buty ^^-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-ethoxyethoxysilane, diphenylethoxy-n-propoxysilane, diphenyl Di-iso-propoxysilane, diphenyloxy-n-butoxysilane, diphenylol-sec-butoxysilane, diphenylino-tert-butoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, di-gamma-aminopyrudylmethoxysilane, Di-γ-aminopropyljetoxysilane, di-γ-glycidoxypropyldimethoxysilane, di-γ-glycidoxypropyljetoxirane, di-γ-trifluoropropione> ^ resinmethoxysilane Toxisila And the like.

Silane compounds (5)

In the general formula (Α), a is 3, R ¹ is an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group, a vinyl group or a fuel group, and R ² is an alkyl group having 1 to 5 carbon atoms or a fuel. Silane compound

Specific examples thereof Bok Rimechirumonome Tokishishiran, Torimechirumono silane, Torimechirumono - n- Purobokishishiran, Torimechirumono - IS _o - Purobokishishiran, trimethylene mono- n- Butokishishishiran, Torimechinore mono- sec- Butokishishishiran, Torimechinoremono one tert —Butoxysisilane, Trimethylmonophenoxysilane, Triethylmonomethoxysilane, Triethylmonoethoxysilane, Triethylmono— n-Propoxysilane, Triethyl mono — is 0—Propoxysilane, Triethyl mono—n—Butoxysilane, Triethyl —Butoxysilane, triethynolemono— tert —butoxysilane, triethylmonophenoxysilane, tri-n-propylmono-n-propylmethoxysilane, Tree n-propyl mono-n-ethoxysilane, tri-n-propynolemono-n-propoxysilane, tree. Iso-propyl mono-n-propoxysilane, tree n-propy ^^ mono-n-butoxysilane, tree n-propyl mono tert—butoxysilane, tree n-propyl mono-sec—butoxysilane, tri-n-propyl monophenoxysilane, tree iso—propi Lumonomethoxysilane, tri-is 0-propylmono-n-propoxysilane, tri-iso-propylmono-iso-propoxysilane, tri-iso-propylmono-n-butoxysilane, triiso-propylmono-sec-butoxysilane, tri- iso-propylmono-tert-butoxysilane, tree is 0-propylmonophenoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysilane, triphenylmono-n-propoxysilane, triphenylmono_iso-propoxysilane, Triphenylenyl-n-butoxysilane, triphenyl-2-sec-butoxysilane, triphenyleno-tert-butoxysilane and triphenylmonophenoxysilane can be exemplified.

 Among them, preferred as the silane compound (2) are tetramethoxysilane, tetraethoxysilane, tetra-η-propoxysilane, tetra-is0-propoxysilane and tetraphenoxysilane.

 Preferred as the silane compound (3) are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, vinyltriethoxysilane, isotrimethylsilane. —Propyltrimethoxysilane, iso —propyltriethoxysilane, n-butyltrimethoxysilane, n-butylinoletriethoxysilane, iso-butynoletrimethoxysilane, iso —butyltriethoxysilane, tert —butyltrimethoxysilane, tert —butyl Noretriethoxysilane, furtrimethoxysilane and phenyltriethoxysilane.

Preferred as the silane compound (4) are dimethydimethoxysilane, dimethylethylethoxysilane, getyldimethoxysilane, getyljetoxysilane, diphenyldimethoxysilane and diphenylethoxysilane. Preferred as the silane compound (5) are trimethyl monomethoxy silane, trimethyl monoethoxy silane, triethyl monomethoxy silane, triethyl monoethoxy silane, triphenyl monomethoxy silane and triphenyl monoethyl. It is toxic silane.

 The above silane compound (A) may be used alone or in combination of two or more. In the case of using monoalkoxysilane in which the value of a in the general formula (A) is a silane compound (A) having a value of 2 or dianolekoxysilane in which the value of a is a silane compound (A) having a value of 3, In order to obtain a composition having excellent curability, it is preferable to use one or more of tetraalkoxysilanes and trialkoxysilanes, which are silane compounds (A) having a value of 0 to 1. . In this case, the proportion of the monoalkoxysilane or dialkoxysilane is in the range of 1 to 50% by mass of the entire silane compound (A). When two or more silane compounds (A) other than the above are used, their relative proportions are not particularly limited.

 A catalyst is used to hydrolyze and / or condense the silane compound (A).

 Examples of the catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

 Metal chelate compounds used as catalysts include, for example, triethoxy mono (acetyl acetonato) titanium, tri-n-propoxy.mono (acetyl acetonato) titanium, tree iso-propoxy 'mono (acetinol acetonate) Titanium, tri-n-butoxy.mono (acetinolecetate) titanium, tri-sec-butoxy'mono (acetyl acetatetonate) titanium, tri-tert-butoxy * mono (acetylacetonate) titanium, Diethoxy bis (acetylacetonate) Titanium, di-n-propoxy 'bis (acetyacetonate) titanium, di-iso-propoxy' bis (acetylaceto "^") titanium, g-butoxy bis (acetylacetonate) Titanium, G sec-butoxy bis

(Acetyl acetonato) Titanium, di-tert-butoxy bis (acetinolea cetatonate) Titanium, monoethoxy 'tris (acetyl acetonato) Titanium, mono-n-propoxy' tris (acetylacetonato) Titanium, mono-iso-propoxy. Tris (acetylacetonato) Titanium, mono-n-butoxy. Tris (acetylacetonato) titanium, mono-sec-butoxy tris (acetacetate) titanium, mono-tert-butoxy-tris (acetinoleacet ^) titanium, tetrakis (acetisacetonato) titanium,

 Triethoxy 'mono (ethyl acetate) titanium, tree η-propoxy

• Mono (ethyl acetate) Titanium, tri-is 0—Proboxy. Mono (ethyl acetate) Titanium, tri-n-butoxy. Mono (ethyl acetate) Titanium, tri-sec—butoxy 'mono Tinoleacetoacetate) Titanium, tri-tert-butoxy 'mono (ethylacetoacetate) Titanium, diethoxy. Bis (ethylinoacetoacetate) Titanium, di-n-propoxy. Bis (ethylacetoacetate) Titanium, G-iso-propoxy. Bis (ethyl acetate) titanium, di-n-butoxy 'bis (ethyl acetate acetate) titanium, di-sec-butoxy bis (ethylinoacetoacetate) titanium, di _ tert-butoxy 'bis (ethyl acetate) titanium, monoethoxy

'Tris (ethyl acetate) titanium, mono-n-propoxy' Tris (ethyl acetate) titanium, mono-iso-propoxy. Tris (ethyl acetate) titanium, mono-n-butoxy. Tris (ethyl) Titanium, mono-sec-butoxy 'tris (ethy ^^ acetoacetate) titanium, mono-tert-butoxy' tris (ethyl acetate) titanium, tetrakis (ethyl acetate acetate) titanium, mono (monoacetate) Cetyl acetate toner Tris (ethyl acetate acetate) Titanium, bis (acetyl acetate toner) Bis (ethyl acetate acetate) Titanium, tris (acetyl acetate toner) Mono (ethyl acetate acetate) Titanium chelate compounds such as titanium;

Triethoxy .mono (acetylacetonate) dinoreconium, tree _n- propoxy 'mono (acetylacetonate) dinoreconium, tree is ο—propoxy

'Mono (acetyl acetatetonate) zircoium, tri-n-butoxy' Mono (acetyl acetate) dinoreco-pam, tri-sec-butoxy 'mono (acetinoleacetonato) dinorecoium, tri-tert-butoxy. Aceti ^ / acetonato) zinoreconidum, diethoxy 'bis (acetylacetonato) zirconium Gam, G n-propoxy 'bis (acetyl acetate) zirconium, di-iso-propoxy' bis (acetacetonate) dinoreconidum, di-η-butoxy bis (acetia acetate) dinoreco-pam, di- sec —butoxy bis (acety ^ acetonato) dinoreconidum, g-tert-butoxy 'bis (acetyl acetatenato) zirconium, monoethoxy. tris (acetyl acetate naat) zirconium, mono-n-propoxy' tris (acetyl acetate) Natto) dinorecium, mono-iso-propoxy 'tris (acetylacetonato) zirconium, mono-n-putoxy' tris (acetylacetonato) dinorecum, mono-sec — butoxy. Tris (acetylacetate) Nart) zirconium, mono-ter t—butoxy. tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium,

Triethoxy.mono (ethyl acetate) zirconium, tri-n-propoxy 'mono (eth ^^ acetoacetate) zirconium, tree iso-propoxy.mono (ethyl acetate acetate) disresiconium, tri-η-butoxy * Mono (ethyl acetate) zirconium, tri-sec-butoxy 'mono (ethyl acetate acetate) zirconium, tree tert -butoxy' mono (ethyl ^^ acetoacetate) diconium, diethoxy 'bis Ginolecoium, G-n-propoxy 'bis (ethyacetoacetate) gilcoium, di-is 0-Proboxy' bis (ethyacetate acetate) zirconium, di-n-butoxy 'Bis (ethyl acetate acetate) zirconium, di-sec-butoxy · Bis (ethyl acetate) zircoium, g-tert-butoxy 'bis (ethyl acetate acetate) zirconium, monoethoxy, tris (ethyl acetate acetate) zirconium, mono-n-propoxy tris (Cetoacetate) dinoreconidum, mono-iso-propoxy 'tris (eth ^^ acetoacetate) dinolecodium, mono-n-butoxy' tris (ethylinoacetoacetate) zirconium, mono-sec-butoxy 'tris (ethyl acetate) Tetrate) zirconium, mono-tert-butoxy tris (ethyl acetate acetate) zirconium, tetrakis (ethyl acetate acetate) Zirconium, mono (acetyl acetate) tris (ethyl acetate) zirconium, bis (acetyl acetate) bis (ethyl acetate) dinoreconium, tris (acetyl acetate) mono (ethino) Leacoacetate) dinoreconium chelate toys such as ginoreconium;

 Aluminum chelate compounds such as tris (acetyl acetateton) anoreminium, tris (ethinoleacetoacetate) aluminum;

Others can be mentioned.

 Organic acids include, for example, carboxylic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid , Gallic acid, butyric acid, melitic acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p — Toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid tartaric acid, etc. it can.

 Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

 Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethylethanolanolamine, and triethanolamine. Min, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like.

 As the inorganic base, for example, ammonia, sodium hydroxide, potassium hydroxide, hydroxypropyl parium, calcium hydroxide and the like can be mentioned.

Among these catalysts, preferred are a metal chelate compound, an organic acid and an inorganic acid, and more preferred are a titanium chelate compound and an organic acid. These catalysts can be used alone or in combination of two or more. Wear.

 The amount of the catalyst to be used is usually 0.01 to 10 parts by mass, preferably 0.00 parts by mass, per 100 parts by mass of the silane compound (A) (converted as a complete hydrolysis condensate). It is in the range of 1 to 10 parts by mass.

 In order to carry out hydrolysis and partial condensation of the silane compound (A), it is necessary to add 0.25 to 3 monoles, particularly 0.3 to 2.5 mol of water per mole of the alkoxy group in the entire silane compound. Preferably, in this case, the coating film formed by the obtained composition for a resist underlayer film has high uniformity, and the composition surely has high storage stability.

 Specifically, water may be added intermittently or continuously to an organic solvent in which the silane compound (A) is dissolved. The catalyst may be added to an organic solvent in advance, or may be dissolved or dispersed in water to be added. The reaction temperature of the hydrolysis and the partial condensation is usually 0 to: L00 °, preferably 15 to 80 ° C. The heating volatile substance which is blended with the above film-forming components to form the first resist underlayer film composition has a boiling point or decomposition temperature of 200 to 450 ° C and is heated to such a temperature. It is a compound that gasifies and volatilizes when it is burned. Here, the boiling point or the 温度 temperature indicates the temperature at 1 atm.

 Heat-volatile substances include ether bonds, ester bonds, amide bonds, carbonate bonds, urea bonds, sulfide bonds, sulfol bonds, amino bonds, carboyl bonds, hydroxyl groups, thiol groups, amino groups, etc. It is preferably a hydrocarbon organic compound containing a group. Carbon dihydrogen compounds containing no such bond or group have a low compatibility with the film-forming component, so that a transparent coating film cannot be obtained, and large pores tend to be formed in the film. In addition, the resist pattern Jung performance may be deteriorated.

Specific examples of the heating volatile substance include, for example, a compound having a polyalkylene oxide compound, a compound having a naphthoquinonediazide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate polymer, and a lipophilic compound. Examples include a combination of a compound and a dispersant, and ultrafine particles. When the heating volatile substance is a compound having a boiling point or a decomposition temperature of less than 200 ° C, the substance is gasified before the film-forming component is cured, so that the required pores are not formed in the film. On the other hand, if the substance has a boiling point or decomposition temperature of more than 450 ° C, pores are formed in the coating film because the curing of the film-forming components progresses significantly before gasification. Therefore, in each case, it is difficult to obtain a resist underlayer film having a required gas permeability.

 The mixing ratio of the heat-volatile substance in the composition for a resist underlayer film varies depending on the type of the film-forming component and the type of the heat-volatile substance, but is usually 100 parts by mass of the film-forming component. The range is 0.1 to 80 parts by mass, preferably 1 to 50 parts by mass. If the proportion of the heat-volatile substance is too large, the strength of the obtained resist underlayer film will be low, while if it is too small, it is difficult to form the desired porous silicon film. .

 Hereinafter, a substance useful as a heat volatile substance will be described.

 (1) Compound having a polyalkylene oxide structure

 Examples of the polyalkylene oxide structure in this compound include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure.

Specific examples of the compounds include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, Ether-type compounds such as polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sonorebitol fatty acid ester , Ester type compounds such as polyoxyethylene fatty acid alcohol amide sulfate, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty Monoguriseri de, Poridariserin fatty acid esters, sorbitan tail fatty Esuteru, propylene glycol fatty acid Esuteru, sucrose fatty acid E Examples thereof include ether ester type compounds such as stell.

 (2) Compound having naphthoquinonediazide structure

 Examples of the compound having a naphthoquinonediazide structure include naphthoquinone-1,1,2-diazido-5-sulfonic acid ester of a compound having a phenol structure.

Compounds having a phenol structure include phenol, methylphenol, dimethylphenol, trimethylphenol, tetramethylphenol, pentamethylphenylphenol, resorcinol, catechol, hydroquinone, bisphenolenole A, dihydroxybenzophenone, dihydroxydiphenylsulfone, dihydro Examples thereof include xyldiphenyl ether, dihydroxydiphenylmethane, resorcinol allene compound, phyllixallene compound, and the following compounds (2-1) to (2-12) and others.

(3) Compound having sugar chain structure

 Compounds having a sugar chain structure include cyclodextrin, sucrose ester, oligosaccharide, glucose, fructose, mannitol, starch sugar, D-sorbitol, dextra, xanthan gum, curdlan, pullulan, cycloamylose, isomerized sugar, multi Examples thereof include tall, cellulose acetate, cellulose, carboxymethyl cellulose, hydroxyxethylesenorelose, hydroxypropinoresenorelose, methinoresenololose, ethylhydroxyethyl cellulose, chitin, chitosan and the like.

 The cyclodextrin is represented by the following formula (1), wherein n is 6 (hypercyclodextrin), 7 cyclodextrin) or 8 (γ-cyclodextrin).

Equation (1)

The compound having a sugar chain structure used as a heat-volatile substance is preferably a compound in which a part or all of a hydroxyl group or an amino group is modified. Examples of the chemical modification of the hydroxyl group include etherification, esterification, modification including a trialkylsilinole bond and a urethane bond. Examples of the chemical modification of an amino group include introduction of an amide bond, a urea bond, and an imide bond.

Among the compounds having a sugar chain structure described above, cyclodextrin is preferred as a heat-volatile substance because the pores formed in the coating film have a small diameter and the pore diameter can be controlled. When chemically modified, trialkylsilyl modification or ゥ It is preferable to be modified by rethanization, and particularly preferable to be modified by trimethylsilinole.

 In order to modify a compound having a sugar chain structure with a trimethylsilyl group, a compound having a sugar chain structure may be reacted with a trimethylsilylating agent such as trimethylchlorosilane or trimethylsilyl acetamide, which usually has a sugar chain structure. What is necessary is just to substitute 5 to 100% of the hydroxyl groups of the compound.

 In order to urethanize a compound having a sugar chain structure, a compound having a sugar chain structure may be reacted with a urethanizing agent such as pheninoleisocyanate or hexinoleisocyanate. Usually, 5 to 100% of the hydroxyl groups of the compound having a sugar chain structure may be substituted.

 (4) Bullamide polymer

 Examples of the vinylamide polymer include poly (N-vinylacetamide), poly (N-bininolepyrrolidone, poly (2-methyl-2-oxazoline), and poly (N, N-dimethylacrylamide). .

 (5) (Meth) acrylate polymer

 (Meth) acrylate polymers include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, (meth) benzyl acrylate, (meth) tetrahydrofurfuryl acrylate, (meth) ) Glycidyl acrylate, hydroxyxetinole (meth) acrylate, (meth) acrylamide, hydroxypropyl (meth) acrylate, etc. Radical polymerizable monomer polymer or copolymer with (meth) acrylate ester be able to.

 (6) Lipophilic compound and dispersant

 Many lipophilic compounds and dispersants do not have sufficient compatibility with the film-forming components when used alone.However, when combined with a dispersant, sufficient compatibility can be obtained. It can be used as a volatile substance.

Examples of the lipophilic compound include didecyl phthalate, didecinolephthalate, didodecino phthalate, ditridecyl phthalate, tris (2-ethylhexyl) trimellitate, tridecyl trimellitate, tridodecyl trimellitate Polycarboxylates such as, tetraptinolepyromellitate, tetrahexyl trimellitate, tetraoctyl pyromellitate, bis (2-ethylhexyl) dodecandioate, bisdecyldecanedioate, and the like. Monkey

 Dispersants that can be combined with these lipophilic compounds include higher alcohols such as octanol, lauryl alcohol, decyl alcohol, and decyl alcohol.

 The higher alcohol as a dispersant is used in an amount of 0.1 to 10 times the mass of the lipophilic compound.

 (7) Ultra fine particles

 Ultrafine particles are polymer particles having a particle diameter of 100 nm or less. For example, in ordinary emulsion polymerization,? The particle size is controlled by regulating conditions such as the type of precipitating agent, emulsifier concentration, and stirring speed. For example, (meth) atalylate compounds are used as monomers and Some are prepared using a crosslinkable monomer for controlling the particle size.

 The first resist underlayer film composition is prepared by dissolving or dispersing the above film-forming component and the heat-volatile substance in an appropriate solvent.

 Here, the solvent is not particularly limited as long as it is an organic solvent used for this kind of application. In particular, propylene glycol monoethyl ether, propylene glycol monomethyl monomethyl ether ether, propylene glycol Rikonoremonopropinoleter and the like are preferably used.

An acid generator can be added to the first resist underlayer film composition. According to the composition containing an acid generator, an acid is generated in the resist underlayer film by the action of heat or light. As a result, in forming a resist pattern, the reproducibility of a good mask pattern and the rectangularity of the cross-sectional contour are high! _This is preferable because a resist pattern can be formed.

Acid generators include latent thermal acid generators or latent acid generators. The latent thermal acid generator is a compound that generates an acid when heated to usually 50 to 450 ° C., preferably 200 to 350 ° C., and includes a sulfo- ゥ salt and a benzothiazolyte. Salts such as sodium salt, ammonium salt and phosphonium salt are used.

 Specific examples of the sulfonium salt used as the latent thermal acid generator include 4-acetopheno-noresimetinoles / lefonium hexafenoleoantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, Dimethinole-4-(benzinoleoxycarbonyloxy) phenylsolephonium hexafenoleantimonate, dimethyl 41- (benzoinoleoxy) phenyls ^^ lefonium hexafenoleoantimonate, dimethy ^^ — 41- (Benzoinoleoxy) phenylsnorefonium hexafluorene arsenate, dimethyl-3-chloro-1,4-acetoxyphenyl-sulfonium hexolefluoronormonone such as hexafluoroantimonate Pum salt;

To benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, to benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, to 4-acetoxyphenylbenzinolemethylsulfonium Kissuboloantimonate, Benzinole-4-Methoxyphenylmethylsulfodium Hexafluoroantimonate, Benzyl-2-methyl-4-hydroxyphenylenolemethylsnorefonium Hexabutanoleoantimonate Benzinole 3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzointoshi Rate, vanes such as 2-trobensilt syrup / Resunorehoeumu salt;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dipendinoleate 4-hydroxyphenylenolesolenium hexafenoleophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, Dibenzyl-4-methoxyphenylsnorrefuium hexafluo mouth antimonate, dipendinole 3-chloro-1,4-hydroxyhydroxyphenylsnolefonium hexafenoleoloarsenate, dibenzyl-3-methyl-4-hydroxy 1-5-tert-Butylphenylenosulfonium hexafluoroantimonate, benzizole-4-methoxybenzinole-4-dihydroxyphenylenolesnorefonium dibenzylsulfonate such as hexafluorophosphate Salt;

p-Black mouth Benzinole 4—Hydroxypheninolemethinoresnorethoyum hexaforenoantimonate, p-Nitrobenzyl-4-hydroxyphenylmethylsnolehonemexafluoroantimonate, p—Cro mouth Benzyl 4-hydroxyphenyl methinolesnorefonium hexafenoleophosphate, p-nitrobenzyl-3-methyl-4-hydroxyhydroxymethylsulfonium hexafluorate antimonate, 3,5-dichloro Oral Benzinole 4-Hydroxyphenylmethinole Snorrefonium Hexafenoleo Antimonate, o-Chlorovenezynole 3 -Chloro mouth _ 4-Hydroxyphenylemethinoresnorrefoam Hexafenoleo Antimonate Substituted benzylinolesulfo-pium salts.

 Specific examples of benzothiazonium salts include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzinobenzobenzothiazolym hexafluorophosphate, and 3-benzoylbenzo. Thiazolym tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazolym hexafluoroan thymonate, 3-benzyl-2-methylthiobenzothiazolym hexafluoro Mouth antimonate, 3-benzylyl 5 Benzyl benzothiazolym salts such as benzothiazolym hexafluoroantimonate can be mentioned. In addition, thermal acid generators other than the above include 2, 4, 4, 6-tetrabromocyclo Xixenone can be exemplified.

Among these, 4-acetoxyphenyldimethylsulfodium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and 4-acetoxyphenylbenzylmethinoresulfonium hexafnoreole Antimonate, dibenzinole 4 -hydroxyphenolenoresolenium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3 -benzinolebenzothiazolym Hexafluoroantimonate is preferably used.

 These commercial products include San-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (Sanshin Chemical Industries, Ltd.) Co., Ltd.).

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

 The latent photoacid generator is usually a compound that generates an acid by irradiation of an energy of 1 to: L00 mJ, preferably 10 to 50 mJ, with ultraviolet light.

 Latent photoacid generators include, for example, diphenyleododium trifluoromethanesulfonate, diphenyleodoniumpyrenesulfonate, diphenylidenodium dodecamedodecylbenzenesulfonate, diphenyleodomium nononaphnoate N-butanesulfonate, bis (4-tert-butynolephenyl) eodonium trifluoromethanesulfonate, bis (4-tert-butynolephenyl) iodonium dodecylbenzenesulfonate, bis (4-tert-butylphenyl) eodonium Naphthalenesulfonate, bis (4-tert-butylphenyl) eodoniumhexafluoroantimonate, bis (4-tert-butynolephenyl) eodoniumnonafluoro n-butanesulfonate, triffee-noresnolehonimid Fluoromethanesulfonate, triphenylsulfoniumhexahexanol antimonate, triphenylenolesnorehopenymnaphthalenesnorefonate, triphenylsulfonium nonafluoride n-butanesulfonate, diphen- Le (4-1 methylphenyinole) Snorrehoeium trifnoroleolomethanesnolefonate, diphenyl (4-methyltoxyl) sulfoium trifluoromethanesulfonate, (hydroxyphene) benzene methinoresphenol Tonorensurenorehonate, hexyl hexyl methinole (2-oxocyclohexanol) sunorephonium trifluorophenol methanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesnolephonate,

Dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, diphenododenium hexafluoroantimonate, triphenylenole, snorelephonium camphorsolenate, (4-hydroxyphenyole) benzinoleme Chinoles honolemutonoreensunorehonate, 1-naphthinoresmethinolesulfonium trifluoromethanesulfonate, 1-naphthyl getylsulfonium trifluorophenol methanesulfonate, 4-cyano-1-naphthyldimethylsulfonate Mutrif phenol trifluoromethanesulfonate, 4-112 1-naphthinoresmethinolesnorefony dimethyl trifluoromethanesulfonate, 4-methylinole 1-naphthyldimethylsulfonium trifluoromethyl methanesulfonate, 4-cyano-1 1-Naphthyl-Jetyl-sulfonium trifluoromethanesulfonate, 4-Nitro 1-naphthyl-ethyl-sulfoium trifluoromethanesulfonate, 4-Methyl-1-naphthyl-ethyl-sulfonium trifluoromethanesulfonate, 4-H Droxy 1-Naphthyl'dimethylsnolephonium trifluoromethanesulfonate methanesulfonate, 4-hydroxy-1-naphthinoletetrahydrothiophene dimethyl trifluoromethanesulfonate, 4-methoxy-1-naphthyl tetrahydrothiophene trifluoromethanesulfonate Hornet, 4-ethoxy-11-naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4-methoxymethoxyl-naphthyltetrahydrothiophene trifluoromethanesulfonate, 4-ethoxymethoxy1-1- Naphthyltetrahydrothiophene trifluoromethanesulfonate, 4- (1-methoxetoxy) 111-naphthyltetrahydrothiophene trifluoromethanesulfonate, 4- (2-methoxetoxy) 1-1-naphthyltetrahydrotin 4-dimethyltrifluoromethanesulfonate, 4-methoxycarbonyldifluoromethanesulfonate, 4-naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4 — Η-Propoxycarbonyloxy 1-na-fuchinoletetrahydro-drothio-euum-trif-norolelomethanes-norlefonate,

4-is ο-propoxycarbonyloxy 1-naphthyltetrahydrothiophene dimethyltrifluoromethanesulfonate, 41-n-butoxycanolebonyloxy- 1 —naphthyltetrahydrothiophene trifluoromethanesulfonate, 41-tert- Butoxycarbonyloxy— 1-naphthyltetrahydrothiophenyitrifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) 1 1 1-Naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4- (2-tetrahydrobiranyloxy) — 1-naphthyltetrahydrothiophenedimethyltrifluoromethanesulfonate, 4-benzyloxy-1 1-naphthyltetrahydrohydrothio Photoacid generators such as phenyl trifluoromethanesulfonate, 1- (naphthyl acetomethyl) tetrahydrothiophenyl trifluoromethanesulfone, etc .; phos-inolebis (trichloromethinole) — s — triazine; Halogen-containing compound based photoacid generators such as methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthinolebis (trichloromethyl) -s-triazine;

 1,2-Naphthoquinonediazido 4-sulfonyl chloride, 1,2-naphthoquinonediazide—5—Sulfoyurukulide, 2,3,4,4, -tetrabenzophenone 1,2-Naphthoquinonediazido 4-sulfone Acid esters or 1,2-naphthoquinonediazide-5-sulfonic acid esters and other diazoketone compound-based photoacid generators; 4-trisphenacinolesulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, etc. Sulfonic acid compound-based photoacid generators; benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, nitro benzyl-9,10-jetoxyanthracene_2-sulfonate, triflorenomethanesulfonylbicyclo [2,2,1] Heptaw 5 — 2, 3, 3-dical positimide, N — hydro Shisukushinimi de triflate Ruo b methanesulfonate, 1, and the like 8 _ naphthalene dicarboxylic acid imide triflate Ruo b sulfonic acid compound-based photoacid generator such as methanesulfonate.

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

 In the case of the latent thermal acid generator and the latent photoacid generator, the above acid generator is usually used in an amount of 100 parts by mass (converted as a complete hydrolysis condensate) of the film-forming component. It is 1 to 30 parts by mass.

 Auxiliary components such as colloidal silica, colloidal alumina, and a surfactant 14 may be further added to the first resist underlayer film composition.

Colloidal silica is, for example, an average of high-purity silica anhydride dispersed in an organic solvent. The particle size is 5 to 30 μm, preferably the average particle size is 10 to 20 μιη, and the solid concentration is about 10 to 40% by weight. Examples of such colloidal silica include methanol silica sol, isopropanol silica sol (all manufactured by Nissan Chemical Industry Co., Ltd.), and Oscar (manufactured by Catalyst Chemical Industry Co., Ltd.).

 Examples of the colloidal alumina are Alumina Zonore 520, 100, and 200 (hereafter, manufactured by Nissan Chemical Industries, Ltd.), Alumina Clear Sol, Alumina Sol 10, and 132 (all, Kawasaki Manufactured by Ken Fine Chemical Co., Ltd.). Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, and a fluorine-containing surfactant. be able to.

(Second resist underlayer film composition)

 Next, the second composition for a resist underlayer film of the present invention will be described.

 The second resist underlayer film composition of the present invention comprises a film-forming component comprising a specific silane compound (A) and a thermally decomposable group-containing silane compound (B) having a thermally decomposable organic group. .

 In the second resist underlayer film composition, the film-forming components include a silane compound (A) represented by the above general formula (A) and a silane compound containing a thermally decomposable group represented by the above general formula (B). The hydrolyzate of both (B) and Z or a condensate thereof are used.

The silane compound (A) for the second resist underlayer film composition is basically the same as the film-forming component of the first resist underlayer film composition. However, when R ¹ is a monovalent organic group in the general formula (A) of the silane compound (A), the organic group is a thermally decomposable organic group defined as in the general formula (B). Other than the monovalent, thermally decomposable organic group that decomposes at 200 to 400 ° C.

Depending on the type of the silane compound containing a thermally decomposable group (B) described below, When a composition having a curability is obtained, it is also possible to use only monoalkoxysilane as the silane compound (A).

 In the second resist underlayer film composition, as the silane compound constituting the film-forming component, in addition to the silane compound (A), a thermally decomposable group represented by the general formula (B) is contained. A hydrolyzate of the silane compound (B) and / or a condensate thereof are used as essential components.

In the above general formula (B), the number of the thermally decomposable organic groups R ³ is 200 to 400. Represents a monovalent organic group decomposed by 〇, specifically, a group containing an alkyl group having 6 to 25 carbon atoms, a group containing a cyclic aliphatic group, or a repeating group containing an ether group having 2 to 12 carbon atoms. A group containing an aliphatic polyether chain having a unit is shown.

When a silane compound in which R ³ is a group having a decomposition temperature of less than 200 ° C. in the general formula (B) is used, the silane compound generates a gas before the film-forming component is cured. required hole is not formed in the membrane to become, on the other hand, the use of silane compound decomposition temperature of the thermally decomposable organic group exceeds 4 0 0 ^e C, it is a film-forming components prior to generating gas It is difficult for pores to be formed in the coating film due to the significant progress of curing, and in any case, it is difficult to obtain a resist underlayer film having the required gas permeability.

 Specific examples of the thermally decomposable group-containing silane compound (B) are shown below. These may be used alone or in combination of two or more.

When the thermally decomposable organic group R ³ is an alkyl group having 6 to 25 carbon atoms, the alkyl group may be linear or branched, and examples thereof include a hexyl group and a heptyl group. Examples include a tyl group, an octyl group, a nor group, a decyl group, a dodecyl group and an octadecyl group.

Examples of the silane compound (B) in this case include, for example, hexyltrimethoxysilane, hexinoletriethoxysilane, hexinoletributoxysilane, heptinoletrimethoxysilane, heptyltriethoxysilane, heptyltributoxysilane, and octyltrimethyl. Toxysilane, octyltriethoxysilane, octyltributoxysilane, nonyltrimethoxysilane, nunotriethoxysilane, nunore Tributoxysilane, decinoletrimethoxysilane, decyltriethoxysilane, decyltributoxysilane, dodecyltrimethoxysilane, dodecinoletriethoxysilane, dodecyltributoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and otatadecyltrisilane Butoxysilane and the like.

 Of these, preferred are hexinoletrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octinoletrimethoxysilane, octinoletriethoxysilane, octinoletrimethoxysilane, octyltriethoxysilane, and octyltriethoxysilane. Nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecinoletrimethoxysilane and octadecinoletriethoxysilane.

 When R is a group containing an aliphatic polyester chain having an ether bond-containing repeating unit having 2 to 12 carbon atoms, the group may have a functional group at a terminal, and examples thereof include (Polyethyleneoxy) propyl, (polypropyleneoxy) propyl, (polytetramethyleneoxy) propyl, (polyethyleneoxy) ethyl, (polypropyleneoxy) ethyl, (polytetramethyleneoxy) ethyl, (Polyethyleneoxy) methyl group, (polypropyleneoxy) methyl group and (polytetramethyleneoxy) methyl group.

Examples of the silane compound (B) in this case include (polyethylene oxypropyl pill) trimethoxy silane, bis (polyethylene oxypropyl) dimethoxy silane, tris (polyethylene oxypropinole) methoxy silane, and (polyethylene). (Xypropynole) triethoxysilane, bis (polyethyleneoxypropinole) diethoxysilane, tris (polyethyleneoxypropyl) ethoxysilane, (polypropyleneoxypropyl) trimethoxysilane, bis (polypropyleneoxypropyl) dimethoxysilane, tris ( Polypropylene polypropylene) Toxoxysilane, (polypropyleneoxypropyl) triethoxysilane, bis (polypropyleneoxypropyl) ethoxysilane, tris (polypropyleneoxypropyl) ethoxysilane, (polytetramethyleneoxypropyl) trimethoxysilane, bis (polytetramethyleneoxy) Propinole) Dimethoxysilane, Tris (polytetramethyleneoxypropinole) Methoxysilane, (Polytetramethyleneoxypropyl) Triethoxysilane, Bis (Polytetramethyleneoxypropyl) Getoxysilane, Tris (Polytetramethylene) (Xypropyl) ethoxysilane, (polyethyleneoxyshetyl) trimethyoxysilane, bis (polyethyleneoxyshetyl) dimethoxysilane, tris (polyethyleneoxy) (Xichetinole) methoxy silane, (polyethylene oxethyl) triethoxy silane, bis (polyethylene oxethyl) diethoxy silane, tris (polyethylene oxethyl) ethoxy silane, (polypropylene oxethyl) trimethoxy silane, bis (Polypropyleneoxy) Dimethoxysilane, Tris (polypropyleneoxy) methoxysilane, (Polypropyleneoxy) triethoxysilane, Bis (Polypropyleneoxy) Diethoxysilane, Tris (Polypropyleneoxy) ) Ethoxysilane,

(Polytetramethyleneoxyshethyl) Trimethoxysilane, Bis (polytetramethyleneoxyshethyl) dimethoxysilane, Tris (polytetramethyleneoxyshethyl) methoxysilane, (Polytetramethyleneoxyshethyl) triethoxysilane , Bis (polytetramethyleneoxyshetinole) diethoxysilane, tris (polytetramethyleneoxyshetyl) ethoxysilane, (polyethyleneoxymethyl) trimethoxysilane, bis (polyethyleneoxymethyl) dimethoxysilane, tris (Polyethylene oxymethyl) methoxy silane, (polyethylene oxymethyl) triethoxy silane, bis (polyethylene oxymethyl) diethoxy silane, tris (polyethylene oxymethyl) ethoxy silane, (polypropylene) Noki Shimechiru) trimethylamine Tokishishiran, bis (polypropylene O carboxymethyl) dimethyl Toki Shishiran, tris (polypropylene O carboxymethyl) method Tokishishiran, (polypropylene O carboxymethyl) triethoxysilane, bis (polypropylene O carboxymethyl ) Diethoxysilane, Tris (polypropylene oxymethyl) ethoxy silane, (polytetramethylene oxymethyl) trimethoxy silane, Bis (polytetramethylene oxymethylinole) Dimethoxy silane, Tris (polytetramethylene oxymethylinole) methoxy silane, (Polytetramethyleneoxymethyl) trimethoxysilane, bis (polytetramethyleneoxymethyl) dimethoxysilane, and tris (polytetramethyleneoxymethyl) methoxysilane. Of these, preferred are Are (polyethylene oxypropinole) trimethoxysilane, (polyethylene oxypropyl) triethoxy silane, (polypropylene oxypropinole) trimethoxy silane, (polypropylene (Ethoxypropyl) triethoxysilane, (polytetramethyleneoxypropyl) trimethoxysilane, (polytetramethyleneoxypropyl) triethoxysilane, (polyethyleneoxy) trimethoxysilane, (polyethyleneoxy) ) Triethoxysilane, (polypropyleneoxy) trimethoxysilane, (polypropyleneoxy) triethoxysilane, (polytetramethyleneoxyethyl) trimethoxysilane, (polytetramethyleneoxy) triethoxysilane Sisilane, (polyethyleneoxymethyl) trimethoxysilane, (polyethyleneoxymethyl) triethoxysilane, (polypropyleneoxymethyl) trimethoxysilane, (polypropyleneoxymethylinole) triethoxy Silane, (Poriteto La methylene O carboxymethyl) trimethylamine Tokishishiran, and the like (polytetramethylene O Kishime chill) trimethyl Tokishishiran.

When R ³ is a group containing a cycloaliphatic group, examples of the group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentagenole group, a cyclohexynole group, and a cyclohexyl group. Examples thereof include a pentinole group, a cyclooctynole group, a cyclooctenyl group, a cyclohexenyl group, an adamantyl group, a bicycloheptyl group, and a cis-opened heptyl group.

Examples of the silane compound (B) in this case include, for example, cyclopropyl trimethoxy silane, dicyclopropynolemethyxoxysilane, and tricyclopropynolemethoxy silane. Silane, cyclopropylmethyltrimethoxysilane, bis (cyclopropylmethyl) dimethoxysilane, tris (cyclopropylmethyl) methoxysilane, cyclopropylethyltrimethoxysilane, bis (cyclopropyl acetyl) dimethoxysilane, tris (cyclopropylethyl) Tyl) methoxysilane, octyl butyl trimethoxy silane, dicyclo butyl / dimethoxy silane, tricyclo butyl methoxy silane, cycl butyl methyl trimethoxy silane, bis (cyclo butyl methyl) dimethoxy silane, tris (cyclobutylmethyl) methoxy silane , Cyclobutylethyltrimethoxysilane, bis (cyclobutylethyl) dimethoxysilane, tris (cyclobutylethyl) methoxysilane, cyclopentyltri Toxisilane, cyclopentene ^^ triethoxysilane, dicyclopentene ^^ dimethoxysilane, dicyclopentylmethoxysilane, tricyclopentylmethoxysilane, cyclopentylmethyltrimethoxysilane, bis (cyclopentylmethyl) dimethoxysilane, tris (cyclopentylmethyl) ) Methoxysilane, cyclopentinoethyltrimethoxysilane, bis (cyclopentylethyl) dimethoxysilane, tris (cyclopentylethyl) methoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentene Lujetoxysilane, tricyclopentenylmethoxysilane, cyclopentylmethyltrimethoxysilane, bis (Cyclopentenylmethyl) dimethoxysilane, tris (cyclopentylmethyl) methoxysilane, cyclopentenylethyl trimethoxysilane, bis (cyclopentylethyl) dimethoxysilane, tris (cyclopentenylethyl) methoxysilane, cyclopentane Genyl trimethoxy silane, cyclopentagenenyl triethoxy silane, dicyclo pentagen ^ res ethoxy silane, dicyclo penta ge res ethoxy silane, cyclopenta geninole methoxy silane, cyclopenta geninole methyl tri methoxy silane, bis (cyclopenta Genylmethyl) dimethoxysilane, tris (cyclopentadienylmethyl) methoxysilane, cyclopentadienylethyltrimethoxysilane, Clopentajeruethyl) dimethoxysilane, tris (cyclopentagenylethyl) methoxysilane, cyclohexane Xinoletrimethoxysilane, cyclohexyltriethoxysilane, dicycloheximedimethoxysilane, dicyclohexexethoxysilane, tricyclohexylmethoxysilane, cyclohexinolemethyltrimethoxysilane, bis (cyclohexylmethyl) dimethoxysilane, tris ( Cyclohexynolemethyl) methoxysilane, cyclohexylethyltrimethoxysilane, bis (cyclohexylethyl) dimethoxysilane, tris (cyclohexylethyl) methoxysilane, cycloheptyltrimethoxysilane, cycloheptyltriethoxysilane, dicycloheptyldimethoxysilane, Dicyclohexyl methoxysilane, Tricyclohexyl methoxysilane, cycloheptylmethyltrimethoxysilane, Bis (cycloheptylmethinole) dimethoxysilane, tris (cyclohepty ^^ methinole) methoxysilane, cyclohexheptylethyltrimethyoxysilane, bis (cycloheptylethynole) dimethyoxysilane, tris (cycloheptylethynole) methoxysilane, Cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, dicyclooctyldimethoxysilane, dicyclooctyljetoxysilane, tricyclooctyl ^^ methoxysilane, cyclooctylmethyl ^^ trimethoxysilane, bis (cyclomethylmethinole) dimethoxysilane, triscyclohexyl ) Methoxysilane, cyclooctyl ^^ ethynoletrimethoxysilane, bis (cyclooctyl) dimethoxysilane, tris (cyclooctane) (Cthylethyl) methoxysilane, cyclohexeninoletrimethoxysilane, cyclohexyltriethoxysilane, dicyclohexenyl ^^ dimethoxysilane, dicyclohexenyl ^ rethoxysilane, trisix hexenyl methoxysilane, silicone hexenylmethyltrimethoxysilane, Bis (cyclohexenylmethyl) dimethoxysilane, tris (cyclohexenylmethyl) methoxysilane, cyclohexenylethyltrimethoxysilane, bis (cyclohexenylethynole) dimethoxysilane, tris (cyclohexeninoleethyl) methoxysilane, cyclo Octactenyltrimethoxysilane, cyclooctageninoletriethoxysilane, dicyclooctagenile ^ ^ regismetoxysilane, dicyclooctagenil Kishishiran, tricycloalkyl O Kuta Genis Rume butoxy silane, cycloalkyl O Kuta Genis methyl trimethinecyanine Tokishishiran, di (Shikurookutaji Phenylmethyl) dimethoxysilane, tris (cyclooctagenylmethyl) methoxysilane, cyclooctanej / n-retrimethoxysilane, bis (cyclooctagenylethyl) dimethoxysilane, tris (cyclooctagenylethyl)

) Methoxysilane, adamantyl trimethoxy silane, adamantyl triethoxy silane, diadamanti dimethoxy silane, diadamanchi ^^ diethoxy silane, triadamantyl methoxy silane, adamantyl methyl trimethoxy silane, bis (adamantyl methyl) dimethoxy silane, Tris (adamantyl methinole) methoxy silane, adamantyl acetyl trimethoxy silane, adaman cetinole triethoxy silane, bis (adaman tyl ethyl) dimethoxy silane, bis (adamantyl ethino) diethoxy silane, tris (Adamantylethyl) methoxy silane, tris (adamantylethyl) ethoxysilane,

Bissic mouth heptyltrimethoxysilane, Bissic mouth heptyltriethoxysilane, Dissic mouth heptyldimethoxysilane, Dissic mouth heptyl ^^ ethoxysilane, Trissic mouth heptylmethoxysilane, Bissic mouth heptylmethyltrimethoxysilane, bis (bicycloheptylmethyl) Dimethoxysilane, tris (bicycloheptylmethyl) methoxysilane, bicycloheptylethyltrimethoxysilane, bis (bicycloheptylethyl) dimethoxysilane, tris (bicycloheptylethyl) methoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyl Triethoxysilane, dibicycloheptenyl dimethoxysilane, dibicycloheptenyl ethoxysilane, tribicycloheptenyl methoxy Heptenylmethyltrimethoxysilane, bis (heptenylmethyl) bismethoxysilane, tris (bicyclohepturylmethyl) methoxysilane, heptenylethyltrimethoxysilane in the mouth, bis (heptenylethyl) bismethacrylate and Tris (bicycloheptenylethyl) methoxysilane and the like can be mentioned.

Of these, preferred are cyclopentyltrimethyoxysilane, dicyclopentinoresimethyoxysilane, cyclopentinolemethytrimethyoxysilane, bis (cyclopentylmethyl) dimethyoxysilane, and cyclopentenyltrimethysilane. Xysilane, dicyclopentenyldimethoxysilane, cyclopentagenenyltrimethoxysilane, dicyclopentajenyldimethoxysilane, cyclohexylethoxymethysilane, dicyclohexyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cyclooctyltrimethoxy Sisilane, dicyclooctyl dimethoxy silane, cyclohexenino retrimethoxy silane, dicyclohexenino resie methoxy silane, cyclooctenyl methoxy silane, dicyclo octenyl dimethyl silane, adamantyl trimethoxy silane, diadamantyl dimethyl silane Toxoxysilane, adamantyl methyltrimethoxysilane, bis (adamantylmethyl) dimethoxysilane, α Manchiruechiru trimethylene Tokishishiran, bicycloheptene Saturation belt Increment Tokishishiran, the bicyclo to pteridine sulfonyl triethoxysilane Oyopi Jibishikuro Putenirujime Tokishishiran the like can ani gel.

 In the composition for the second resist underlayer film, the general range of the relative ratio between the silane compound (A) constituting the film-forming component and the silane compound (B) containing the thermally decomposable group is required. It is sufficient that the composition is such that a composition capable of forming a porous silica film having properties such as gas permeability can be obtained.Therefore, the specific range is a force S that differs depending on the type of each silane compound, for example, a mass. 30 to 95: 10 to 70, 50 to 90: preferably 10 to 50, particularly preferably 70 to 90: 10 to 30.

 If the proportion of the silane compound (A) is too large, the proportion of the thermally decomposable group-containing silane compound (B) will be relatively small, resulting in a resist having insufficient gas permeability. A lower layer film is formed. On the other hand, if the proportion of the silane compound (A) is too small, the resulting composition may have a resist underlayer film formed with an excessively high gas permeability and insufficient resistance.

 In order for the obtained composition to have the required curability, it is necessary that at least one of the silane compound (A) and the silane compound (B) containing a thermally decomposable group has at least three alkoxy groups.

From this viewpoint, the value of a in the general formula (A) for the silane compound (A) is 3 or more. Or a silane compound (B) having a thermally decomposable group-containing silane compound (B) in which the value of b in the general formula (B) is 3 or 2. ) And are not preferred, and other combinations are preferred. A catalyst is used to hydrolyze, Z or condense the silane compound (A) and the thermally decomposable group-containing silane compound (B).

 As the catalyst, those listed as catalysts for hydrolyzing, Z-condensing, or silane compound (A) in the first resist underlayer film composition can be used.

 The amount of the catalyst used is usually 0.0 with respect to 100 parts by mass of the silane compound (A) and the thermally decomposable group-containing silane compound (B) (converted as a condensate). The range is from 0.1 to 10 parts by mass, preferably from 0.01 to 10 parts by mass.

 The second resist underlayer film composition is produced by a method of hydrolyzing and partially condensing both the silane compound (A) and the thermally decomposable group-containing silane compound (B).

 In order to carry out this hydrolysis and partial condensation, it is preferable to add 0.25 to 3 moles, particularly 0.3 to 2.5 moles of water per mole of alkoxy group in the entire silane compound. In this case, the composition formed by the obtained resist underlayer film composition has high uniformity, and the composition surely has high storage stability.

 Specifically, water may be intermittently or continuously added to an organic solvent in which the silane compound (A) and the thermally decomposable group-containing silane compound (B) are dissolved. The catalyst may be added to an organic solvent in advance, or may be dissolved or dispersed in water to be added. The reaction temperature of this hydrolysis and partial condensation is usually 0 to 100 ° C, preferably 15 to 80 ° C.

Here, the solvent is not particularly limited as long as it is an organic solvent used for this kind of use, but in particular, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether are used. And the like are preferably used. W

3 9 Also in the second resist underlayer film composition, an acid generator can be added in the same manner as the first resist underlayer film composition, and the acid generator described above can be used. The same effect can be obtained.

 Further, the second resist underlayer film composition contains, similarly to the first resist underlayer film composition, auxiliary components listed as being added to the first resist underlayer film composition. Can be added.

(Formation of resist underlayer film)

 The first resist underlayer film composition and the second resist underlayer film composition of the present invention are used for forming an underlayer of a resist film formed on a substrate to be processed.

 Specifically, a solution of the composition is applied to a surface on which a resist underlayer film is to be formed to form a coating film, and the coating film is dried and then cured by heating. Then, by controlling the heating temperature in this curing to an appropriate temperature, in the first resist underlayer film composition, the heating volatile substance is gasified and volatilized, and the second resist underlayer film composition In this method, a gas was generated by thermally decomposing the thermally decomposable organic group derived from the thermally decomposable group-containing silane compound (B) in the film-forming component, whereby many or innumerable pores were formed. A resist underlayer film made of a porous silica film is formed. This resist underlayer film usually has a refractive index of 1.2 to 1.6.

 The surface on which the resist underlayer film of the present invention is formed is not particularly limited as long as the resist film is formed on the resist underlayer film. In a specific example, the resist underlayer film is formed on the surface of the processing underlayer film formed on the oxide film of the substrate to be processed. In this case, the resist underlayer film is used as a mask for processing the underlayer film. To form a film.

In the process of forming a resist underlayer film using the first resist underlayer film composition, the temperature at which the coating film is heated is a temperature higher than the boiling point or decomposition temperature of the heating volatile substance contained in the composition. Therefore, the temperature is set to 200 ° C. to 450 ° C. or more, but the type of the film forming component actually used, the type of the curing catalyst, etc. The appropriate temperature is selected depending on the type and ratio of the heating volatile substance, the type and ratio of other additives, and other conditions.

In the process of forming the resist underlayer film using the second resist underlayer film composition, the temperature at which the coating film is heated depends on the decomposition of the thermally decomposable organic group R ³ of the thermally decomposable group-containing silane compound (B). It is necessary that the temperature be higher than the temperature, so that the force is set to a temperature of 200 to 400 ° C. or higher. The silane conjugate (A) and the thermally decomposable group-containing silicon compound that are actually used An appropriate temperature is selected depending on the type and relative ratio of (B), the type and ratio of the curing catalyst, the type and ratio of other additives, and other conditions.

 By adjusting the heating temperature and heating time of the coating film, the porous state of the formed resist underlayer film, specifically, the average diameter of the formed holes and the degree of distribution were controlled. It can be.

The density of the porous silicon film constituting the resist underlayer film thus formed is preferably, for example, 0.7 to 1.8 gZcm ³ . By having a relatively low density in such a range, the resist underlayer film itself has good gas permeability, and therefore, by sufficiently transmitting the etching gas, it can be used as a lower layer of the resist underlayer film. The required gas etching can be reliably and easily achieved on the formed processing lower layer film.

 Further, as is clear from the examples described later, the composition for a resist underlayer film of the present invention is formed because the film-forming component is composed of a hydrolyzate of a specific silane compound and Z or a condensate. The cured film is porous but has high adhesion to the resist, has sufficiently high resistance to resist developing solution and oxygen gas for ashes for removing the resist, and has high reproducibility in the resist film It is possible to form a resist underlayer film on which a resist pattern is formed, and it is possible to obtain excellent storage stability and strength.

 Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

The following Examples A1 to A3 are based on the first resist underlayer film composition. It is.

Example A 1,

 (1) Dissolve 30.lg of tetramethoxysilane of silane compound (Α) and 2.6 g of methyltrimethoxysilane in 154 g of propylene dalycol monopropyl ether, an organic solvent, and stir with a three-one motor to adjust the solution temperature. Was stabilized at 60. To this solution, an aqueous solution in which 0.12 g of maleic acid as a catalyst was dissolved in 15.7 g of ion-exchanged water was added over 1 hour, and the mixture was reacted at 60 C for 4 hours. Cooled down. Then, after removing 51 g of a solution containing methanol from the reaction solution at a temperature of 50 ° C. by evaporation, 51 g of propylene glycol monopropyl ether was added to obtain a film-forming component solution.

 (2) To 50 g of the film-forming component liquid obtained in (1) above, 0.09 g of triphenylsulfonium trifluoromethanesulfonate, a latent photoacid generator, and a decomposition temperature of 330 ° C 1.20 g of polytetrahydrofurfuryl methacrylate having a weight-average molecular weight of 7,000, which is a volatile substance heated by heating, is stirred well, and the solution is filtered through a filter with a pore size of 0.2 μπι. Thus, a composition for a resist underlayer film was obtained.

Example A 2

 To 50 g of the film-forming component liquid obtained in the same manner as in Example A1, 0.09 g of triphenylsulfonium trifluoromethanesulfonate as a latent photoacid generator and heating at a decomposition temperature of 300 ° C 1.20 g of polyethylene oxide having a weight-average molecular weight of 2000, which is a volatile substance, was added, and the mixture was sufficiently stirred. The solution was further filtered through a filter having a pore size of 0.2 fim to obtain a composition for a resist underlayer film. I got

Example A 3

To 50 g of the film-forming component liquid obtained in the same manner as in Example A1, 0.09 g of triphenylsulfonium trifluoromethanesulfonate, a latent photoacid generator, and a decomposition temperature of 350 ° C 4- (naphthoquinone-1,2-diazido-5-sulfonyl) -4,1- (1-methyl (4-bis (naphthoquinone-1,1,2-diazido-5-snorefonyl) -11, 1 diphenyl / le) Methyl isopropylide Then, 1.20 g of N. dipheninole was added and stirred well, and the solution was filtered through a filter having a pore size of 0.2 μπι to obtain a composition for a resist underlayer film.

Comparative example A1

 In Example A1, the decomposition temperature was 340 in place of polytetrahydrofurfuryl methacrylate as the heat-volatile substance. A composition for a resist underlayer film was obtained in the same manner as in Example 1 except that polystyrene C was used.

Comparative Example A 2

 In Example A1, a resist underlayer film was prepared in the same manner as in Example 1 except that poly-α-methylstyrene having a decomposition temperature of 70 ° C. was used instead of polytetrahydrofurfuryl methacrylate as the heating volatile substance. A composition for use was obtained.

 (Evaluation of composition for resist underlayer film)

 The following items were evaluated for each of the resist underlayer film compositions according to Examples A1 to A3 and Comparative Examples A1 to A2 in the above case.

 (1) Film density and refractive index

 (2) Adhesion of resist

 (3) Reproducibility of resist pattern

 (4) Alkali resistance

 (5) Oxygen assing resistance

 (6) Storage stability of solution

 The evaluation methods for the above items (1) to (6) are as follows.

 [Formation of resist pattern]

 Using the sample resist underlayer film composition, a resist underlayer film was formed as follows, and a resist film was further formed to form a resist pattern.

 That is, a material for an anti-reflection film “NFC B 007” (manufactured by JSR Corporation) was applied to the surface of a silicon wafer by a spin coater, and 190. An anti-reflection film having a thickness of 300 nm was used as a substrate to be processed by drying on a hot plate of C for 1 minute.

A resist underlayer film composition is spin-coated on the surface of the antireflection film of the substrate to be processed. After coating on a hot plate at 200 ° C for 1 minute, the resist was baked on a hot plate at 300 ° C to form a resist underlayer film having a thickness of 7 Onm.

 Further, a positive photoresist “M20G” (manufactured by JSR Corporation) is applied to the surface of the resist underlayer film, and dried at 130 ° C. for 90 seconds to form a resist coating film having a thickness of 700 nm. Then, a KrF excimer laser (wavelength: 248 nm) with a liner and space pattern of 0.2 // m using a Nikon KrF excimer laser irradiation device The resist coating was irradiated with an energy of 25 mJ through a quartz optical mask. The resist film is heated at 130 ° C for 90 seconds, and then developed for 30 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide aqueous solution. A pattern was formed.

 (1) Film density and refractive index

 The film density was measured by the X-ray scattering method.

 For the value of the refractive index, the refractive index at 50 points was measured using an optical refractometer “UV-1280 SE” (manufactured by KLA-Tencor), and the average value was determined.

 (2) Adhesion with resist

 The resist pattern was observed with a scanning electron microscope, and the case where the resist film was not peeled from the resist underlayer film was evaluated as “good”, and the case where the resist film was peeled was evaluated as “bad”.

 (3) Reproducibility of resist pattern

 Observing the resist pattern with a scanning electron microscope, there was no residual resist film at the place where the laser was irradiated, and the 0.2 μπι line and space pattern of the optical mask was faithfully reproduced. Was evaluated as “good”, and the case where the pattern was not reproduced was evaluated as “poor”.

 (4) Evaluation of alkali resistance

In the development process, the film thickness of the resist underlayer film before immersion in the developing solution is compared with the film thickness of the resist underlayer film after immersion, and when the difference between the two is 2 nm or less, `` good J, A case exceeding 2 nm was evaluated as “poor”. (5) Oxygen ashesing resistance

 The resist underlayer film was subjected to oxygen ashes at 300 W for 15 seconds using a barrel-type oxygen plasma ashing device “PR-501” (manufactured by Yamato Scientific Co., Ltd.). The case where the difference from the thickness of the resist underlayer film was 5 nm or less was evaluated as “good”, and the case where the difference was more than 5 nm was evaluated as “bad”.

 (6) Storage stability of solution

 Using each of the resist underlayer film compositions according to Examples A1 to A3 and Comparative Examples A1 to A2 as a sample, the storage stability of the solution was determined as follows.

 The composition for a resist underlayer film was applied to the surface of a silicon wafer using a spin coater at 2000 rpm for 20 seconds, and then 190. Using a hot plate maintained at a temperature of C, the silicon wafer coated with the resist underlayer film composition was heated for 2 minutes. With respect to the obtained resist underlayer film, the film thickness was measured at 50 points using an optical film thickness meter (manufactured by KLA-Tencor, UV-1280SE), and the average film thickness was obtained.

 Further, using the composition for a resist underlayer film after storage at a temperature of 40 ° C. for one month, a resist underlayer film was formed in the same manner as described above, the film thickness was measured, and the average film thickness was obtained.

 The average film thickness T of the coating film of the resist underlayer film composition before storage. And the average film thickness T of the coating film of the resist underlayer film composition after storage (T−T.) Was calculated. Is calculated as the film thickness change rate. If the value is 10% or less, it is judged as “good”, and if it exceeds 10%, it is judged as “good”. Poor ".

 The evaluation results are as follows.

Example A 1

 (1) Film density: 1.54, refractive index: 1.34

 (2) Resist adhesion: good

 (3) Reproducibility of resist pattern: good

(4) Alkali resistance: good (film thickness change width 0.4 nm) (5) Oxygen assing resistance: good (film thickness change width 2.5 nm)

(6) Solution storage stability: good (film thickness increase rate 4.5%) Example A 2

 (1) Film density: 1.60, refractive index: 1.37

 (2) Resist adhesion: good

 (3) Reproducibility of resist pattern: good

 (4) Alkali resistance: good (film thickness change width 0.5 nm)

(5) Oxygen assing resistance: good (film thickness change width 2.6 nm)

(6) Solution storage stability: good (thickness increase rate 4.3%)

 (1) Film density: 1.40, refractive index: 1.32

 (2) Resist adhesion: good

 (3) Reproducibility of resist pattern: good

 (4) Alkali resistance: good (film thickness variation 0.7 nm)

(5) Oxygen assing resistance: good (film thickness change width: 2.9 nm)

(6) Solution storage stability: good (thickness increase rate 3.4%) Comparative Example A 1

 (1) Film density: 1.85, refractive index: 1.43

 (2) Adhesion of resist: poor

 (3) Register pattern reproducibility: poor

 (4) Alkali resistance: poor (film thickness change width 7 nm)

 (5) Oxygen ashing resistance: good (thickness change width 3.2nm)

(6) Solution storage stability: poor (film thickness increase rate 16.3%) Comparative Example A 2

 (1) fl density: 2.0, refractive index: 1.49

 (2) Adhesion of resist: poor

 (3) Register pattern reproducibility: poor

(4) Alkali resistance: good G1 thickness variation 0.9 nm W 02

46

(5) Oxygen assing resistance: poor (pattern destruction)

 (6) Solution Storage Stable '(4: Poor (Thickness Increase Rate 16.3%)) The following Examples B1 to B2 are based on the second resist underlayer film composition.

Example B 1

 55.2 g of tetramethoxysilane of silane compound (A) and bicycloheptenyltriethoxysilane (triethoxysilylnorbornene) of silane compound (B) having a thermally decomposable group were added to 10.74 g of propylene glycol as an organic solvent. The resulting mixture was dissolved in a flask having a capacity of 50 OmL together with 190.89 g of ethyl ether, and the mixture was heated to 60 ° C. while stirring with a magnetic stirrer. Here, the decomposition temperature of the bicycloheptenyl group which is the thermally decomposable organic group of the thermally decomposable group-containing silane compound (B) is 350 ° C.

 To this mixed solution, an aqueous solution in which 0.99 g of a maleic acid catalyst was dissolved in 42.17 g of ion-exchanged water was added over 1 hour. Thereafter, a hydrolysis and condensation reaction was performed at 60 ° C. for 4 hours, and the obtained reaction solution was cooled to room temperature. Then, 55.99 g of methanol and ethanol by-produced by the reaction were distilled off from the reaction solution under reduced pressure. 11.88 g of the reaction product liquid obtained by such an operation was mixed with 0.01 g of triphenylsulfoium trifluoromethanesulfonate, a latent photoacid generator, in propylene glycol monoethyl ether 17.3 g. This solution was dissolved in 9 g, and the solution was filtered through a filter having a pore size of 0.2 μm to obtain a composition for a resist underlayer film.

Example B 2

55.88 g of tetramethoxysilane of the silane compound (A) and 16.40 g of dodecinoletrimethoxysilane of the silane compound (B) having a thermally decomposable group were converted to 1.38.54 The resulting mixture was dissolved in a flask having a capacity of 50 OmL together with g, and the mixture was heated to 60 ° C. while stirring with a magnetic stirrer. Here, the thermal decomposability of the thermally decomposable group-containing silane compound (B) The decomposition temperature of the organic dodecyl group is 2.50. C.

 To this mixture, an aqueous solution in which 1.00 g of a maleic acid catalyst was dissolved in 42.48 g of ion-exchanged water was added over 1 hour. Thereafter, hydrolysis and condensation were performed at 60 ° C. for 4 hours, and the obtained reaction solution was cooled to room temperature. Then, 55.77 g of methanol produced as a by-product of the reaction was distilled off from the reaction solution under reduced pressure.

 11.88 g of the reaction solution obtained by such an operation was mixed with 0.01 g of the latent photoacid generator trifluorene resulfonium trifnoroleolomethanesulfonate to propylene glycol monoethyl ether 17. This solution was dissolved in 39 g, and the solution was filtered through a filter having a pore size of 0.2 μπι to obtain a composition for a resist underlayer film. Comparative Example Β 1

 (1) Dissolve 30.lg of tetramethoxysilane corresponding to the silane compound (Α) and 20.lg of methyltrimethoxysilane corresponding to the silane compound (A) in 154 g of an organic solvent, propylene daricol monopropyl ether. The solution was stirred at a constant temperature to stabilize the solution temperature at 60 ° C.

 To this solution, an aqueous solution in which 0.12 g of maleic acid as a catalyst was dissolved in 15.7 g of ion-exchanged water was added over 1 hour. Thereafter, the reaction was performed at 60 C for 4 hours, and the reaction solution was cooled to room temperature. Then, 51 g of a solution containing methanol by-produced by the reaction was distilled off from the reaction solution under reduced pressure, and 51 g of propylene glycol monopropyl ether was added to obtain a reaction product solution.

 (2) To 50 g of the reaction product liquid obtained in (1) above, 0.09 g of triphenylsulfonium trifluoromethanesulfonate, which is a latent photoacid generator, was added and sufficiently stirred. This solution was filtered through a filter having a pore size of 0.2 μιη to obtain a composition for a resist underlayer film.

Comparative Example Β 2

(1) Cycloheptyltrimethoxysilane corresponding to the thermally decomposable group-containing silane compound (Β) (The thermal decomposition temperature of the heptyl group at the mouth is 270 ° C) 12.4 g and the silane compound (B) (polyethylene 25.1 g ((polyethyleneoxy) propyl group has a thermal decomposition temperature of 220 ° C). The solution was dissolved in 154 g of propylene glycol monopropyl ether as a solvent, and stirred with a three-one motor to stabilize the temperature of the solution at 60 ° C.

 An aqueous solution obtained by dissolving 0.22 g of maleic acid as a catalyst in 20.7 g of ion-exchanged water was added to this solution over 1 hour. Thereafter, the reaction was performed at 60 ° C. for 4 hours, and the reaction solution was cooled to room temperature. Then, 61 g of a solution containing methanol produced as a by-product of the reaction was distilled off from the reaction solution under reduced pressure, and 61 g of propylene daricol monopropyl ether was added to obtain a reaction product solution.

 (2) To 50 g of the reaction product liquid obtained in the above (1), 0.09 g of triphenylenoles norephonium trifenolene, a latent photoacid generator, was added and sufficiently stirred. . This solution was filtered through a filter having a pore size of 0.2 μιη to obtain a composition for a resist underlayer film.

 (Evaluation of composition for resist underlayer film)

 For each of the resist underlayer film compositions according to Examples Β1 to Β2 and Comparative Examples Β1 to Β2 in the above case, the same items as in the case of the first resist underlayer film composition (1) (6) was evaluated.

 The evaluation method for each of the items (1) to (6) is the same as that for the first resist underlayer film composition.

Example Β 1

 (1) Film density: 1.65, refractive index: 1.34

 (2) Resist adhesion: good

 (3) Reproducibility of resist pattern: good

 (4) Alkali resistance: good (film thickness variation 0.4 nm)

 (5) Oxygen ashing resistance: good (thickness change width 3.5nm)

 (6) Solution storage stability: good (film thickness increase rate 3.5%)

Example B 2

 (1) Film density: 1.55, refractive index: 1.32

 (2) Resist adhesion: good

(3) Reproducibility of resist pattern: good (4 Alkali resistance: good (thickness variation 0.3 nm)

 (5 Oxygen assing resistance: good (film thickness change width 4.5 nm)

 (6 Solution storage stability: good (thickness increase rate 3.5%)

Comparative Example B 1

 (1) Film density: 2.0, refractive index: 1.47

 (2) Resist adhesion: good

 (3) Reproducibility of resist pattern: good

 (4) Alkali resistance: good (film thickness change width 0.4 nm)

 (5) Oxygen assing resistance: poor (film peeling)

 (6) Solution storage stability: good (film thickness increase rate 4.5%)

Comparative Example B 2

 (1) Film density: 0.60, refractive index: 1.19

 (2) Resist adhesion: poor

 (3) Reproduction of resist pattern ②: defective

 (4) Alkali resistance: poor (film thickness variation width 6 nm)

 (5) Oxygen ashing resistance: poor (film thickness change width 20 nm)

 (6) Solution storage stability: good (thickness increase rate 3.5%)

 Since the first resist underlayer film composition of the present invention contains a heat-volatile substance together with a film-forming component formed by hydrolysis and partial condensation of a silane compound, the film-forming component is cured by heating. As a result, the volatilizable substance is sometimes gasified and volatilized, resulting in a relatively low-density porous silica film having many or innumerable pores formed, and a resist underlayer film having good gas permeability formed. Is done. Therefore, the resist underlayer film can reliably and easily achieve the required gas etching with respect to the lower processing lower layer film by sufficiently transmitting the etching gas.

The second composition for a resist underlayer film of the present invention contains a film-forming component composed of a silane compound obtained by hydrolysis and partial condensation of a silane compound. Contains silane compound (B) W

When 50 is cured by heating, the silane compound (B) generates a force gas, resulting in the formation of a porous silica film having a relatively low density in which many or innumerable pores are formed. A resist underlayer film having a gas permeability is formed. Accordingly, the resist underlayer film can easily and easily achieve required gas etching with respect to the lower processing lower layer film by sufficiently transmitting the etching gas.

 In addition, since the above-described composition for a resist underlayer film of the present invention has a film-forming component consisting of a hydrolyzate and Z or a condensate of a specific silane compound, it has a high adhesion to a resist while being porous. The resist underlayer film, which has high resistance to resist developing solution and oxygen gas for ashes for removing the resist and has a highly reproducible resist pattern on the resist film, can be formed. Moreover, excellent storage stability can be obtained.

Claims

The scope of the claims

 1. It comprises a film-forming component composed of a silane compound (A) represented by the following general formula (A) and Z or a condensate thereof, and a heat-volatile substance which is heated and gasified,

 A composition for a resist underlayer film, wherein a film-forming component is cured by heating, and a heat-volatile substance is gasified to form pores, thereby forming a porous silicon film.

—General formula (A) S i (OR ² ) ₄ -a

(R ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, and a represents an integer of 0 to 3.)

2. The composition for a resist underlayer film according to claim 1, wherein the silane compound (A) relating to the film-forming component is a silane compound in which _a is 0 or 1 in the general formula (A). .

3. The composition for a resist underlayer film according to claim 1, wherein the heat-volatile substance is a substance having a boiling point or a decomposition temperature of 200 to 450 ° C.

4. The heat-volatile substance has an aliphatic polyester compound composed of poly (meth) acrylate, a polyalkylene oxide having a repeating unit containing 2 to 12 carbon atoms and having a naphthoquinonediazide structure. 4. The composition for a resist underlayer film according to claim 3, wherein the composition is at least one selected from compounds.

5. The resist underlayer film according to any one of claims 1 to 4, further comprising an acid generating compound which generates an acid by at least one of irradiation with ultraviolet light and heating. Composition.

6. A thin film formed from the composition for a resist underlayer film according to any one of claims 1 to 5, which is cured by heating, and has a density of 0.7 to 1.8 g / cm. ^3. A resist underlayer film comprising a porous silica film which is ^3.

7. A thin film is formed from the composition for a resist underlayer film according to any one of claims 1 to 5, and the thin film is heated to a temperature equal to or higher than the boiling point or the decomposition temperature of the heat-volatile substance contained in the composition. Manufacturing a resist underlayer film characterized by forming a porous silicon film by heating to a temperature to harden film forming components and to gasify a heat-volatile substance to form pores. Method.

8. From the hydrolyzate and / or condensate of the silane compound (A) represented by the following general formula (A) and the thermally decomposable group-containing silane compound (B) represented by the following general formula (B) Containing a film forming component

A resist lower layer characterized in that a film-forming component is cured by heating, and a thermally decomposable group-containing silane compound (B) generates gas to form pores, thereby forming a porous silicon film. Composition for membrane. General formula (A) S i (OR ² ) 4— _a

CR ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group (however, excluding a thermally decomposable organic group defined as in the general formula (B) below), and R ² represents a monovalent organic group. And a represents an integer of 0 to 3. ]

Formula _{^{(B) R 3 b S i}} (OR 4) 4-b (R: ' shows a 2 0 0-4 0 monovalent thermally decomposable organic group which decomposes at 0.C, R ⁴ is 1 And b represents an integer of 1 to 3. )

9. The thermally decomposable group-containing silane compound (B) is a compound represented by the formula (B), wherein R ³ is a thermally decomposable organic group containing a cycloaliphatic group, a linear or branched C 6 to C 25 group. Or a silane compound which is a heat-decomposable organic group containing an aliphatic polyether chain having a repeating unit having 2 to 12 carbon atoms and having an ether bond containing 2 to 12 carbon atoms. 9. The composition for a resist underlayer film according to claim 8, wherein

10. The composition for a resist underlayer film according to claim 8, further comprising an acid generating compound that generates an acid by at least one of irradiation with ultraviolet light and heating.

11. The step of hydrolyzing and partially condensing the silane compound (A) and the thermally decomposable group-containing silane compound (B) according to claim 8 in an organic solvent in the presence of water and a catalyst. A method for producing a composition for a resist underlayer film, comprising:

1 2. A thin film formed by the composition for a resist underlayer film according to any one of claims 8 to 10 is cured by heating, and has a density of 0.7 to 1.8. g Z c ni ^{: i} below the resist characterized by comprising a porous silica film

13. A thin film is formed from the composition for a resist underlayer film according to any one of claims 8 to 10, and the thin film is formed from the thermally decomposable group-containing silane compound (B) contained in the composition. ), By heating to a temperature not lower than the decomposition temperature of the thermally decomposable organic group, thereby curing the film-forming components and generating gas to form pores, thereby forming a porous silica film. Manufacturing method of resist underlayer film.