JP5776301B2 - Polysiloxane composition and pattern forming method - Google Patents

Description

  The present invention relates to a polysiloxane composition and a pattern forming method. Specifically, it is suitable for forming a resist underlayer film, has excellent adhesion to the resist, has little film loss during oxygen etching of the resist, and can be obtained by either positive development with an alkali solution or negative development with an organic solvent. The present invention relates to a polysiloxane composition having a good resist pattern shape and less collapse, and a pattern forming method having a good resist pattern shape and less collapse and capable of being miniaturized.

For pattern formation of semiconductor elements and the like, a development process using a resist formed on an antireflection film and etching of an organic material and an inorganic material using a resist pattern after development as a mask are frequently used.
However, with the high integration of semiconductor elements and the like, there is a problem that the resist pattern after development is peeled off. Further, with the miniaturization and thinning of the resist, the etching rate between the resist and the antireflection film is similar, so that there is a problem that the organic material and inorganic material under the antireflection film cannot be processed finely.

  In order to solve the above problems, an inorganic resist underlayer film is provided between the resist and the organic antireflection film, and the resist underlayer film is first etched using the resist pattern as a mask. A technique for etching a lower organic material using the above pattern as a mask has been studied (see Patent Document 1).

  On the other hand, as a technique for enhancing the resolving power by utilizing the characteristics of a chemically amplified resist material, a technique for forming an exposed portion as a pattern by using an organic solvent having a polarity lower than that of an alkaline aqueous solution as a developer is disclosed (Patent Literature). 2). In such a negative development process in which the exposed part remains as a pattern after development and a positive development process in which the unexposed part remains as a pattern after development, the properties of the resist remaining as a pattern are different. Generally different.

WO2006 / 126406 JP 2000-199953 A

  As the pattern becomes finer, higher performance is required for the resist underlayer film. That is, there is a demand for a resist underlayer film that has excellent adhesion to a resist and has high pattern transferability by etching in both processes of positive development using an alkali solution and negative development using an organic solvent. Thus, there is a need for a resist underlayer film and a pattern forming method in which the resist pattern formed on the resist underlayer film has a good shape and less collapse in both processes of negative development with an organic solvent.

  That is, the object of the present invention is suitable for forming a resist underlayer film, and can form a silicon-containing film having excellent adhesion with a resist film in both processes of positive development with an alkali solution and negative development with an organic solvent, A polysiloxane composition having a high pattern transferability, a resist pattern formed on the lower layer film obtained in both processes of positive development with an alkali solution and negative development with an organic solvent, and having a low collapse, and a resist An object of the present invention is to provide a pattern forming method in which the pattern shape is good, the collapse is small, and miniaturization is possible.

The polysiloxane composition of the present invention comprises:
(A) polysiloxane (hereinafter also referred to as “polysiloxane (A)”),
(B) a nitrogen-containing compound having at least one selected from a polar group and an ester group (hereinafter, also referred to as “compound (B)”), and (C) a compound that generates an acid upon irradiation with ultraviolet light or heating (hereinafter, referred to as “compound (B)”). Also referred to as “compound (C)”
It is characterized by including.
The compound (B) is preferably a compound having a polar group and an ester group.
The compound (B) is preferably a compound having at least one selected from a hydroxyl group and a carboxyl group as a polar group.
The compound (B) is preferably a compound having a structure in which a group represented by the following formula (X) is bonded to a nitrogen atom as an ester group.

(In formula (X), * represents a bonding position with a nitrogen atom, and R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic ring having 4 to 12 carbon atoms. R ¹ and R ² are combined to form an alicyclic hydrocarbon group having 4 to 12 carbon atoms together with the carbon atom to which both are bonded, and R ³ is carbon. A C1-C4 alkyl group or a C4-C12 monovalent alicyclic hydrocarbon group is shown.)

  Furthermore, the compound (B) is preferably a compound represented by the following formula (X-1).

(In the formula (X-1), R ¹ , R ² and R ³ have the same definition as in the above formula (X), Z represents a heterocyclic structure formed with a nitrogen atom, and A is present in a plurality. Each independently represents a single bond, a divalent hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 1 to 8 carbon atoms, R ⁴ represents a hydroxyl group or a carboxyl group, and n is an integer of 1 to 6 Is shown.)

The polysiloxane (A) includes a compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”) and a compound represented by the following general formula (2) (hereinafter referred to as “compound (2)”. It is preferable to include a polysiloxane obtained by hydrolytic condensation.
R _a SiX _4-a (1)
(In general formula (1), R represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group, or an aryl group, and X represents a halogen atom. Or -OR ¹ , R ¹ represents a monovalent organic group, a represents an integer of 1 to 3. In addition, when a plurality of R and X are present, they may be the same as or different from each other. May be.)
SiX ₄ (2)
(In general formula (2), X is the same as defined in general formula (1).)

Further, the polysiloxane composition of the present invention, the content of the polysiloxane (A) with respect to (SiO ₂ equivalent) 100 parts by weight, it is preferable that the content of the compound (B) is 1 to 30 parts by weight.
Further, in the polysiloxane composition of the present invention, the content of the compound (C) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the polysiloxane (A) (in terms of SiO ₂ ). preferable.
Furthermore, the polysiloxane composition of the present invention may contain water.
The polysiloxane composition of the present invention is suitably used as a resist underlayer film composition.

The pattern forming method of the present invention comprises:
(1) A silicon-containing film obtained by applying polysiloxane, an acid diffusion controlling agent, and a compound that generates an acid upon irradiation with ultraviolet light or heating (hereinafter also referred to as an “acid generator”) onto a substrate to be processed. Forming a step;
(2) A step of applying a resist composition on the obtained silicon-containing film to form a resist film;
(3) The step of exposing the resist film by selectively irradiating radiation by allowing the obtained resist film to pass through a photomask;
(4) developing the exposed resist film to form a resist pattern;
(5) A step of forming a pattern by dry etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask.

The polysiloxane composition used in the pattern forming method of the present invention preferably contains an acid diffusion controller.
The polysiloxane composition used in the pattern forming method of the present invention is preferably the polysiloxane composition of the present invention.

The details of the present invention will be described below.
<Polysiloxane composition>
The polysiloxane composition of the present invention comprises a polysiloxane (A), a nitrogen-containing compound (B) having at least one selected from a polar group and an ester group, and a compound (C) that generates an acid upon irradiation with ultraviolet light or heating. ). The use of the polysiloxane composition of the present invention is not particularly limited and can be used as a film forming material such as an interlayer insulating film, a protective film, an antireflection film, etc., but is particularly suitable as a resist underlayer film composition. Used. Especially, it can use suitably as a composition for forming the resist underlayer film in the pattern formation method of this invention.

Polysiloxane (A)
The structure of the polysiloxane (A) is not particularly limited, but preferably the compound (1) represented by the general formula (1) and the compound (2) represented by the general formula (2) ) Is hydrolyzed and condensed, and the compound (1) and the compound (2) may be used singly or in combination.

As the alkyl group having 1 to 5 carbon atoms of R in the general formula (1), a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group; Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group and isoamyl group. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
Examples of the cyanoalkyl group include a cyanoethyl group and a cyanopropyl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.

Preferred examples of the alkenyl group include groups represented by the following general formula (i).
_{CH 2 = CH- (CH 2)} n - * (i)
(In general formula (i), n represents an integer of 0 to 4, and “*” represents a bond.)
N in the general formula (i) is an integer of 0 to 4, preferably an integer of 0 or 1, and more preferably 0 (vinyl group).
Examples of the alkenyl group other than the group represented by the general formula (i) include a butenyl group, a pentenyl group, and a hexenyl group that can be represented by other than the general formula (i).

  Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

X in the general formulas (1) and (2) is a halogen atom such as a fluorine atom or a chlorine atom, or —OR ¹ . Examples of the monovalent organic group in R ¹ include 1 carbon atom such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. ˜4 alkyl groups are preferred. Furthermore, a in the general formula (1) is an integer of 1 to 3, and is more preferably 1 or 2.

Specific examples of the compound (1) represented by the general formula (1) include, for example, phenyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltri Methoxysilane, 4-methoxyphenyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 4-acetylaminophenyltri Methoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethyl Xysilane, 3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxy Silane, 2-phenoxyphenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylaminophenyltrimethoxysilane, 2,4,6- Trimethylphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimeth Aromatic ring-containing trialkoxysilanes such as xoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-aminobenzyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane, 4-acetylaminobenzyltrimethoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, methylsilane, ethyltrimethoxysilane Ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n- Toxisilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethylbistris (trimethylsiloxy) silane, ethyldichlorosilane, ethyltriacetoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyl Tri-tert-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, iso-propyltrimethoxysilane, iso-propyltrie Xysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-sec-butoxysilane, iso-propyltri-tert-butoxy Silane, iso-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane, 2-methylpropyltriethoxysilane Lan, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2-methylpropyl Tri-tert-butoxysilane, 2-methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltri-n-propoxysilane, 1-methylpropyltri-iso- Propoxysilane, 1-methylpropyltri-n-butoxysilane, 1-methylpropyltri-sec-butoxysilane, 1-methylpropyltri-tert-butoxysilane, 1-methylpropyltriphenoxysilane, tert-butyltrimethoxy Orchid, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltri-iso-propoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert -Alkyltrialkoxysilanes such as butoxysilane and tert-butyltriphenoxysilane;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, allyl Alkenyl such as trimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, allyltri-tert-butoxysilane, allyltriphenoxysilane Trialkoxysilanes;
Etc.

  Of these, phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, methyltrimethoxysilane, from the viewpoints of reactivity and ease of material handling, Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxy Lan, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, allyltrimethoxysilane, allyltriethoxysilane and the like are preferable.

Specific examples of the compound (2) represented by the general formula (2) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n- Examples include butoxylan, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, and tetrachlorosilane.
Among these, tetramethoxysilane and tetraethoxysilane are preferable from the viewpoints of reactivity and ease of handling of substances.

  As the hydrolyzable silane compound for obtaining the polysiloxane (A), in addition to the compounds (1) and (2), a hydrolyzable silane compound represented by the following general formula (ii) (hereinafter referred to as the following formula (ii)). , Also referred to as “compound (ii)”).

(In General Formula (ii), R ² and R ⁵ are each independently a hydrogen atom, a hydroxyl group, a fluorine atom, an alkoxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, or a cyano group. Represents an alkyl group or an alkylcarbonyloxy group, each R ³ independently represents a monovalent organic group, R ⁴ represents an arylene group, a methylene group, or an alkylene group having 2 to 10 carbon atoms; ^{And a} plurality of ⁴ may be the same or different, b represents an integer of 1 to 3, and m represents an integer of 1 to 20.)

Examples of the alkoxyl group in R ² and R ⁵ of the general formula (ii) include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, and 1-methyl. Propoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n- A decyloxy group etc. can be mentioned.
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
Examples of the cyanoalkyl group include a cyanoethyl group and a cyanopropyl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.

Examples of the monovalent organic group in R ³ of the general formula (ii) include groups having a cyclic ether structure such as an alkyl group, an alkoxyl group, an aryl group, and an alkenyl group; a glycidyl group. Among these, an alkyl group, an alkoxyl group, and an aryl group are preferable.
As said alkyl group, a C1-C5 linear or branched alkyl group is mentioned. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
As said alkoxyl group, a C1-C10 linear or branched alkoxyl group is mentioned. Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neo Examples include pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, a phenethyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Among these, a phenyl group is preferable.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 3-butenyl group, 3-pentenyl group, and 3-hexenyl group.
When a plurality of R ⁴ are present (that is, when m is an integer of 2 to 20), the plurality of R ⁴ may be the same or different.

As an arylene group in R < ⁴ > of the said general formula (ii), a C6-C10 arylene group is preferable, for example. Specific examples include a phenylene group, a naphthylene group, methylphenylene, ethylphenylene, chlorophenylene group, bromophenylene group, and fluorophenylene group.
Moreover, as a C2-C10 alkylene group, ethylene group, a propylene group, a butylene group etc. are mentioned, for example.

B in the general formula (ii) is an integer of 1 to 3, and preferably 1 or 2.
Moreover, m is an integer of 1-20, Preferably it is 5-15, More preferably, it is 5-10.

  Specific examples of the compound (ii) include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2- Pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1, 2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1, 1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyl Disilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1 , 2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2- Tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane,

  1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2-trimethyl Disilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2 -Triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1 1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dipheno 1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1, 2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane;

  Bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-isopropoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis ( Tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis ( Tri-n-propoxysilyl) ethane, 1,2-bis (tri-isopropoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ) Ethane, 1,2-bis (tri-tert-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimeth) Sisilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di -Isopropoxymethylsilyl) -1- (tri-isopropoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxy Methylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (Trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethyl) Yl) -2- (tri-n-propoxysilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (tri-isopropoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2 -(Tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- ( Tri-tert-butoxysilyl) ethane,

  Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-isopropoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-isopropoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1, 2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) Ethane, bis (dimethylmethoxysilyl) methane, bis (dimethylethoxysilyl) methane, bis (dimethyl-n-propoxysilyl) methane, bis (dimethyl-isopropoxysilyl) methane, bis (dimethyl-n-butoxysilyl) methane, Bis (dimethyl-sec-butoxysilyl) methane, bis (dimethyl-tert-butoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1,2- Bis (dimethyl-n-propoxysilyl) ethane, 1,2-bis (dimethyl-isopropoxysilyl) ethane, 1,2-bis (dimethyl-n-butoxysilyl) ethane, 1,2-bis (dimethyl-sec- Butoxysilyl) ethane, 1,2-bis (dimethyl-tert-but Shishiriru) ethane,

  1- (dimethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-isopropoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-sec-butoxymethylsilyl) -1 -(Trimethylsilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2 -(Trimethylsilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- ( Limethylsilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-sec-butoxymethyl) Silyl) -2- (trimethylsilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (trimethylsilyl) ethane,

  1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-isopropoxysilyl) ) Benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) benzene, 1, 3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri-isopropoxysilyl) benzene 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri tert-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4- Bis (tri-isopropoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-tert- Butoxysilyl) benzene and the like.

  Furthermore, polycarbosilanes such as polydimethoxymethylcarbosilane and polydiethoxymethylcarbosilane are exemplified.

  Among these compounds, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2 -Tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, bis (trimethoxysilyl) methane, bis (Triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxy Methylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxy) Methylsilyl) ethane, bis (dimethylmethoxysilyl) methane, bis (dimethylethoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1- (dimethoxymethyl) Silyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) 1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1, 4-bis (triethoxysilyl) benzene, polydimethoxymethylcarbosilane, polydiethoxymethylcarbosilane and the like are preferable.

  Compound (ii) may be used alone or in combination of two or more.

In addition, 1 type of polysiloxane (A) may be contained in the insulating pattern formation material in this invention, and may be contained 2 or more types.
The molecular weight of the polysiloxane (A) is preferably a polystyrene-reduced weight average molecular weight by size exclusion chromatography, preferably 1,000 to 100,000, more preferably 1,000 to 50,000, particularly preferably 1,000 to 30. , 000.
In addition, the molecular weight of the polysiloxane (A) in the present specification uses a GPC column manufactured by Tosoh Corporation (trade name “G2000HXL”, product name “G3000HXL”, product name “G4000HXL” 1), Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C.

  As a method of hydrolyzing and / or partially condensing the compound (1), the compound (2), and other hydrolyzable silane compounds as required, known hydrolysis and condensation methods can be used.

  In constituting the polysiloxane composition of the present invention, the content of alcohol having a boiling point of 100 ° C. or less in the composition is preferably 20% by weight or less, particularly preferably 5% by weight or less. Alcohol having a boiling point of 100 ° C. or less may be generated during hydrolysis and / or partial condensation of the compounds represented by the above compounds (A) and (C), and the content thereof is 20% by weight or less, preferably It is preferable to remove it by distillation or the like so as to be 5% by weight or less.

Compound (B)
The compound (B) is a nitrogen-containing compound having at least one selected from a polar group and an ester group.
The compound (B) is a compound having a basic amino group or a compound that becomes a basic amino group by the action of an acid. When the polysiloxane composition of the present invention is used for a resist underlayer film composition, It has the effect of improving the lithography performance of the resist on the lower layer film obtained from the product. This effect is due to the presence of the compound (B) in the lower layer film, which suppresses the diffusion of acid in the lower layer film from the resist film during post-exposure baking (PEB) after exposure. It is considered that the lithography performance is further improved. This effect is remarkable as compared with conventional amine compounds. By using a compound having at least one selected from a polar group and an ester group as compared with a conventional amine compound, sublimation of the amine compound is suppressed during baking of the lower layer film, and the above effect is sufficiently exhibited because it remains in the lower layer film. Conceivable.
Further, the compound (B) is preferably a compound having a cyclic structure, and specifically, preferably has a nitrogen-containing heterocyclic structure. By using such a structure, it is considered that there is an effect in improving the storage stability as the lower layer film composition.

  Examples of the nitrogen-containing heterocyclic structure in the compound (B) include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2 In addition to imidazoles such as methyl-4-phenylimidazole, 2-methylbenzimidazole, 2-phenylbenzimidazole, indole, pyrrole, pyrazole, adenine, guanine, purine, pyrrolidine, 2-pyrrolidinemethanol, 3-pyrrolidinol, piperidine Morpholine, 4-hydroxypiperidine, 2,6-dimethylpiperidine, 4-hydroxy-2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6- Tramethylpiperidine, piperazine, homopiperazine, 1-methylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1-isopropylpiperazine, 1-piperazineethanol, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 3- Aminopyrrolidine, L-proline, 4-hydroxy-L-proline, pipecolic acid, nipecotic acid, isonipecotic acid, 2-piperazinecarboxylic acid, 1,4,7-triazacyclononane, 1,4,7,10-tetra And azacyclododecane.

The polar group and the ester group in the compound (B) may be bonded to the nitrogen-containing heterocyclic structure or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain —O—, —CO—, —NH—, —SO ₂ — and the like.
Examples of the polar group include a hydroxyl group, a carboxyl group, a cyano group, and an oxetanyl group. A hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable.
Examples of the ester group include an alkyl ester group, an aryl ester group, and a cycloalkyl ester group, and a group represented by the above formula (X) is preferable. The compound (B) having the above formula (X) is a compound in which the —CR ¹ R ² R ³ group is dissociated by the action of an acid to become a basic amino group, and the effect of excellent storage stability in a liquid state Have
In the formula ^(X), the alkyl group having 1 to 4 carbon atoms represented by R 1, ^{R 2} and ^{R 3,} methyl, ethyl, n- propyl, i- propyl, n- butyl group , I-butyl group and the like. 4 to 12 carbon atoms formed together with a monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ¹ , R ² and R ³ , and the carbon atoms to which R ¹ and R ² are bonded to each other. Examples of the divalent alicyclic hydrocarbon group include cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cyclooctane, and cyclodecane; and bridged alicyclics such as norbornane, tricyclodecane, tetracyclododecane, and adamantane. Examples include derived groups.

Examples of the monovalent group represented by —CR ¹ R ² R ³ in the above formula (1) include a t-butyl group, a t-amyl group, a 1-ethyl-1-methylpropyl group, and 1,1-diethylpropyl. A branched alkyl group such as a group; a group having an alicyclic structure represented by the following formulas (i-1) to (i-15) is preferable. Among these, a t-butyl group and a t-amyl group are more preferable because they can be easily synthesized.

As the compound (B), a compound having both a polar group and an ester group is more preferable, and a compound represented by the above formula (X-1) is particularly preferable.
In the above formula (X-1), the divalent hydrocarbon group having 1 to 8 carbon atoms represented by A includes a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, n A divalent chain hydrocarbon group such as an octylene group; a divalent alicyclic hydrocarbon obtained by removing one hydrogen atom from the alicyclic hydrocarbon group represented by R ¹ , R ^{2 or} R ³ described above Groups and the like. n is an integer of 1 to 6, preferably 1 or 2, and more preferably 1.
Specific preferred specific examples of the compound represented by the formula (X-1) include, for example, the following formulas (X-1-1) to (X-1-4).

  Moreover, as the compound (B) other than the compound represented by the formula (X-1), the following compounds are preferably used.

In addition, these compounds (B) may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the compound (B) used is usually 1.0 to 30 parts by mass, preferably 1 with respect to 100 parts by mass of the polysiloxane (SiO ₂ equivalent) (A) from the viewpoint of improving the pattern shape. 0.0 to 10 parts by mass.

Compound (C)
The compound (C) is an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating, and examples of the acid generator (C) include onium salts such as sulfonium salts and iodonium salts, and organic halogen compounds. And sulfone compounds such as disulfones and diazomethane sulfones.

Specific examples of the compound (C) include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl ) -1,1-difluoroethanesulfonate, triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium salicylate, triphenylsulfonium camphorsulfonate, triphenylsulfone Umutorishikuro [3.3.1.1 ^{3, 7]} decanyl difluoromethane sulfonate, triphenylsulfonium salts and the like compounds;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7, 10]} dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds.
In addition, these compounds (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the compound (C) used is usually 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polysiloxane (A) from the viewpoint of improving the pattern shape. Parts, more preferably 0.1 to 10 parts by mass.

  In the present invention, water may be added to the composition. When water is added, the silicon-containing compound is hydrated, so that the storage stability is improved. Further, when water is added, curing during film formation is promoted, and a dense film can be obtained. The water content in the solvent component of the composition is 0 to 30% by mass, preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass. If the amount of water added is too large, the storage stability may deteriorate and the uniformity of the coating film may deteriorate.

Other Components The polysiloxane composition of the present invention may further contain a β-diketone. By using β-diketone, the effect of improving coating properties and storage stability can be obtained. β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3 , 5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2 , 4-heptanedione, or two or more.
In the present invention, the β-diketone content in the film-forming composition is 50% by weight or less, preferably 30% by weight or less of the total solvent.
If β-diketone is added in such a range, a certain storage stability can be obtained, and there is little possibility that characteristics such as coating film uniformity of the composition will deteriorate.

Further, the polysiloxane composition of the present invention may further contain components such as colloidal silica, colloidal alumina, organic polymer, surfactant, base generator and the like.
The colloidal silica is a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent. Usually, the average particle size is 5 to 30 nm, preferably 10 to 20 nm, and the solid content concentration is 10 to 40% by mass. It is about. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol, isopropanol silica sol; Catalyst Chemical Industry Co., Ltd., Oscar. These colloidal silicas may be used alone or in combination of two or more.
Examples of the colloidal alumina include alumina sol 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemical Co., Ltd. These colloidal aluminas may be used alone or in combination of two or more.

Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, an acrylate compound, a methacrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, and a polyamide. , Polyquinoxaline, polyoxadiazole, fluorine-based polymer, and the like. These organic polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. Surfactant etc. are mentioned. These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

Production method of polysiloxane composition The production method of the polysiloxane composition of the present invention is not particularly limited. For example, polysiloxane (A), compound (B), compound (C), and water as necessary, It is obtained by mixing an additive and dissolving or dispersing in an organic solvent. As the organic solvent, a known organic solvent can be used, and a solvent similar to that used when hydrolyzing and / or partially condensing the hydrolyzable silane compound can be used.
In addition, solid content concentration of the polysiloxane composition of this invention is 0.5 to 20 weight%, Preferably it is 0.6 to 15 weight%.

Resist Underlayer Film The resist underlayer film obtained from the composition of the present invention has a high adhesion to the resist film and other underlayer films (antireflection films), and a resist pattern having an excellent bottom shape without skirting or the like is obtained. Has characteristics. Therefore, it can be suitably used in a multilayer resist process. Further, among multilayer resist processes, it is particularly preferably used in pattern formation using a multilayer resist process in a region finer than 90 nm (ArF, ArF, F ₂ , EUV, nanoimprint in immersion exposure). it can.
This resist underlayer film can be obtained by using the above-described polysiloxane composition of the present invention. Specifically, by applying to the surface of the resist film and other lower layer film (antireflection film), etc., to form a coating film of the resist underlayer film forming composition, by heating this coating film, By curing, a resist underlayer film (silicon-containing film) can be formed.
As a method for applying the polysiloxane composition, a spin coating method, a roll coating method, a dipping method, or the like can be used.
Moreover, the heating temperature of the coating film formed is 50-450 degreeC normally, and the film thickness after heat processing is 10-200 nm normally.

<Pattern formation method>
The pattern forming method of the present invention comprises (1) a step of forming a silicon-containing film by applying a polysiloxane composition containing a polysiloxane, an acid diffusion controller and an acid generator on a substrate to be processed (hereinafter referred to as “a silicon-containing film”). (Hereinafter referred to simply as “step (1)”) and (2) a step of applying a resist composition on the obtained silicon-containing film to form a resist film (hereinafter simply referred to as “step (2)”). And (3) a process of exposing the resist film by selectively irradiating the resist film by transmitting the obtained resist film through a photomask (hereinafter, simply referred to as “process (3)”). (4) developing the exposed resist film to form a resist pattern (hereinafter simply referred to as “step (4)”), and (5) using the resist pattern as a mask (etching mask), Silicon-containing film and the step of forming a pattern to be processed substrate by dry etching (hereinafter, simply "step (5)" hereinafter.) Includes a, a.
According to the pattern forming method of the present invention, a resist pattern can be faithfully transferred to a substrate to be processed with high reproducibility in a dry etching process.

Process (1)
In the step (1), a silicon-containing film is formed on a substrate to be processed using a polysiloxane composition containing polysiloxane, an acid diffusion controller, and an acid generator. Thereby, a substrate with a resist underlayer film in which an underlayer film is formed on a substrate to be processed can be obtained.
As the polysiloxane composition used in the step (1), the polysiloxane composition of the present invention is particularly preferably used, but the structures of the polysiloxane, the acid diffusion controller and the acid generator are particularly limited. is not.
The acid diffusion controller is a compound having a function of preventing the acid generated by exposure from diffusing into the silicon-containing film obtained in the step (1), and a basic compound is generally used. The compound (B) described above is particularly preferable, but other amino compounds other than the compound (B), onium salts that generate a weak acid by the action of an acid and lose basicity, and the like may be used.

  As the substrate to be processed, for example, an insulating film such as silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, etc., hereinafter all trade names are black diamond (manufactured by AMAT), silk (manufactured by Dow Chemical), LKD5109. An interlayer insulating film such as a wafer coated with a low dielectric insulating film such as [manufactured by JSR] can be used. As the substrate to be processed, a patterned substrate such as a wiring course (trench) or a plug groove (via) may be used.

In addition, another lower layer film (another resist lower layer film different from the silicon-containing film obtained from the above-described polysiloxane composition) may be formed in advance on the substrate to be processed.
This resist underlayer film has a predetermined function (for example, reflection) required for further supplementing the function of the silicon-containing film and / or the resist film in the formation of the resist pattern or for obtaining the function that these do not have. It is a film provided with a prevention function, coating film flatness, and high etching resistance against a fluorine-based gas such as CF ₄ .

In order to further improve the adhesion between the silicon-containing film and the resist, the surface of the silicon-containing film may be subjected to methylsilylation treatment.
Examples of the silylation treatment agent include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, bis (trimethylsilyl) urea, trimethylchlorosilane, N- (trimethylsilyl) acetamide, trimethylsilylazide, Trimethylsilyl cyananide, N- (trimethylsilyl) imidazole, 3-trimethylsilyl-2-oxazolidinone, trimethylsilyltrifluoromethanesulfonate, hexamethyldisilazane, heptamethyldisilazane, hexamethyldisiloxane, N-methyl-N-trimethylsilyltrifluoro Acetamide, (N, N-dimethylamino) trimethylsilane, nonamethyltrisilazane, 1,1,3,3-tetramethyldisilazaza , And the like trimethyl iodo silane.
Methylsilylation of a silicon-containing film can be performed by dip coating or spin coating the silylating agent on the silicon-containing film, or by exposing the silicon-containing film to the vapor atmosphere of the silylating agent. Thereafter, the coating film may be heated to 50 to 300 ° C.

  The silicon-containing film can also be formed on the antireflection film. Examples of the antireflection film include materials commercially available under trade names such as NFC HM8006 (manufactured by JSR Corporation).

The method for forming the silicon-containing film is not particularly limited. For example, a coating film formed by applying a polysiloxane composition on a substrate to be processed by a known method such as a spin coating method is exposed and / or heated. It can be formed by curing.
Examples of the radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ-rays, molecular beams, and ion beams.
Moreover, the temperature at the time of heating a coating film is although it does not specifically limit, It is preferable that it is 90-550 degreeC, More preferably, it is 90-450 degreeC, More preferably, it is 90-300 degreeC.

  The thickness of the silicon-containing film is not particularly limited, but is preferably 100 to 20,000 nm.

Process (2)
In the step (2), a resist film is formed on the silicon-containing film obtained in the step (1) using the resist composition.
The resist composition used in this step (2) includes, for example, a chemically amplified resist composition having a resin whose solubility in an alkaline developer is increased by the action of an acid, an alkali-soluble resin, and a quinonediazide-based photosensitizer. Preferred examples include positive resist compositions, negative resist compositions containing an alkali-soluble resin and a crosslinking agent. For the formation of the resist pattern, a double patterning method, a double exposure method, or the like, which is a method for forming a fine pattern, may be used as appropriate. A method of forming a negative pattern by developing a resist composition having a resin whose solubility in an alkali developer increases by the action of an acid as described in JP-A-2008-292975 with an organic solvent. May be used, and the method and the double exposure method may be used in combination.

Moreover, the solid content concentration of the resist composition is not particularly limited, but is preferably 5 to 50% by mass, for example.
Moreover, as a resist composition, what was filtered using the filter with a hole diameter of about 0.2 micrometer can be used conveniently. In the pattern forming method of the present invention, a commercially available resist composition can be used as it is as such a resist composition.

  The method for applying the resist composition is not particularly limited, and for example, it can be applied by a conventional method such as spin coating. In addition, when apply | coating a resist composition, the quantity of the resist composition to apply | coat is adjusted so that the resist film obtained may become a predetermined film thickness.

The resist film may be formed by volatilizing a solvent (that is, a solvent contained in the resist composition) in the coating film by pre-baking the coating film formed by applying the resist composition. it can.
Although the temperature at the time of prebaking is suitably adjusted according to the kind etc. of resist composition to be used, it is preferable that it is 30-200 degreeC, More preferably, it is 50-150 degreeC.

Step (3)
In the step (3), the resist film obtained in the step (2) is selectively irradiated with radiation through a photomask to expose the resist film.

The radiation used in this step (3) includes visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, molecular beams, ions, depending on the type of acid generator used in the resist composition. Although it is appropriately selected from a beam or the like, it is preferable to use far ultraviolet rays, and in particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm) ), ArKr excimer laser (wavelength 134 nm), extreme ultraviolet light (wavelength 13 nm, etc.) and the like can be mentioned as preferred examples.
The exposure method is not particularly limited, and can be performed in accordance with a conventionally known method for pattern formation.

Step (4)
In the step (4), the resist film exposed in the step (3) is developed to form a resist pattern.

  The developing solution used for development can be appropriately selected according to the type of resist composition used. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n -Propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5 4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, and other alkaline aqueous solutions can be used. These alkaline aqueous solutions may be those obtained by adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant.

  In the case of a negative resist composition, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc., first amines such as ethylamine, n-propylamine, etc. Secondary amines such as amines, diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Aqueous solutions of alkalis such as quaternary ammonium salts such as copper and choline and cyclic amines such as pyrrole and piperidine can be used.

  Furthermore, as an organic solvent-based developer that can be used to form a negative pattern by developing a resist composition having a resin whose solubility in an alkaline developer is increased by the action of an acid, an ketone solvent, Alcohol solvents, amide solvents, ether solvents, ester solvents and the like can be used.

  For example, ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone. Etc.

Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n- Alcohols such as octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether and triethylene glycol mono List glycol ether solvents such as ethyl ether and methoxymethylbutanol. Can.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy. Examples include propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate.

A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.

  In step (4), after developing with the developer, washing and drying can form a predetermined resist pattern corresponding to the photomask.

  In this step (4), in order to improve resolution, pattern profile, developability, etc., it is preferable to perform post-bake before development (that is, after exposure in step (3)). The post-baking temperature is appropriately adjusted according to the type of resist composition used, but is preferably 50 to 200 ° C, more preferably 80 to 150 ° C.

Process (5)
In the step (5), the silicon-containing film and the substrate to be processed are dry-etched using the resist pattern formed in the step (4) as a mask (etching mask) to form a pattern. When a substrate to be processed on which another resist underlayer film is formed is used, the resist underlayer film is also dry etched together with the silicon-containing film and the substrate to be processed.

The dry etching can be performed using a known dry etching apparatus.
The source gas during dry etching depends on the elemental composition of the film to be etched, but includes oxygen atoms such as O ₂ , CO, and CO ₂ , inert gases such as He, N ₂ , and Ar, Cl ₂ , chlorine gas such as BCl ₄ , H ₂ , NH ₃ gas, or the like can be used. These gases can be used in combination.

  In the pattern forming method of the present invention, a predetermined pattern for substrate processing can be formed by appropriately performing the steps (1) to (5) described so far.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. In addition, determination of the content rate of the solid content in a present Example and the measurement of a weight average molecular weight (Mw) were performed with the following method.
<Determination of solid content>
By baking 0.5 g of the siloxane resin solution at 250 ° C. for 30 minutes, the weight of the solid content relative to 0.5 g of the resin solution was measured, and the solid content of the siloxane resin solution was determined.
<Measurement of weight average molecular weight (Mw)>
Tosoh GPC columns (trade name "G2000HXL", trade name "G3000HXL", trade name "G4000HXL" 1), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature : Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

[1] Synthesis of Polymer [Polysiloxane (A)] In each of the synthesis examples described later, a polymer was synthesized using a monomer having the following structure.
Compound (M-1); tetramethoxysilane compound (M-2); phenyltrimethoxysilane compound (M-3); 4-methylphenyltrimethoxysilane compound (M-4); 1,2-bis (triethoxy) Silyl) benzene compound (M-5); methyltrimethoxysilane

Synthesis Example 1 [Polysiloxane (A-1)]
1.28 g of oxalic acid was dissolved in 12.85 g of water by heating to prepare an aqueous oxalic acid solution. Then, 25.05 g of tetramethoxysilane [formula (M-1)], 3.63 g of phenyltrimethoxysilane [formula (M-2)], and 57.19 g of propylene glycol monoethyl ether were placed in a flask. A condenser tube and a dropping funnel containing the prepared aqueous oxalic acid solution were set. Subsequently, after heating to 60 degreeC with an oil bath, the oxalic acid aqueous solution was dripped slowly, and it was made to react at 60 degreeC for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and methanol generated by the reaction was removed to obtain 97.3 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-1).
The content ratio of the solid content in the obtained resin solution was 18.0%. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane was 2000.

Synthesis Example 2 [Polysiloxane (A-2)]
2.92 g of tetramethylammonium hydroxide was dissolved by heating in 8.75 g of water to prepare an aqueous solution of tetraammonium hydroxide. Then, in a flask containing 11.67 g of the prepared tetraammonium hydroxide aqueous solution, 4.53 g of water, and 20 g of methanol, a condenser tube, 10.66 g of tetramethoxysilane [formula (M-1)], 4-methyl A dropping funnel containing 2.12 g of phenyltrimethoxysilane [formula (M-3)], 2.72 g of methyltrimethoxysilane [formula (M-4)] and 20 g of methanol was set. Then, after heating to 50 ° C. in an oil bath, a methanol solution of the monomer was slowly dropped and reacted at 50 ° C. for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.
Thereafter, 4.39 g of maleic anhydride was dissolved in 16.14 g of water and 16.14 g of methanol, and 36.67 g of a maleic acid methanol solution separately prepared, the reaction solution cooled as described above was added dropwise, Stir for 30 minutes. Subsequently, 50 g of 4-methyl-2-pentenone was added and then set in an evaporator, and the reaction solvent and methanol produced by the reaction were removed to obtain a 4-methyl-2-pentenone resin solution. After the obtained resin solution was transferred to a separatory funnel, 80 g of water was added to perform first washing with water, and 40 g of water was added to perform second washing with water. Thereafter, 50 g of propylene glycol-1-ethyl ether was added to the 4-methyl-2-pentenone resin solution transferred from the separatory funnel to the flask, and then set in an evaporator to remove 4-methyl-2-pentenone. 51 g of resin solution was obtained. Let the solid content in this resin solution be polysiloxane (A-2).
The content rate of solid content in the obtained resin solution was 14.5%. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane was 4000.

Synthesis Examples 3 to 9 [Polysiloxane (A-3) to (A-5)]
<Polysiloxane (A-3) to (A-5)>
Polysiloxanes (A-3) to (A-5) were synthesized in the same manner as in Synthesis Example 1 except that the monomers shown in Table 1 were used in the amounts shown in Table 1.
The solid content of the obtained resin solution and the weight average molecular weight (Mw) of the obtained polysiloxane are shown in Table 1 together with Synthesis Examples 1 and 2.

[2] Production of polysiloxane composition Polysiloxane (A) [polysiloxane (A-1) to (A-5)] obtained in each of the above synthesis examples, compound (B) [compound (B-1) To (B-6)], compound (C) [compounds (C-1) to (C-3)], water and organic solvent (E) [organic solvents (E-1) to (E-2)]. Using, the polysiloxane composition (coating liquids 1-19) of Examples 1-14 and Comparative Examples 1-5 was prepared as follows. The compound (B), compound (C) and organic solvent (E) used are as follows.

<Compound (B)>

<Compound (C)>

<Organic solvent (E)>
(E-1): Propylene glycol monoethyl ether (E-2): Propylene glycol monomethyl ether acetate

<Example 1>
As shown in Table 2, 9.40 parts of polysiloxane (A-1) obtained in Synthesis Example 1, 0.05 part of compound (B-1), 0.05 part of compound (C-1), water, After dissolving in 21.75 parts of organic solvent (E-1) and 68.75 parts of organic solvent (E-2), this solution was filtered with a filter having a pore size of 0.2 μm to obtain the polysiloxane of Example 1. A composition was obtained.
<Examples 2 to 16 and Comparative Examples 1 to 4>
Polysiloxane compositions of Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same manner as Example 1 except that each component was used in the ratio shown in Table 2.

<Formation of resist underlayer film and its evaluation>
The compositions obtained in Examples and Comparative Examples were applied on a silicon wafer by a spin coating method. (The trade name “CLEAN TRACK ACT12 (manufactured by Tokyo Electron Co., Ltd.)” was used for the spin coating. Hereinafter, the same applies to those not specifically described) 220 ° C. hot plate for the obtained coating film PB was performed for 1 minute to form a resist underlayer film. The thickness of the obtained resist underlayer film was 30 nm when measured with a film thickness measuring device (trade name “M-2000D”, manufactured by JA Woollam). About the obtained resist underlayer film, the resist underlayer film was evaluated by the method shown below.
(Substrate reflectance)
Refractive index parameter (n) and extinction coefficient (k) of each silicon-containing film, composition for forming a lower layer film (trade name “NFC HM8006”, manufactured by JSR Co., Ltd.), resist material, and high-speed spectroscopic ellipsometer “M” -2000 "(manufactured by JA Woollam), and based on this measurement value, using simulation software" Prolith "(manufactured by KLA-Tencor), resist material under NA 1.3, Dipole conditions / each The substrate reflectance of the film in which the silicon-containing film / underlayer film forming composition film was laminated was determined. When the reflectance was 1% or less, “◯” and when it exceeded 1% were designated as “X”.
(Oxygen etching resistance)
The resist underlayer film was O ₂ treated at 100 W for 120 seconds using a dry etching apparatus (manufactured by Tokyo Electron, Telius SCCM), and the film thickness difference before and after the treatment was measured. When the difference between the two is less than 10 nm, the oxygen etching resistance is very good, and when it is within the range of 10 to 15 nm, it can be evaluated that it is usable, and when it exceeds 15 nm, it is poor.

(Lithography evaluation, alkaline aqueous solution development)
After spin coating a 12-inch silicon wafer with a lower antireflection film (trade name “HM8006”, manufactured by JSR Corporation), PB (250 ° C., 60 seconds) is performed to form a coating film having a thickness of 100 nm. did. The coating composition prepared in Examples or Comparative Examples was spin coated on the coating film, PB (220 ° C., 60 seconds), and then cooled (23 ° C., 60 seconds) to form a resist underlayer film having a thickness of 30 nm. Formed. Next, a resist composition (trade name “ARF AR2772JN”, manufactured by JSR Corporation) is spin-coated on the resist underlayer film, PB (100 ° C., 60 seconds), and then cooled (23 ° C., 30 seconds). As a result, a resist layer having a thickness of 100 nm was formed. Further, the upper layer film forming composition is spin-coated on the formed resist film using a trade name “Lithius Pro-i (manufactured by Tokyo Electron Ltd.)”, and PB (90 ° C., 60 seconds) is performed. Thus, an upper layer film having a thickness of 90 nm was formed.

  Next, using an ArF immersion exposure apparatus (trade name “S610C”, manufactured by NIKON) through a mask having a mask size of 42 nm line / 84 nm pitch under the optical conditions of NA: 1.30 and Dipole. Exposed. PEB (100 ° C., 60 seconds) on a hot plate of the product name “Lithius Pro-i”, cooled (23 ° C., 30 seconds), and then paddled with TMAH aqueous solution as a developer at the LD nozzle of the developing cup. Development (30 seconds) and rinsing with ultrapure water. The substrate for evaluation on which a resist pattern of 42 nm line / 84 nm pitch was formed was obtained by spin-drying by shaking off at 2000 rpm for 15 seconds, and the dimensions before collapse and the pattern shape were evaluated as described later. A scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi High-Technologies Corporation) was used for measuring and observing the resist pattern of the evaluation substrate.

When the substrate for evaluation was obtained, the exposure amount formed a resist pattern having a line width of 42 nm and a distance (space) between adjacent lines of 84 nm (line and space is 1 to 2). With (mJ / cm ² ) as the optimum exposure amount, the exposure was sequentially performed with an exposure amount stepwise larger than the optimum exposure amount. At this time, since the line width of the obtained pattern is gradually narrowed, the collapse of the resist pattern is finally observed at the line width corresponding to a certain exposure amount. Therefore, the line width corresponding to the maximum exposure amount at which the resist pattern is not confirmed to be collapsed is defined as the minimum dimension before collapse (nm) and used as an index for pattern collapse resistance. The evaluation standard of the dimension before the minimum collapse is good when it is 30 nm or less, is usable when it is in the range of more than 30 nm and not more than 40 nm, and is poor when it exceeds 40 nm. In the case of 30 nm to 40 nm or less, “◯”, and in the case where it is larger than 40 nm, or “×” when evaluation is impossible due to pattern collapse. The pattern shape was evaluated as “◯” when the bottom of the resist pattern was not skirted, and “X” when the pattern was collapsed or skirted.

(Lithography evaluation, organic solvent development)
An antireflective film forming material (trade name “HM8006”, manufactured by JSR Corporation) is spin-coated on a 12-inch silicon wafer, and then subjected to PB (250 ° C., 60 seconds) to form an antireflective film having a thickness of 100 nm. Formed. A polysiloxane composition was spin-coated on the film, PB (220 ° C., 60 seconds), and then cooled (23 ° C., 60 seconds) to form a resist underlayer film having a thickness of 30 nm. Subsequently, a radiation sensitive resin composition was spin-coated on the resist underlayer film, PB (90 ° C., 60 seconds), and then cooled (23 ° C., 30 seconds) to form a resist film having a thickness of 100 nm. .

  Next, using an ArF immersion exposure apparatus (trade name “S610C”, manufactured by NIKON) through a mask having a mask size of 40 nm line / 80 nm pitch under the optical conditions of NA: 1.30 and Dipole. Exposed. After PEB (100 ° C., 60 seconds) on a hot plate of the product name “Lithius Pro-i”, cooling (23 ° C., 30 seconds), paddle development (30 seconds) using butyl acetate as a developer, methyl Rinse with isobutyl carbinol (MIBC). An evaluation substrate on which a resist pattern having a 40 nm line / 80 nm pitch was formed was obtained by spin-drying at 2000 rpm for 15 seconds, and the dimensions before collapse and the pattern shape were evaluated as described later. A scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi High-Technologies Corporation) was used for measuring and observing the resist pattern of the evaluation substrate.

When the evaluation substrate was obtained, the exposure amount formed a resist pattern having a line width of 42 nm and a distance (space) between adjacent lines of 80 nm (line and space is 1 to 2). With (mJ / cm ² ) as the optimum exposure amount, exposure was sequentially performed with an exposure amount stepwise smaller than the optimum exposure amount. At this time, since the line width of the obtained pattern is gradually narrowed, the collapse of the resist pattern is finally observed at the line width corresponding to a certain exposure amount. Therefore, the line width corresponding to the maximum exposure amount at which the resist pattern is not confirmed to be collapsed is defined as the minimum dimension before collapse (nm) and used as an index for pattern collapse resistance. The evaluation standard of the dimension before the minimum collapse is good when it is 30 nm or less, is usable when it is in the range of more than 30 nm and not more than 40 nm, and is poor when it exceeds 40 nm. In the case of 30 nm to 40 nm or less, “◯”, and in the case where it is larger than 40 nm, or “×” when evaluation is impossible due to pattern collapse. The pattern shape was evaluated as “◯” when the bottom of the resist pattern was not skirted, and “X” when the pattern was collapsed or skirted.
The obtained evaluation results are also shown in Table 3.

The resist underlayer composition of the present invention has excellent antireflection performance, excellent adhesion to a chemically amplified resist, excellent resistance to a developer used after exposure of the resist, and resist residue after development. Less pattern transferability. In addition, the sensitivity, resolution, exposure margin, and pattern shape of the resist material are also satisfied. In particular, among multilayer resist processes, it can be suitably used in pattern formation using a multilayer resist process in a region finer than 60 nm (ArF, ArF in immersion exposure, F ₂ , EUV, nanoimprint).

Claims (10)

A polysiloxane composition for resist underlayer film,
(A) polysiloxane,
(B) a hydroxyl group, seen containing at least one selected from a carboxyl group and an ester group, a nitrogen-containing compound having a cyclic structure, and (C) a compound that generates an acid by irradiation or heating of the ultraviolet light,
(A) The polysiloxane composition, wherein the content of the compound (C) is 0.1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polysiloxane content (in terms of SiO ₂ ) . (B) The polysiloxane composition according to claim 1 , wherein the nitrogen-containing compound is a compound having a nitrogen-containing heterocyclic structure. A polysiloxane composition for resist underlayer film,
(A) polysiloxane,
(B) viewed contains a hydroxyl group and a nitrogen-containing compound having at least one ester group selected from a carboxyl group, and (C) a compound which generates an acid by irradiation or heating of the ultraviolet light,
(A) The polysiloxane composition, wherein the content of the compound (C) is 0.1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polysiloxane content (in terms of SiO ₂ ) . A polysiloxane composition for resist underlayer film,
(A) polysiloxane,
(B) As an ester group, a nitrogen-containing compound having a structure in which a group represented by the following formula (X) is bonded to a nitrogen atom , and (C) a compound that generates an acid by irradiation with ultraviolet light or heating,
(A) The polysiloxane composition, wherein the content of the compound (C) is 0.1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polysiloxane content (in terms of SiO ₂ ) .

(In formula (X), * represents a bonding position with a nitrogen atom, and R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic ring having 4 to 12 carbon atoms. R ¹ and R ² are combined to form an alicyclic hydrocarbon group having 4 to 12 carbon atoms together with the carbon atom to which both are bonded, and R ³ is carbon. A C1-C4 alkyl group or a C4-C12 monovalent alicyclic hydrocarbon group is shown.) (B) The polysiloxane composition according to claim 4 , wherein the nitrogen-containing compound is a compound represented by the following formula (X-1).

(In the formula (X-1), R ¹ , R ² and R ³ have the same definition as in the above formula (X), Z represents a heterocyclic structure formed with a nitrogen atom, and A is present in a plurality. Each independently represents a single bond, a divalent hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 1 to 8 carbon atoms, R ⁴ represents a hydroxyl group or a carboxyl group, and n is an integer of 1 to 6 Is shown.) (A) polysiloxane, claim from claim 1 comprising a polysiloxane obtained by hydrolysis and condensation of compounds represented by compounds represented by the following general formula (1), the following general formula (2) 5 The polysiloxane composition according to any one of the above.
R _a SiX _4-a (1)
[In General Formula (1), R represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group, or an aryl group, and X represents a halogen atom. or indicates -OR ^{1, R 1} represents a monovalent organic group, a is an integer of 1-3. In addition, when there exist two or more R and X, respectively, they may mutually be same or different. ]
SiX ₄ (2)
[In General Formula (2), X is the same as the definition of General Formula (1). ] The polysiloxane composition according to claim 6 , wherein (A) the polysiloxane includes a polysiloxane obtained by hydrolytic condensation of a compound in which X in the general formulas (1) and (2) represents —OR ¹ . The content of (A) a polysiloxane relative to (SiO ₂ equivalent) 100 parts by weight, any one of claims 1 to 7 30 parts by weight or less content than 1 part by weight of (B) a nitrogen-containing compound 2. The polysiloxane composition according to item 1. The polysiloxane composition according to claim 1, further comprising water. (1) A step of applying the polysiloxane composition according to any one of claims 1 to 9 on a substrate to be processed to form a silicon-containing film;
(2) A step of applying a resist composition on the obtained silicon-containing film to form a resist film;
(3) The step of exposing the resist film by selectively irradiating radiation by allowing the obtained resist film to pass through a photomask;
(4) developing the exposed resist film to form a resist pattern;
(5) A pattern forming method comprising: forming a pattern by dry etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask.