WO2016111210A1

WO2016111210A1 - Composition for forming silicon-containing film and pattern forming method using said composition

Info

Publication number: WO2016111210A1
Application number: PCT/JP2015/086381
Authority: WO
Inventors: 博允田中; 真義石川; 智昭瀬古; 智晴河津; 準也鈴木; 酒井　達也; 準人生井
Original assignee: Jsr株式会社
Priority date: 2015-01-09
Filing date: 2015-12-25
Publication date: 2016-07-14
Also published as: TW201627771A

Abstract

To provide a novel composition for forming a silicon-containing film, which exhibits good removability when wet removal is carried out using a basic liquid; and a pattern forming method which uses this composition. A composition for forming a silicon-containing film, which is used for a multilayer resist process that comprises a step wherein a silicon-containing film is formed on the surface of a resist underlayer film and the silicon-containing film is removed by means of a basic liquid, and which is characterized by containing a compound that has one or more partial structures that are selected from the group consisting of partial structures represented by general formula (1) and partial structures represented by general formula (2). (In formula (1), in cases where L, -SO₂-O-* and X¹ do not constitute a ring, L represents a single bond or a divalent organic group, and X¹ represents a hydrogen atom or a monovalent organic group; and in cases where L, -SO₂-O-* and X constitute a ring, L represents a trivalent organic group, and X¹ represents a divalent organic group. (In this connection, * represents the bonding position of O and X¹.)) (In formula (2), X² represents a hydrogen atom or a monovalent organic group.)

Description

Silicon-containing film forming composition and pattern forming method using the composition

The present invention relates to a silicon-containing film forming composition and a pattern forming method using the composition.

In pattern formation when manufacturing a semiconductor device or the like, fine processing of a substrate made of an organic material or an inorganic material is performed by a pattern transfer method using a lithography technique, a resist development process, and an etching technique.
However, as the integration of semiconductor elements and the like on a circuit board progresses, it becomes difficult to accurately transfer the pattern of the optical mask to the resist film in the exposure process. For example, it is formed in the resist film in a microfabrication process for the substrate. Due to the influence of the standing wave of the generated light, an error (inconsistency) may occur in the dimension of the formed pattern. In order to reduce the influence of such standing waves, an antireflection film is formed between the resist film and the substrate surface.

Further, when processing a substrate on which a silicon oxide film, an inorganic interlayer insulating film, or the like is processed, a resist pattern is used as a mask. However, as the pattern becomes finer, it is necessary to make the resist film and the antireflection film thinner. . As the resist film becomes thinner in this way, the mask performance of the resist film decreases, and it tends to be difficult to perform desired fine processing without damaging the substrate.

Therefore, a silicon-containing film is formed on the oxide film or interlayer insulating film of the substrate to be processed, a resist pattern is transferred to this, and the oxide film or interlayer insulating film is etched using this silicon-containing film as a mask. The process is taking place.
Examples of silicon-containing films that have been proposed so far include silicon-containing films made of a composition containing a hydrolyzate of a specific silane compound and / or a condensate thereof (Patent Documents 1 to 4). 3 etc.).

JP-A-3-45510 JP 2000-356854 A Japanese Patent Laid-Open No. 2002-40668

However, the silicon-containing film used as a mask and the altered photoresist layer in which the silicon-containing film reacts with the etching gas remain on the etched substrate. Further, the sidewall protective deposition film also remains on the etched material sidewall exposed on the surface by etching. Therefore, it is necessary to remove these residues from the substrate before proceeding to the next manufacturing process.
For removing the residue on the substrate, a chemical called stripping solution is used to remove the residue by dissolving or partially dissolving the residue, and plasma state oxygen gas called ashing, etc. And dry stripping to ash and remove the residue.
In recent years, dry peeling has been mainly used because control is easy and a clear pattern can be generated.

However, recently, further miniaturization of devices has progressed, and along with this, further miniaturization of resist patterns has progressed, so that etching conditions have become very strict. Therefore, the frequency of occurrence of residues on the substrate is increased, and it is difficult to reliably remove ash from the residues by dry peeling, resulting in a problem that the required level of miniaturization cannot be met. I came. Furthermore, in the case of dry peeling, there is a problem that damage to the substrate to be processed is large.

Moreover, even if wet peeling is performed instead of dry peeling, conventional silicon-containing films are fragile to fluorine compounds that are frequently used as a peeling liquid during wet peeling, and even solutions with low concentrations were used. Even so, it was difficult to avoid damage to the substrate. Further, when a conventional silicon-containing film is used, it is necessary to set the temperature condition at the time of wet stripping to a high temperature, which causes a problem that the substrate to be processed is damaged.

As described above, due to the recent trend toward ultra-fine resist patterns, wet stripping has attracted attention as an alternative to dry stripping in order to reliably remove residues on the substrate. However, when a conventional silicon-containing film is used, there is a problem that it is difficult to avoid damage to the substrate during wet peeling.

Accordingly, the present invention mainly aims to provide a novel composition for forming a silicon-containing film having good releasability when performing wet stripping using a basic liquid, and a pattern forming method using the composition. And

In order to solve the above problems, the inventors of the present application focused on the structure of the compound constituting the composition for forming a silicon-containing film, and as a result of intensive studies, the present inventors include a copolymer or compound having a specific structure. Thus, the inventors have found that excellent basic liquid peeling performance is exhibited during wet peeling with a basic liquid, and have completed the present invention.
That is, in the present invention, first, a silicon-containing film forming composition used in a multilayer resist process including a step of forming a silicon-containing film on the resist underlayer film surface and peeling the silicon-containing film with a basic liquid,
A silicon-containing film-forming composition comprising a compound having one or more selected from the group consisting of a partial structure represented by the following general formula (1) and a partial structure represented by the following general formula (2) Offer things.

(In the formula (1), when L, —SO ₂ —O— * and X ¹ do not form a ring, L is a single bond or a divalent organic group, and X ¹ is a hydrogen atom or a monovalent organic group. It is.
When L, —SO ₂ —O— * and X form a ring, L is a trivalent organic group and X ¹ is a divalent organic group. (Note, * represents a bonding position between the O and ^{X 1.))}

(In Formula (2), X ² is a hydrogen atom or a monovalent organic group.)
In the present invention, the compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is (A) the general formula (1). ) And a polysiloxane having one or more selected from the group consisting of the partial structure represented by the general formula (2).
In the present invention, the (A) polysiloxane is derived from at least one compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). It may be a polysiloxane having the structural unit (I).

(In Formulas (3) and (4), p is an integer of 1 or more, R ¹ is a single bond or a (p + 1) -valent group. R ² and R ³ are each independently a hydrogen atom or a fluorine atom. Or R ² and R ³ may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, and l is an integer of 0 to 2. And m + 1 + n is 4.
In formula (3), Y is a hydrogen atom or a monovalent organic group.
In the formula (4), q and r are each independently an integer of 0 to 3. )
In this case, Y may be an alkyl group in the general formula (3). The proportion of the structural unit (I) in the (A) polysiloxane may be 1 to 60 mol% based on the raw material monomer.
In the present invention, the (A) polysiloxane may be a polysiloxane having at least a structural unit (II) derived from a compound represented by the following general formula (5).

(In the formula (5), p is an integer of 1 or more, R ¹ is a single bond or a (p + 1) -valent group. R ² and R ³ are each independently a hydrogen atom, a fluorine atom or a monovalent group. An organic group, R ² and R ³ may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, l is an integer of 0 to 2, and m + 1 + n Is 4. X ² is a hydrogen atom or a monovalent organic group.)
In this case, in the general formula (5), R ¹ may be a single bond, a sulfur atom or a group containing a sulfur atom. In the general formula (5), X ² may be an alkyl group. Further, in the general formula (5), X ² may be a monovalent acid dissociable group. Furthermore, the proportion of the structural unit (II) in the (A) polysiloxane may be 5 to 30 mol% based on the raw material monomer.
In the present invention, the compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is (B) a sulfo group and a sulfonic acid. It is good also as a thing containing the compound (however, except the said (A) polysiloxane) which has at least 1 or more types chosen from ester group.
In this case, it may further contain (A ′) a polysiloxane having neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2). Further, the compound (B) may be a vinyl polymer. Furthermore, the content of the compound (B) may be 0.1 to 80 parts by weight with respect to 100 parts by weight of the (A ′) polysiloxane.

In the present invention, (1) a step of forming a silicon-containing film on the upper surface side of the substrate using the composition for forming a silicon-containing film,
(2) forming a resist pattern on the upper surface side of the silicon-containing film;
(3) forming a pattern on the silicon-containing film by one or more etchings using the resist pattern as a mask;
(4) forming a pattern on the substrate by one or more etchings using the pattern formed on the silicon-containing film as a mask; and
(5) a step of peeling the silicon-containing film with a basic liquid;
A pattern forming method for performing
The composition for forming a silicon-containing film includes a compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2). A featured patterning method is also provided.
In the present invention, the compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is (A) the general formula (1). ) And a polysiloxane having one or more selected from the group consisting of the partial structure represented by the general formula (2).
In the present invention, the (A) polysiloxane is derived from at least one compound selected from the group consisting of a compound represented by the general formula (3) and a compound represented by the general formula (4). It may be a polysiloxane having the structural unit (I).
In this case, Y may be an alkyl group in the general formula (3). The proportion of the structural unit (I) in the (A) polysiloxane may be 1 to 60 mol% based on the raw material monomer.
In the present invention, the (A) polysiloxane may be a polysiloxane having a structural unit (II) derived from at least the compound represented by the general formula (5).
In this case, in the general formula (5), R ¹ may be a single bond, a sulfur atom or a group containing a sulfur atom. In the general formula (5), X ² may be an alkyl group. Further, in the general formula (5), X ² may be a monovalent acid dissociable group. Furthermore, the proportion of the structural unit (II) in the (A) polysiloxane may be 5 to 30 mol% based on the raw material monomer.
In the present invention, the compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is (B) a sulfo group and a sulfonic acid. It may contain a compound having at least one selected from ester groups (excluding the (A) polysiloxane).
In this case, the composition for forming a silicon-containing film further includes (A ′) a poly structure having neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2). It may contain siloxane. Further, the compound (B) may be a vinyl polymer. Furthermore, the content of the compound (B) may be 0.1 to 80 parts by weight with respect to 100 parts by weight of the (A ′) polysiloxane.
In the present invention, (6) a step of forming a resist underlayer film on the substrate,
And further
In the step (1), a silicon-containing film may be formed on the resist underlayer film using the silicon-containing film forming composition.

According to the present invention, the releasability at the time of wet stripping using a basic liquid is good. Moreover, if the composition for forming a silicon-containing film of the present invention is used, a silicon-containing film having excellent solvent resistance and excellent organic developer resistance can be formed. Note that the effects described here are not necessarily limited, and may be any of the effects described in the present disclosure.

Hereinafter, preferred embodiments for carrying out the present invention will be described. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.

1. Silicon-containing film-forming composition The silicon-containing film-forming composition according to this embodiment is a step of forming a silicon-containing film on the resist underlayer film surface and peeling the silicon-containing film with a basic liquid, that is, wet peeling. It is used for a multilayer resist process including a step of performing.
The silicon-containing film formed by the composition for forming a silicon-containing film according to the present embodiment removes only a portion where the solubility of the exposed portion in the developer is increased by selecting the developer, so-called “positive type” , And a pattern forming method called a “negative type” that reduces the solubility of the exposed portion in the developer by selecting a developer and leaves the exposed portion after development. In any case, it exhibits excellent solvent resistance and TMAH developer resistance or organic developer resistance. Therefore, even when used for both positive and negative applications, it exhibits excellent basic liquid peeling performance.

The silicon-containing film formed by the composition for forming a silicon-containing film according to the present embodiment uses another fluorine compound that is less damaged to the substrate without using a fluorine compound that is frequently used as a peeling solution during wet peeling. Even when the acidic liquid is used, the residue on the substrate can be reliably removed, so that damage to the substrate can be avoided. Furthermore, since it is not necessary to set the temperature condition to a high temperature when the silicon-containing film is wet-peeled, damage to the substrate due to heat can be reduced.

The composition for forming a silicon-containing film according to this embodiment includes at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2). (Hereinafter also referred to as “(a) compound”). (A) Although a more specific structure is not specifically limited as a compound, In this embodiment, (A) The partial structure represented by the said General formula (1), and the part represented by the said General formula (2) Those containing a polysiloxane having at least one selected from the group consisting of structures (hereinafter also referred to as “(A) polysiloxane”) are preferred.

<(A) Polysiloxane>
In this embodiment, (A) polysiloxane has 1 or more types chosen from the group which consists of the partial structure represented by the said General formula (1), and the partial structure represented by the said General formula (2).

In the general formula (1), when L, —SO ₂ —O— * and X ¹ do not form a ring, L is a single bond or a divalent organic group, and X ¹ is a hydrogen atom or a monovalent organic group. It is a group. Incidentally, * represents a bonding position between the O and ^{X 1.}
In the present embodiment, the single bond directly binds the substituents to be linked.

Examples of the divalent organic group represented by L include a divalent hydrocarbon group, a divalent hydrocarbon group, and a group formed by combining a linking group containing atoms other than carbon atoms and hydrogen atoms, or these groups. And a group in which a part of the hydrogen atoms is substituted with a halogen atom.

The monovalent organic group represented by X ¹ is a group containing at least one carbon atom, such as a cyano group, an alkyl group having 1 to 5 carbon atoms, a cyanoalkyl group having 2 to 6 carbon atoms, or an alkylcarbonyloxy group. And an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like. In addition, some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms.

In the general formula (1), when L, —SO ₂ —O— * and X ¹ form a ring, L is a trivalent organic group and X ¹ is a divalent organic group. In addition, * shows the coupling | bonding position of O and X.
Examples of the trivalent organic group include a group formed by combining a trivalent hydrocarbon group, a trivalent hydrocarbon group, and a linking group containing an atom other than a carbon atom and a hydrogen atom, or hydrogen of these groups. Examples thereof include a group in which a part of atoms are substituted with a halogen atom, and a group constituting a ring together with X ¹ and adjacent —SO ₂ —O— *.
The divalent organic group is a group formed by combining a divalent hydrocarbon group, a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom, or a hydrogen atom of these groups. Examples thereof include a group partially substituted with a halogen atom and the like, and a group constituting a ring together with L and adjacent —SO ₂ —O— *.

X ^{2 in the} general formula (2) is a hydrogen atom or a monovalent organic group.
The monovalent organic group of X ^2, can be exemplified monovalent organic groups exemplified in the description of R ² in the general formula (5) described later.

In the present embodiment, X ² is preferably an alkyl group from the viewpoint of easy handling of the substance.

The more specific structure of (A) polysiloxane that can be used in the present embodiment is not particularly limited. For example, polysiloxane having the following structural unit (I) or the following structural unit (II) is used. it can.

[Structural unit (I)]
The structural unit (I) is derived from, for example, a compound represented by the general formula (3) and a compound represented by the general formula (4).

In the present embodiment, R ¹ in the general formulas (3) and (4) is a single bond or a (p + 1) -valent group.
In the general formulas (3) and (4), p is an integer of 1 or more, p is preferably an integer of 1 to 2, and more preferably p = 1.
In the general formulas (3) and (4), n is an integer of 1 to 3, and preferably n = 1.
Incidentally, sites that are not involved in the main chain bond of R ¹ in the general formula (3) and (4) may be substituted.

When p = 1, R ¹ is a divalent group, and examples of the divalent group include an oxygen atom, a sulfur atom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms, —CO—, —OCO—, —CS—, —SO—, —SO ₂ — or —NR— (R: a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms) or a combination thereof A bivalent group etc. are mentioned.

Examples of the divalent hydrocarbon group having 1 to 30 carbon atoms include, for example, a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms, and a divalent alicyclic carbon group having 3 to 30 carbon atoms. Examples thereof include a hydrogen group, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group obtained by combining these groups.

Examples of the linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, tetramethylene group, and pentamethylene. Group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, hepta Linear alkylene groups such as decamethylene group, octadecamethylene group, nonadecamethylene group, icosalen group; 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl- 1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, methylidene group, ethyl Alkylidene group, propylidene group, etc. branched alkylene group such as 2-propylidene group.

Examples of the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclohexane. Monocyclic cycloalkylene groups having 3 to 30 carbon atoms such as octylene groups; 1,4-norbornylene groups, 2,5-norbornylene groups, 1,5-adamantylene groups, 2,6-adamantylene groups, etc. Examples thereof include a cyclic cycloalkylene group.

Examples of the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group.

Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms represented by R in —NR— include, for example, a linear or branched monovalent chain hydrocarbon group having 1 to 30 carbon atoms, carbon number And a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination thereof.

Examples of the linear or branched monovalent chain hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methyl. Examples include propyl group, 1-methylpropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group and the like.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, norbornyl group, adamantyl group and the like. Can be mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include phenyl group, tolyl group, naphthyl group, anthryl group, benzyl group, phenethyl group, and naphthylmethyl group.

Examples of the monovalent oxyhydrocarbon group having 1 to 30 carbon atoms include an alkoxy group having 1 to 30 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; and a carbon number such as a cyclopentyloxy group and a norbornyloxy group. A cycloalkyloxy group having 3 to 30; an aryloxy group having 6 to 30 carbon atoms such as a phenoxy group, a tolyloxy group and a naphthyloxy group; an aralkyloxy group having 7 to 30 carbon atoms such as a benzyloxy group and a naphthylmethoxy group; Can be mentioned.

Examples of the monovalent sulfanyl hydrocarbon group having 1 to 30 carbon atoms include alkyl sulfanyl groups having 1 to 30 carbon atoms such as methylsulfanyl group and ethylsulfanyl group; cycloalkyl having 3 to 30 carbon atoms such as cyclopentylsulfanyl group. Examples thereof include sulfanyl groups; arylsulfanyl groups having 6 to 30 carbon atoms such as phenylsulfanyl groups and naphthylsulfanyl groups; and aralkylsulfanyl groups having 7 to 30 carbon atoms such as benzylsulfanyl groups.

When p is an integer of 2 to 5, R ¹ is a (p + 1) valent group. Examples of the (p + 1) valent group include a substituted or unsubstituted (p + 1) valent group having 1 to 30 carbon atoms. A hydrocarbon group, or an oxygen atom, a sulfur atom, —CO—, —OCO—, —CS—, —SO—, —SO ₂ — or —NR— (R; a hydrogen atom or a carbon number of 1 to 30) For example, a (p + 1) -valent group containing a sulfur atom in a part of the main chain.

Examples of the (p + 1) valent hydrocarbon group having 1 to 30 carbon atoms include, for example, a linear or branched (p + 1) valent hydrocarbon group having 1 to 30 carbon atoms, and (p + 1) having 3 to 30 carbon atoms. Valent alicyclic hydrocarbon group, (p + 1) valent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination of these groups.

Examples of the straight-chain or branched (p + 1) -valent hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methyl. And (p + 1) -valent groups derived from a propyl group, a 1-methylpropyl group, a t-butyl group, a vinyl group, an ethynyl group, and the like.

Examples of the (p + 1) -valent alicyclic hydrocarbon group having 3 to 30 carbon atoms include a (p + 1) -valent group derived from a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and the like. Can be mentioned.

Examples of the (p + 1) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms include a (p + 1) -valent group derived from a phenyl group, a naphthyl group, an anthracenyl group, a pyrene group, a coronene group, and the like.

Since the monovalent hydrocarbon group having 1 to 30 carbon atoms represented by R in —NR— is the same as described above, the description thereof is omitted here.

In the general formula (1), a site not participating in the main chain bond of R ¹ may be substituted.
The substituent for substituting the site that does not participate in the main chain bond of R ¹ is not particularly limited, but is a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a straight chain having 1 to 5 carbon atoms, A branched alkoxy group is preferred.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group. Examples thereof include a propyl group and a tert-butyl group.
Examples of the linear or branched alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a 2-methylpropoxy group, A 1-methylpropoxy group, a tert-butoxy group and the like can be mentioned.
In addition, these alkyl groups and alkoxy groups may be substituted. Examples of the substituent include trifluoromethyl group, pentafluoroethyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, and amino group. And dimethylamino group.

In the present embodiment, R ² in the general formulas (3) and (4) is a hydrogen atom, a fluorine atom, or a monovalent organic group.
In the general formulas (3) and (4), m is an integer of 1 to 3, and preferably m = 3.

Examples of the monovalent organic group for R ² include the monovalent organic groups exemplified in the above description of X ¹ .

In the present embodiment, R ³ in the general formulas (3) and (4) is a hydrogen atom, a fluorine atom, or a monovalent organic group.
In the general formulas (3) and (4), l is an integer of 0 to 2, and it is preferable that l = 0.
Examples of the monovalent organic group for R ³ include the monovalent organic groups exemplified in the description of R ² .

In the present embodiment, Y in the general formula (3) is a hydrogen atom or a monovalent organic group.
The monovalent organic group Y, mention may be made of a monovalent organic group exemplified in the description of X ¹ described above.

Among these, from the viewpoint of improving storage stability, Y in the general formula (3) is preferably an alkyl group, more preferably a methyl group, an n-butyl group, or a tert-butyl group. .

Specific examples of the structural unit (I) represented by the general formula (3) include structural units represented by the following chemical formulas (I-1-1) to (I-1-9). .

Specific examples of the structural unit (I) represented by the general formula (4) include structural units represented by the following chemical formulas (I-2-1) to (I-1-4). .

(A) The proportion of the structural unit (I) in the polysiloxane is preferably 1 to 60 mol%, more preferably 2 to 25 mol%, and more preferably 5 to 20 mol%, based on the raw material monomer. Further preferred. If this content is less than 1 mol%, the effects of the present invention may not be sufficiently exhibited, and if it exceeds 60 mol%, storage stability may be deteriorated.

In the present embodiment, the “raw material monomer standard” refers to the ratio of the raw material monomer for obtaining the corresponding structural unit with respect to the total amount of the raw material monomer used in the production of the copolymer.
Such a content ratio of each structural unit can be estimated from an analysis result of ²⁹ Si-NMR spectrum, for example.

[Structural unit (II)]
The structural unit (II) is derived from, for example, a compound represented by the general formula (5).

In the present embodiment, R ^{1 in the} general formula (5) is a single bond or a (p + 1) -valent group.
In the general formula (5), p is an integer of 1 or more, p is preferably an integer of 1 to 2, and more preferably p = 1.
In the general formula (5), n is an integer of 1 to 3, and preferably n = 1.
Incidentally, sites that are not involved in the main chain bond of R ¹ in the general formula (5) may be substituted.

Examples of R ¹ in the general formula (5), since the formula (3) and (4) are the same as those described in R ¹ of, the description thereof is omitted, for example, is p = 1 In this case, R ¹ is a divalent group, and can be a divalent group containing a sulfur atom.

Examples of the divalent group containing a sulfur atom include divalent groups derived from structures represented by the following chemical formulas (R ¹ -1) to (R ¹ -11). * Represents a bonding site with the carbonyl carbon or Si atom in the general formula (5).

For example, when p is an integer of 2 to 5, R ¹ is a (p + 1) valent group, and may be a (p + 1) valent group containing a sulfur atom.

In the general formula (5), the site not participating in the main chain bond of R ¹ may be substituted.
Specific examples of substituents replacing a portion not involved in the main chain bond of R ¹ are the same as those described in R ¹ in the general formula (3) and (4), description thereof is omitted .

In the present embodiment, from the viewpoint of improving the adhesion to the resist, R ^{1 in the} general formula (5) is preferably a single bond, a sulfur atom or a group containing a sulfur atom, Among these, a divalent group derived from the structure represented by the chemical formula (R ¹ -1) or (R ¹ -2) is more preferable.

In the present embodiment, R ^{2 in the} general formula (5) is a hydrogen atom, a fluorine atom, or a monovalent organic group.
In the general formula (5), m is an integer of 1 to 3, and preferably m = 3.

The monovalent organic group represented by R ^{2 in} the general formula (5) is a group containing at least one carbon atom such as a cyano group, an alkyl group, a cyanoalkyl group having 2 to 6 carbon atoms, or an alkylcarbonyloxy group. Group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like.
In addition, some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms.

Among these, R ^{2 in the} general formula (5) is preferably an alkyl group from the viewpoint of reactivity and ease of handling of the substance.

In the present embodiment, R ^{3 in the} general formula (5) is a hydrogen atom, a fluorine atom, or a monovalent organic group.
In the general formula (5), l is an integer of 0 to 2, and preferably 1 = 0.
Examples of the monovalent organic group for R ³ include the monovalent organic groups exemplified in the description of R ^{2 in} the general formula (5).

In the present embodiment, X ^{2 in the} general formula (5) is a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group for X ² include the monovalent organic groups exemplified in the description of R ^{2 in} the general formula (5).

In the present embodiment, from the viewpoint of reactivity, X ² is particularly preferably a monovalent acid dissociable group. In the present embodiment, the “acid-dissociable group” refers to a group that substitutes a hydrogen atom of a carboxy group and dissociates by the action of an acid.
The acid dissociable group X ^2, for example, include groups of the following general formula (X 2 ^-1).

(In the formula (X ² -1), each R ⁴ independently represents a linear or branched alkyl group having 1 to 5 carbon atoms or a monovalent alicyclic hydrocarbon having 4 to 20 carbon atoms. A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a substitution thereof, together with any two R ⁴ 's bonded to each other, or a R ⁴ group or a substituted derivative thereof, A derivative is formed, and the remaining R ⁴ is a linear or branched alkyl group having 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a substituted derivative thereof.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group. Examples thereof include a propyl group and a tert-butyl group.

A monovalent alicyclic hydrocarbon group of 4 to 20 carbon atoms of R ⁴ and 2 of 4 to 20 carbon atoms formed together with any two R ⁴ 's bonded to each other and the carbon atoms to which each is bonded. Examples of the valent alicyclic hydrocarbon group include groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cyclooctane, or cycloalkenes; ] Heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] groups derived from alicyclic hydrocarbons such as dodecane and adamantane.

Examples of the substituent in the substituted derivative of the monovalent or divalent alicyclic hydrocarbon group include the same groups as those described as the substituent for substituting the site not participating in the main chain bond of R ^1. .
One or more or one or more of these substituents may be present in each substituted derivative.

Examples of the group represented by the general formula (X ² -1) include tert-butyl group, tert-amyl group, 2-ethyl-2-butyl group, 3-methyl-3-pentyl group, 1,1 -Alkyl groups such as diethylpropyl group; 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-n-propylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-n-propylcyclohexyl group, etc. A 1-alkylcycloalkyl group;

2-methylbicyclo [2.2.1] heptan-2-yl group, 2-methyl-5-hydroxybicyclo [2.2.1] heptan-2-yl group, 2-methyl-6-hydroxybicyclo [2] 2.1] heptan-2-yl group, 2-methyl-5-cyanobicyclo [2.2.1] heptan-2-yl group, 2-methyl-6-cyanobicyclo [2.2.1] heptane -2-yl group, 2-ethylbicyclo [2.2.1] heptan-2-yl group, 2-ethyl-5-hydroxybicyclo [2.2.1] heptan-2-yl group, 2-ethyl- 6-hydroxybicyclo [2.2.1] heptan-2-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-methyl-4-hydroxytri A cyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-methyl-4-cyanotricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl Group, 8-ethyl-4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-10-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-10-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyl-9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyl-10-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 2-methyladamantan-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-ethyl- 3-hydroxyadamantan-2-yl group, 2-n-propyladamantan-2-yl group, 2-n-butyladamantan-2-yl group, 2-methoxymethyladamantan-2-yl group, 2-methoxymethyl- An alicyclic hydrocarbon group substituted with an alkyl group such as a 3-hydroxyadamantan-2-yl group, a 2-ethoxymethyladamantan-2-yl group, or a 2-n-propoxymethyladamantan-2-yl group;

1-methyl-1-cyclopentylethyl group, 1-methyl-1- (2-hydroxycyclopentyl) ethyl group, 1-methyl-1- (3-hydroxycyclopentyl) ethyl group, 1-methyl-1-cyclohexylethyl group, 1-methyl-1- (3-hydroxycyclohexyl) ethyl group, 1-methyl-1- (4-hydroxycyclohexyl) ethyl group, 1-methyl-1-cycloheptylethyl group, 1-methyl-1- (3- Hydroxycycloheptyl) ethyl group, 1-methyl-1- (4-hydroxycycloheptyl) ethyl group, 1-methyl-1- (bicyclo [2.2.1] heptan-2-yl) ethyl group, 1 -Methyl-1- (5-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl group, 1-methyl-1- (6-hydroxybicyclo [2 2.1] heptan-2-yl) ethyl group, 1-methyl-1- (tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7]} dodecane-4-yl) ethyl group, 1-methyl -1- (9-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) ethyl group, 1-methyl-1- (10-hydroxytetracyclo [6. 2.1.1 ^3,6 0.0 ^2,7 ] dodecan-4-yl) ethyl group, 1-methyl-1- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl 1-methyl-1- (4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl group, 1-methyl-1- (adamantan-1-yl) ethyl group 1-methyl-1- (3-hydroxyadamantan-1-yl) ethyl group, 1,1-disi An ethyl group having an alicyclic hydrocarbon group substituted with an alkyl group such as a lopentylethyl group, 1,1-di (2-hydroxycyclopentyl) ethyl group, 1,1-di (3-hydroxycyclopentyl) ethyl group ;

1,1-dicyclohexylethyl group, 1,1-di (3-hydroxycyclohexyl) ethyl group, 1,1-di (4-hydroxycyclohexyl) ethyl group, 1,1-dicycloheptylethyl group, 1,1-di (3-hydroxycycloheptyl) ethyl group, 1,1-di (4-hydroxycycloheptyl) ethyl group, 1,1-di (bicyclo [2.2.1] heptan-2-yl) ethyl group, 1,1-di (5-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl group, 1,1-di (6-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl group, 1,1-di (tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7]} dodecane-4-yl) ethyl group, 1,1-di (9-hydroxy-tetracyclo [6.2 .1.1 ^3,6 .0 ^2,7] de de Down-4-yl) ethyl group, 1,1-di (10-hydroxy-tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7]} dodecane-4-yl) ethyl group, 1,1 Di (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl group, 1,1-di (4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8 Alicyclic hydrocarbons substituted with hydroxyl groups such as -yl) ethyl group, 1,1-di (adamantan-1-yl) ethyl group, 1,1-di (3-hydroxyadamantan-1-yl) ethyl group And an ethyl group having a group.

Among these, from the viewpoint of improving peelability, X ² is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a tert-butyl group.

Specific examples of the structural unit (II) represented by the general formula (5) include structural units represented by the following chemical formulas (II-3-1) to (II-3-9). .

(A) The proportion of the structural unit (II) in the polysiloxane is preferably 5 to 30 mol%, more preferably 5 to 25 mol%, more preferably 10 to 25 mol%, based on the raw material monomer. Further preferred. This is because when the content ratio is less than 5 mol%, the effect of the present invention may not be sufficiently exhibited, and when it exceeds 30 mol%, storage stability may be deteriorated.

(A) The polysiloxane may contain only one type of structural unit (II), or may contain two or more types in combination.

[Structural unit (III)]
Moreover, (A) polysiloxane may contain the structural unit (III) derived from tetraalkoxysilane from the viewpoint of oxygen ashing resistance.

In the tetraalkoxysilane that gives the structural unit (III), all four alkoxy groups bonded to the Si atom may be the same, or all or part of them may be different.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms.
Further, the alkoxy group is not limited to a linear one, and may be branched or cyclic.

Specific examples of the structural unit (III) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra -Tert-butoxysilane, tetrakis (2-ethylbutoxy) silane and the like.

Among these, from the viewpoint of reactivity and ease of handling of substances, the structural unit (III) includes tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n- Butoxysilane and tetra-sec-butoxysilane are preferable, and tetraethoxysilane is more preferable.

(A) The proportion of the structural unit (III) in the polysiloxane is preferably 55 to 85 mol%, more preferably 60 to 80 mol%, based on the raw material monomer. This is because when the content ratio is 55 to 85 mol%, a silicon-containing film having excellent oxygen ashing resistance can be formed, and a composition having excellent oxygen ashing resistance can be obtained.

(A) The polysiloxane may contain only one type of structural unit (III), or may contain two or more types.

[Structural unit (IV)]
Moreover, (A) polysiloxane may contain the structural unit (IV) derived from the compound represented by the following general formula (12) from the viewpoint of imparting an antireflection function.

(In the formula (12), R ⁹ is a light-absorbing group, R ¹⁰ and R ¹¹ are monovalent organic groups, a is an integer of 1 to 3, and b is an integer of 1 to 3. And c is an integer from 0 to 2, and a + b + c is 4.)

Examples of the light absorbing group of R ^{9 in} the general formula (12) include a group having an aromatic ring and a carbonyl group.
In the general formula (12), when b is 2 or 3, all of the two or three R ^{5 s} may be the same or all or part of them may be different.

R ¹⁰ and R ^{11 in} the general formula (12) are monovalent organic groups.
Examples of the monovalent organic group of R ¹⁰ and R ¹¹ include the monovalent organic groups exemplified in the above description of X ¹ .

Among these, R ¹⁰ and R ^{11 in} the general formula (12) are preferably a methyl group or an ethyl group, and more preferably a methyl group.
In the general formula (12), when a is 2 or 3, all of the two or three R ⁷ bonded to the oxygen atom may be the same or all or a part thereof may be different. .
Further, in the general formula (12), when c is 2, the two R ⁶ may be the same or different.

Specific examples of the structural unit (IV) include, for example, phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4- (n-propyl) phenyltrimethoxysilane, 4- (iso -Propyl) phenyltrimethoxysilane, 4- (n-butyl) phenyltrimethoxysilane, 4- (2-methylpropyl) phenyltrimethoxysilane, 4- (1-methylpropyl) phenyltrimethoxysilane, 4- (tert -Butyl) phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 4 - Cetylaminophenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 3-amino Phenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxy Phenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetyl Aminophenyltrimethoxysilane, 2,4,6-trimethylphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-aminobenzyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane, 4-acetylaminobenzyltrimethoxysilane, N-3- (triethoxysilyl) propylbenzylsulfonamide, N- 3- (triethoxysilyl) propylbenzoylsulfonamide, N-3- (triethoxysilyl) propylbenzylsulfonamide, N-3- (triethoxysilyl) propyl-2-oxo-2-phenyl Ethylsulfonamide, N-3- (triethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N-3- (triethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N- 2- (triethoxysilyl) ethylbenzylsulfonamide, N-2- (triethoxysilyl) ethylbenzoylsulfonamide, N-2- (triethoxysilyl) ethyl-2-phenylethylsulfonamide, N-2- (tri Ethoxysilyl) ethyl-3-nitrophenylsulfonamide, N-3- (trimethoxysilyl) propylbenzylsulfonamide, N-3- (trimethoxysilyl) propylbenzoylsulfonamide, N-3- (trimethoxysilyl) propyl Benzylsulfonamide, N-3- (tri Toxisilyl) propyl-2-oxo-2-phenylethylsulfonamide, N-3- (trimethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N-3- (trimethoxysilyl) propyl-C- Benzoxazol-2-ylsulfonamide, N-2- (trimethoxysilyl) ethylbenzylsulfonamide, N-2- (trimethoxysilyl) ethylbenzoylsulfonamide, N-2- (trimethoxysilyl) ethyl-2- Phenylethylsulfonamide, N-2- (trimethoxysilyl) ethyl-3-nitrophenylsulfonamide, N-2- (trimethoxysilyl) ethyl-4-nitrophenylsulfonamide, diphenyldimethoxysilane, allylphenyldimethoxysilane, Diphenyldiethoxy Orchids, diphenyl dichlorosilane, tert- butylphenyl dichlorosilane, phenyl methyl dichlorosilane, phenethylmethyldichlorosilane, di (p- tolyl) dichlorosilane, and the like.

Among these, from the viewpoint of reactivity and ease of handling of substances, the structural unit (IV) includes phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4- (n- Propyl) phenyltrimethoxysilane, 4- (iso-propyl) phenyltrimethoxysilane, 4- (n-butyl) phenyltrimethoxysilane, 4- (2-methylpropyl) phenyltrimethoxysilane, 4- (1-methyl) Propyl) phenyltrimethoxysilane, 4- (tert-butyl) phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, and 4-methylbenzyltrimethoxysilane are preferable, and phenyltrimethoxysilane is more preferable. .

(A) The proportion of the structural unit (IV) in the polysiloxane is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, and more preferably 10 to 20 mol%, based on the raw material monomer. Further preferred. This is because when the content ratio is 10 to 40 mol%, a composition having an excellent antireflection function can be obtained.

(A) The polysiloxane may contain only one type of structural unit (IV), or may contain two or more types.

[Structural unit (V)]
Moreover, (A) polysiloxane may contain the structural unit (V) as another structural unit.

Specific examples of the structural unit (V) include N-3- (triethoxysilyl) propylmethylsulfonamide, N-3- (triethoxysilyl) propylvinylsulfonamide, and N-3- (triethoxysilyl). Propyl cyanomethylsulfonamide, N-3- (triethoxysilyl) propyl-3-mercaptopropyl-1-sulfonamide, N-3- (triethoxysilyl) propyl-C- (2-cyanophenyl) methylsulfonamide, N-3- (triethoxysilyl) propyl-3,3-dimethylbutylsulfonamide, N-3- (triethoxysilyl) propyl-2- (2,5-dioxoimidazolin-4-yl) ethylsulfonamide, N-2- (triethoxysilyl) ethylmethylsulfonamide, N-2- (triethoxy Ryl) ethylethylsulfonamide, N-2- (triethoxysilyl) ethyl-n-butylsulfonamide, N-2- (triethoxysilyl) ethyl-iso-butylsulfonamide, N-2- (triethoxysilyl) Ethyloctylsulfonamide, N-2- (triethoxysilyl) ethylvinylsulfonamide, N-2- (triethoxysilyl) ethylallylsulfonamide, N-2- (triethoxysilyl) ethyl-3-aminopropylsulfonamide N-2- (triethoxysilyl) ethyl-2-cyanoethylsulfonamide, N-2- (triethoxysilyl) ethyl-4-nitrophenylsulfonamide,

N-3- (trimethoxysilyl) propylvinylsulfonamide, N-3- (trimethoxysilyl) propylcyanomethylsulfonamide, N-3- (trimethoxysilyl) propyl-3-mercaptopropyl-1-sulfonamide, N-3- (trimethoxysilyl) propyl-C- (2-cyanophenyl) methylsulfonamide, N-3- (trimethoxysilyl) propyl-3,3-dimethylbutylsulfonamide, N-3- (trimethoxy Silyl) propyl-2- (2,5-dioxoimidazolin-4-yl) ethylsulfonamide, N-2- (triethoxysilyl) ethylmethylsulfonamide, N-2- (trimethoxysilyl) ethylethylsulfonamide N-2- (trimethoxysilyl) ethyl-n-butylsulfonamide, -2- (trimethoxysilyl) ethyl-iso-butylsulfonamide, N-2- (trimethoxysilyl) ethyloctylsulfonamide, N-2- (trimethoxysilyl) ethylvinylsulfonamide, N-2- (tri Methoxysilyl) ethylallylsulfonamide, N-2- (trimethoxysilyl) ethyl-3-aminopropylsulfonamide, N-2- (trimethoxysilyl) ethyl-2-cyanoethylsulfonamide,

Dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, di-tert-butyldichlorosilane, diethoxydivinylsilane, di (3-methacryloxypropyl) dimethoxysilane, dimethyldi Ethoxysilane, dimesityldimethoxysilane, dimesityldichlorosilane, di-iso-propyldimethoxysilane, di-iso-butyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, dicyclopentyldimethoxysilane, di-n -Butyldichlorosilane, di-tert-butyldichlorosilane, dicyclohexyldichlorosilane, acetoxypropyldichlorosilane, (3-acryloxypropyl) methyldichlorosilane , Allylhexyldichlorosilane, allylmethyldichlorosilane, aminopropylmethyldiethoxysilane, dimethacryloxydimethoxysilane, tert-butylmethyldichlorosilane, 2- (carbomethoxy) ethylmethyldichlorosilane, 2-cyanoethylmethyldichlorosilane 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldimethoxysilane, 3-cyanopropylphenyldichlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldichlorosilane, mercaptomethylmethyldi Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, isobutylmethyldimethoxysilane, ethylmethyldichlorosilane, 3-methacryloxyp Pills methyl diethoxy silane, p- tolyl methyldichlorosilane, di (3-glycidoxypropyl) dimethoxysilane, di (3-glycidoxypropyl) diethoxysilane, (3-cyclohexenyl) propyl dimethoxysilane,

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, Methyltriacetoxysilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec- Toxisilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethyltris (trimethylsiloxy) silane, ethyltriacetoxysilane, 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-propyltriphenoxysilane, n-propyl Triacetoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyl Pirutori -n- butoxysilane, iso- propyl trimethoxy -sec- butoxysilane, iso- propyl tri -tert- butoxysilane, iso- propyl triphenoxy silane,

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, 2-methylpropyltrimethoxysilane, 2-methylpropyltriethoxysilane, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso -Propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2-methylpropyltri-tert-butoxysilane, 2-methylpropyltriphenoxysilane, 1-methylpropylto Methoxysilane, 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-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltri -Iso-propoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxy Structural units derived from compounds such emissions and the like.

(A) The proportion of the structural unit (V) in the polysiloxane is preferably 10 mol% or less, more preferably 7 mol% or less, based on the raw material monomer. This is because when the content ratio is 10 mol% or less, a composition excellent in resist pattern adhesion by controlling surface hydrophilicity / hydrophobicity can be obtained.

(A) The polysiloxane may contain only one type of these structural units (V), or may contain two or more types.

(A) The polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC) of polysiloxane is preferably 1,000 to 15,000, It is more preferably from 000 to 10,000, and even more preferably from 1,500 to 6,000. This is because when Mw is 1,000 to 15,000, coating properties and storage stability are good.

(A) The production method of polysiloxane is not particularly limited, and can be obtained by hydrolytic condensation reaction using the above-mentioned compounds giving structural units (I) to (V) as raw material monomers (starting raw materials). .
Specifically, for example, it can be prepared by dissolving a starting material in an organic solvent, adding water intermittently or continuously to this solution, and causing a hydrolysis condensation reaction. At this time, the catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in the added water. The temperature for carrying out the hydrolysis condensation reaction is usually 0 to 100 ° C.

In preparing (A) polysiloxane, (1) a mixture of each compound as a starting material may be subjected to a hydrolytic condensation reaction, or (2) a hydrolyzate of each compound and its condensate. Hydrolysis condensation reaction or condensation reaction may be performed using at least one of at least one of them, a hydrolyzate of a mixture of selected compounds, and a condensate thereof.

The water for performing the hydrolysis condensation reaction is not particularly limited, but it is preferable to use ion-exchanged water. Water is used in an amount of 0.25 to 3 mol, preferably 0.3 to 2.5 mol, per mol of alkoxy group of the compound used as a raw material. This is because by using water in an amount in the above range, the uniformity of the formed coating film is not lowered, and the storage stability of the composition is less likely to be lowered.

The organic solvent is not particularly limited as long as it is an organic solvent used for this kind of application. For example, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, glycerin, 1-butanol, 2 -Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1,4-butanediol, 1-pentanol, 1-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl -1-butanol, cyclopentanol, 1-hexanol, 4-methyl-2-pentanol, cyclohexanol, 1-heptanol, cycloheptanol, 1-octanol, n-nonyl alcohol, n-decyl alcohol, diethylene glycol, di Propylene glycol, triethylene glycol , Tripropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol mono-iso-butyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ethanol, diethylene glycol monobenzyl Ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 4-methoxy-1-butanol, 2-methoxyethanol, 2-iso-propoxyethanol, 2-butoxyethanol 2-iso-butoxyethanol, 2-hexyloxyethanol, 2- (2-ethyl) hexyloxyethanol, 2-allyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2-propanol, Examples include 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, and 1-phenoxy-2-propanol.

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

Examples of metal chelate compounds include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-iso-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-iso-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Naruto) Titanium, die ert-butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, mono-iso-propoxy tris (acetylacetonato) titanium , Mono-n-butoxy tris (acetylacetonato) titanium, mono-sec-butoxy tris (acetylacetonato) titanium, mono-tert-butoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium ,

Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-iso-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-iso-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-tert- Buto Si-bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-iso-propoxy tris (ethyl acetoacetate) titanium, mono -N-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (Acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium Nkireto compound;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-iso-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-iso-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylato) Tonato) zirconium, di-tert-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-iso-propoxy tris (Acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) zirconium, tetrakis (Acetylacetonate) zirconium,

Triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-iso-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) Zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-tert-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl aceto) Acetate) zirconium, di-iso-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy・ Bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono- iso-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-tert-butoxy tris (ethyl aceto) Acetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetate) Zirconium chelate compounds such as nattobis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum Can be used.

Examples of organic acids include acetic 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 Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

Among these, as the catalyst, a base catalyst such as an organic base or an inorganic base is preferable.
In addition, these catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the raw material compounds.

Moreover, after performing a hydrolysis condensation reaction, it is preferable to perform the removal process of reaction by-products, such as lower alcohols, such as methanol and ethanol, for example. Thereby, since the purity of the organic solvent becomes high, it is possible to obtain a composition having excellent coating properties and good storage stability.
The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate or its condensate does not proceed. For example, the reaction by-product has a boiling point lower than that of the organic solvent. In some cases, it can be distilled off under reduced pressure.

In this embodiment, the amount of (A) polysiloxane used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the silicon-containing film forming composition according to this embodiment. The amount is more preferably 1 to 3 parts by mass, still more preferably 0.5 to 2 parts by mass.

(A) The polysiloxane may be contained in the silicon-containing film forming composition according to the present embodiment alone, or may be contained in two or more kinds.

<(B) Compound>
In the present embodiment, the compound (a) is a compound having at least one selected from (B) a sulfo group and a sulfonate group (excluding (A) polysiloxane) (hereinafter also referred to as “(B) compound”). Can be included).

(B) The specific structure of the compound is not particularly limited. For example, the compound is represented by the following general formulas (6) to (8) or the following general formula (9) or (10). It is preferable to use a vinyl polymer having a repeating unit and a compound having a structure represented by the following general formula (11).
The said compound and vinyl polymer may be contained only 1 type in the composition for silicon-containing film formation concerning this embodiment, and may be contained 2 or more types.

(In the formulas (6), (7) and (9), Y is a hydrogen atom or a monovalent organic group.
In formula (6), n is an integer of 2 or more, p is an integer of 1 or more, and R ¹ is a single bond or a (p + 1) -valent group.
In formulas (7) and (8), n is an integer of 1 to 4, p is an integer of 1 or more, and R ¹ is a single bond or a (p + 1) -valent group.
In the formulas (6) to (8), Z is an n-valent organic group or —Si (OH) ₃ (in this case, n is an integer of 1).
In formulas (8) and (10), q and r are each independently an integer of 0 to 3.
In formulas (9) and (10), R ⁵ is a hydrogen atom, a fluorine atom or a monovalent organic group, and R ¹ is a single bond or a (p + 1) valent group.
Wherein (11), ^{X B} is a carbonyl group, a sulfonyl group or a single bond. )

In the general formulas (6), (7) and (9), Y is a hydrogen atom or a monovalent organic group.
In the general formula (6), the monovalent organic group of Y is a group containing at least one carbon atom, such as a cyano group, an alkyl group having 1 to 5 carbon atoms, and a cyano group having 2 to 6 carbon atoms. Examples thereof include an alkyl group or an alkylcarbonyloxy group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.
In addition, some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms.
In the general formulas (7) and (9), the monovalent organic group represented by Y is a group containing at least one carbon atom, such as an alkyl group having 1 to 5 carbon atoms or a group having 2 to 6 carbon atoms. Examples thereof include a cyanoalkyl group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.
In addition, some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms.

In the present embodiment, R ¹ in the general formulas (6) to (10) is a single bond or a (p + 1) -valent group.
In the general formulas (6) to (10), p is an integer of 1 or more, p is preferably an integer of 1 to 2, and more preferably p = 1.
Further, n in the general formula (6) is preferably an integer of 2 to 4, n is particularly preferably an integer of 2, and n in the general formulas (7) and (8) is 1 to 4 It is preferable that n is an integer of 1 to 2.
In the general formulas (6) to (10), the portion not participating in the main chain bond of R ¹ may be substituted.

Examples of ^{R 1} in the general formula (6) to (10), is similar to those described in ^{R 1} in the general formula (3) and (4), description thereof is omitted.

In the general formulas (6) to (10), the portion not participating in the main chain bond of R ¹ may be substituted.
Specific examples of substituents replacing a portion not involved in the main chain bond of R ¹ are the same as those described in R ¹ in the general formula (3) and (4), description thereof is omitted .

In the present embodiment, in the general formulas (6) to (8), Z is an n-valent organic group or —Si (OH) ₃ (in this case, n is an integer of 1).
When Z is an n-valent organic group, examples of the n-valent group include a substituted or unsubstituted n-valent hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, a sulfur atom,- CO—, —OCO—, —COO—, —CONH—, —CS—, —SO—, —SO ₂ — or —NR— (R: a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms) And, for example, an n-valent group containing a sulfur atom in a part of the main chain.
In addition, when Z is a monovalent organic group, examples of Z include —Si (OR ² ) _m R ³ _l .

Specific examples of the compound in which R ¹ is a single bond, p = 1, and n = 2 in the general formula (6) include compounds represented by the following chemical formulas (6a) to (6d).

When Z is —Si (OR ² ) _m R ³ _l , n is an integer of 1 to 3, m is an integer of 1 to 3, l is an integer of 0 to 2, and m + 1 + n is 4. (Including -Si (OH) ₃ as Z).
^{_{^{_{-Si (OR 2) m R 3}}}} l of ^{R 2} is hydrogen atom, a fluorine atom or a monovalent organic group. M in —Si (OR ² ) _m R ³ _l is an integer of 1 to 3, and preferably m = 3.

Examples of the monovalent organic group for R ² include the monovalent organic groups exemplified in the description of Y in the general formulas (6), (7), and (9).

In the present ^{_{^{embodiment, -Si (OR 2) m R}}} 3 l of ^{R 3} is hydrogen atom, a fluorine atom or a monovalent organic group.
_L of —Si (OR ² ) _m R ³ _l is an integer of 0 to 2, and preferably 1 = 0.
Examples of the monovalent organic group for R ³ include the monovalent organic groups exemplified in the description of Y in the general formulas (6), (7), and (9).

Specific examples of the compound in which Z in the general formula (6) is —Si (OR ² ) _m R ³ _l include compounds represented by the following chemical formulas (6e) to (6m).

Specific examples of the compound in which Z in the general formula (7) is —Si (OR ² ) _m R ³ _l include compounds represented by the following chemical formulas (7a) to (7i).

Specific examples of the compound in which Z in the general formula (8) is —Si (OR ² ) _m R ³ _l include compounds represented by the following chemical formulas (8a) to (8d).

In the present embodiment, in the general formulas (9) and (10), R ⁵ is a hydrogen atom, a fluorine atom or a monovalent organic group, and R ¹ is a single bond or a (p + 1) valent group.
Examples of the monovalent organic group for R ⁵ include the monovalent organic groups exemplified in the description of Y in the general formulas (6), (7), and (9).

Specific examples of the vinyl polymer having repeating units represented by the general formulas (9) and (10) include, for example, polymers having repeating units represented by the following chemical formulas (9a) to (10a). It is done.

The ratio of the repeating units represented by the general formulas (9) and (10) is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on the raw material monomer. More preferably.
The weight average molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC) is preferably 1,000 to 15,000, and preferably 2,000 to 13, 000 is more preferable, and 5,000 to 12,000 is still more preferable.

As the monomer copolymerized with the repeating units represented by the general formulas (9) and (10), for example, a compound represented by the following chemical formula (M-0) is preferable.

Examples of the onium cation of the compound having the structure represented by the general formula (11) include S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb, Te, and Bi. Onium cations containing these elements.
Examples of the cation containing S (sulfur) as an element include a sulfonium cation, and examples of the cation containing N (nitrogen) as an element include an ammonium cation.

Examples of the sulfonium cation include a cation represented by the following general formula (C-1), and examples of the ammonium cation include a quaternary ammonium cation represented by the following general formula (C-2), And cations represented by formula (C-3).

(In the formula (C-1), Ar ^C1 , Ar ^C2 and Ar ^C3 are each independently a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.
In the formula (C-2), R ^C1 , R ^C2 , R ^C3 and R ^C4 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms.
In the formula (C-3), R ^C5 and R ^C6 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 7 carbon atoms. )

Examples of the aryl group (Ar ^C1 , Ar ^C2 and Ar ^C3 ) of the general formula (C-1) include a phenyl group and a naphthyl group. Specific examples of the compound represented by the general formula (C-1) Includes compounds represented by the following chemical formulas (C-1a) and (C-1b).

Specific examples of the cation represented by the general formula (C-2) include a compound represented by the following chemical formula (C-2a), and a specific example of the compound represented by the general formula (C-3). Includes a cation represented by the following chemical formula (C-3a).

The onium cation of the compound having the structure represented by the general formula (11) includes two monovalent cations in the compound, such as a compound represented by the chemical formula (C-3a). Including onium cations.

Examples of the anion of the compound having the structure represented by the general formula (11) include an anion represented by the following general formula (A-1), an anion represented by the following general formula (A-2), and the like. .

(In the formulas (A-1) and (A-2), X ^B has the same ^{meaning as} in the general formula (11).
In formula (A-1), R ⁶ and R ⁷ are each independently a monovalent organic group having 1 to 20 carbon atoms.
In the formula (A-2), R ⁸ is a divalent organic group having 1 to 20 carbon atoms. )

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ⁶ and R ⁷ include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon-carbon bond or a bond of this hydrocarbon group. A group (q) containing a divalent heteroatom-containing group at the terminal on the side, a group in which part or all of the hydrogen atoms of the hydrocarbon group and group (q) are substituted with a monovalent heteroatom-containing group, etc. Can be mentioned.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms. A hydrocarbon group etc. are mentioned.

As the chain hydrocarbon group, for example,
Alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl;
An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group;
Examples thereof include alkynyl groups such as ethynyl group, propynyl group, and butynyl group.

As the alicyclic hydrocarbon group, for example,
A monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group;
A monocyclic cycloalkenyl group such as a cyclobutenyl group, a cyclopentenyl group, or a cyclohexenyl group;
A polycyclic cycloalkyl group such as a norbornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group;
And polycyclic cycloalkenyl groups such as a norbornenyl group, a tricyclodecenyl group, and a tetracyclododecenyl group.

As an aromatic hydrocarbon group, for example,
Aryl groups such as phenyl, tolyl, xylyl, naphthyl and anthryl;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group.

Examples of heteroatoms possessed by monovalent and divalent heteroatom-containing groups include halogen atoms such as oxygen atom, sulfur atom, nitrogen atom, silicon atom, phosphorus atom, fluorine atom, chlorine atom and bromine atom. . Among these, an oxygen atom, a sulfur atom, a nitrogen atom and a halogen atom are preferable, and an oxygen atom and a fluorine atom are more preferable.

Examples of the divalent hetero atom-containing group include —O—, —CO—, —CS—, —NR ′ (R ′: a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms) — Examples include a combined group.

Examples of the monovalent heteroatom-containing group include a hydroxy group, a carboxy group, a sulfanyl group (—SH), an amino group, a cyano group, and a halogen atom.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by R ⁸ include, for example, removing one hydrogen atom from the monovalent organic group having 1 to 20 carbon atoms exemplified as R ⁶ and R ^7. And the like.

Examples of the anion represented by the general formula (A-1) include anions represented by the following chemical formulas (A-1a) to (A-1f).

Examples of the anion represented by the general formula (A-2) include anions represented by the following chemical formulas (A-2a) to (A-2f).

Specific examples of the compound having an anion represented by the general formula (A-2) include compounds represented by the following chemical formulas (11a) to (11d).

The content of the compound (B) in the silicon-containing film forming composition according to the present embodiment is 0.1 parts by mass relative to 100 parts by mass of the solid content of the silicon-containing film forming composition according to the present invention. It is preferably at least part by mass, more preferably at least 5 parts by mass, and even more preferably at least 10 parts by mass. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less.

(B) 1 type of compounds may be contained in the composition for silicon-containing film formation which concerns on this embodiment, and may be contained 2 or more types.

<(A ') Polysiloxane>
The composition for forming a silicon-containing film according to the present embodiment further has (A ′) neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2). Polysiloxane (hereinafter also referred to as “(A ′) polysiloxane”) may be included. As (A ′) polysiloxane, a specific structure is particularly limited as long as neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2) is present. Although it is not, it is preferable that it is a hydrolysis-condensation product of the compound containing the silane compound represented, for example by the following general formula (i).

(In the formula (i), R ^A represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group. Some or all of the hydrogen atoms in the alkyl group may be substituted with an epoxyalkyloxy group, an acid anhydride group, or a cyano group, and some or all of the hydrogen atoms in the aryl group are substituted with a hydroxy group. X ^A is a halogen atom or —OR ^B , where R ^B is a monovalent organic group, a is an integer of 0 to 3, provided that R ^A and X ^A When there are a plurality of each, R ^A and X ^A may be the same or different.)

In addition, the "hydrolysis condensate of a compound containing a silane compound" here refers to a hydrolysis condensate of a silane compound represented by the general formula (i) or a silane compound represented by the general formula (i) It means a hydrolysis-condensation product with a silane compound other than the silane compound represented by the general formula (i) (hereinafter also referred to as “other silane compound”). Other silane compounds are not particularly limited as long as they are hydrolyzed to generate silanol groups.

Examples of the alkyl group having 1 to 5 carbon atoms represented by ^RA include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group; an isopropyl group And branched alkyl groups such as isobutyl group, sec-butyl group, t-butyl group and isoamyl group.
In this embodiment, a methyl group and an ethyl group are particularly preferable among these, and a methyl group is more preferable.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ^A include ethenyl group, 1-propen-1-yl group, 1-propen-2-yl group, 1-propen-3-yl group, 1 -Buten-1-yl group, 1-buten-2-yl group, 1-buten-3-yl group, 1-buten-4-yl group, 2-buten-1-yl group, 2-buten-2- Yl, 1-penten-5-yl, 2-penten-1-yl, 2-penten-2-yl, 1-hexen-6-yl, 2-hexen-1-yl, 2- And a hexen-2-yl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^A include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

In this embodiment, “epoxy” includes both oxiranyl and oxetanyl.

Examples of the alkyl group substituted with an epoxyalkyloxy group include oxiranylalkyloxy groups such as 2-glycidyloxyethyl group, 3-glycidyloxypropyl group, 4-glycidyloxybutyl group; 3-ethyl-3- Examples thereof include oxetanylpropyloxy groups such as oxetanylpropyl group, 3-methyl-3-oxetanylpropyl group, 3-ethyl-2-oxetanylpropyl group, and 2-oxetanylethyl group.
In the present embodiment, among these, a 3-glycidyloxypropyl group and a 3-ethyl-3-oxetanylpropyl group are particularly preferable.

Examples of the alkyl group substituted with an acid anhydride group include a 2-succinic anhydride group-substituted ethyl group, a 3-succinic anhydride group-substituted propyl group, and a 4-succinic anhydride group-substituted butyl group.
In the present embodiment, among these, a 3-succinic anhydride group-substituted propyl group is more preferable.

Examples of the alkyl group substituted with a cyano group include a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, and the like.

Examples of the aryl group substituted with a hydroxy group include a 4-hydroxyphenyl group, a 4-hydroxy-2-methylphenyl group, and a 4-hydroxynaphthyl group.
In the present embodiment, among these, a 4-hydroxyphenyl group is particularly preferable.

In the general formula (i), X ^A is a halogen atom or —OR ^B. However, ^{R B} is a monovalent organic group.

The halogen atom represented by X ^A, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the present embodiment, the “monovalent organic group” refers to a monovalent group containing at least one carbon atom.

In the present embodiment, the monovalent organic group represented by R ^B is preferably an alkyl group or an alkylcarbonyl group.
The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group, more preferably a methyl group or an ethyl group, Is more preferable.
The alkylcarbonyl group is preferably a methylcarbonyl group or an ethylcarbonyl group.

In the present embodiment, in the general formula (i), a is an integer of 0 to 3.
However, in the case of multiple ^{R A} and ^{X A} are each, a plurality of ^{R A} and ^{X A} may each be the same or different.

Examples of the silane compound represented by the general formula (i) include phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4-hydroxyphenyl as an aromatic ring-containing trialkoxysilane. Trimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane Silane, 2,4,6-trimethylphenyltrimethoxysilane, etc .;
As alkyltrialkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-t-butoxy Silane, methyltriphenoxysilane, methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane , Methylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propyl Poxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-t-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-propyltri-t-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, iso-propyltrimethoxysilane, i o-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-sec-butoxysilane, iso-propyl Tri-t-butoxysilane, iso-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri- n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-t-butoxysilane, n-butyltriphenoxysilane, n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane, 2-methylpropyltrie Toxisilane, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2-methylpropyl Tri-t-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-t-butoxysilane, 1-methylpropyltriphenoxysilane, t-butyltrimethoxysilane , T Butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-t-butoxysilane, t-butyltriphenoxysilane, t-butyltrichlorosilane, t-butyldichlorosilane and the like;
As alkenyltrialkoxysilanes, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-t-butoxysilane Vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, allyltri-t-butoxysilane, Allyltriphenoxysilane and the like;
Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, and the like;
Tetraarylsilanes such as tetraphenoxysilane;
Examples of epoxy group-containing silanes include 3-oxetanylmethyloxypropyltrimethoxysilane, 3-oxetanylethyloxypropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane;
Examples of acid anhydride group-containing silanes include 3- (trimethoxysilyl) propyl succinic anhydride, 2- (trimethoxysilyl) ethyl succinic anhydride, 3- (trimethoxysilyl) propyl maleic anhydride, 2- (trimethoxy Silyl) ethyl glutaric anhydride and the like;
Examples of tetrahalosilanes include tetrachlorosilane.

Examples of other silane compounds include benzyltrimethoxysilane, phenethyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 4-acetylaminophenyltrimethoxysilane. Methoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methoxyphenyltri Methoxysilane, 2-phenoxyphenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylamino Enyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-aminobenzyltri Examples include methoxysilane, 4-dimethylaminobenzyltrimethoxysilane, 4-acetylaminobenzyltrimethoxysilane and the like.

The conditions for hydrolytic condensation include hydrolysis of at least a part of the silane compound represented by the general formula (i) to convert a hydrolyzable group (—OR ^B ) into a silanol group, and a condensation reaction. Although it will not specifically limit as long as it is made to raise | generate, For example, it can implement as follows.

The water used for the hydrolysis condensation is not particularly limited, but it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.
The amount of water used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, relative to 1 mol of the total amount of hydrolyzable groups of the silane compound represented by formula (i). More preferably, the amount is 0.5 to 1.5 mol. By using such an amount of water, the hydrolysis / condensation reaction rate can be optimized.

The solvent that can be used for the hydrolysis condensation is not particularly limited, but ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionic acid esters are preferable, diethylene glycol dimethyl ether, Diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate and 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) are more preferred.

The hydrolysis condensation reaction is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, etc.), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate Carboxylates such as sodium acetate; various Lewis bases), alkoxides (for example, zirconium alkoxides, titanium alkoxides, aluminum alkoxides, etc.) and the like.
As the aluminum alkoxide, for example, tri-i-propoxyaluminum can be used.
The amount of the catalyst used is preferably 0.2 mol or less with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction, More preferably.

In the present embodiment, the reaction temperature and reaction time in hydrolysis condensation can also be set as appropriate. For example, the following conditions can be employed.

The reaction temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 150 ° C.
The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours.
By setting such reaction temperature and reaction time, the hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis condensation, the hydrolyzable silane compound, water and catalyst may be added to the reaction system at one time and the reaction may be carried out in one step, or the hydrolyzable silane compound, water and catalyst may be added in several steps. The hydrolysis condensation reaction may be carried out in multiple stages by adding it in the reaction system in batches.
In addition, after a hydrolysis condensation reaction, water and the produced | generated alcohol can be removed from a reaction system by adding a dehydrating agent and then subjecting to evaporation.

The composition for forming a silicon-containing film according to the present embodiment may contain only one (A ′) polysiloxane or two or more kinds.

(A ') The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of polysiloxane is usually 500 to 50,000, preferably 1,000 to 30,000, preferably 1,000. To 15,000 is more preferred, and 1,000 to 5,000 is even more preferred.

<(C) Acid generating compound>
The composition for forming a silicon-containing film according to the present embodiment may contain (C) an acid generating compound as necessary as long as the effects of the present invention are not impaired.
When such an acid generating compound is contained, an acid is generated in the silicon-containing film by exposing the resist or heating after the exposure, and an acid is generated at the interface between the silicon-containing film and the resist film. Is supplied. By this acid, in particular, when (A) the polysiloxane has a partial structure represented by the general formula (2), the protector of the carboxy group in the (A) polysiloxane is deprotected. A silicon-containing film formed by the composition for forming a silicon-containing film according to the embodiment exhibits excellent basic liquid peeling performance, and a favorable resist pattern can be formed while avoiding damage to the substrate.

Examples of the acid generating compound include a compound that generates an acid by heat treatment (hereinafter, also referred to as “latent thermal acid generating compound”) and a compound that generates an acid by an ultraviolet irradiation treatment (hereinafter, “ Also referred to as “latent photoacid generator compound”).

The latent thermal acid generating compound is a compound that generates an acid when heated to 50 to 450 ° C., preferably 200 to 350 ° C.

Examples of latent thermal acid generating compounds include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and the like.

Examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- Alkylsulfonium salts such as (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl-4 -Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxy Enylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl Benzylsulfonium salts such as -3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzoin tosylate, 2-nitrobenzyl tosylate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as p-chlorobenzyl-4-hydroxy Enylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4- Substituted benzyl such as hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate A sulfonium salt;

Examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- (p-methoxy) Benzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate and other benzylbenzothiazolium salts Is mentioned.
Moreover, 2,4,4,6-tetrabromocyclohexadienone may be mentioned as the thermal acid generating compound other than the above.

Among these, the latent thermal acid generating compounds include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl. -4-Hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazolium hexafluoroantimonate are preferable.
Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).

The latent photoacid-generating compound is a compound that generates an acid upon irradiation with ultraviolet light of usually 1 to 100 mJ, preferably 10 to 50 mJ.

Examples of latent photoacid generating compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, halogen-containing compounds, diazoketone compounds, sulfonic acid compounds, and the like.

Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept. -2-yl-1,1,2,2-tetrafluoroethanesulfonate, 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-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenyl Sulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylphosphonium 1, 1,2,2-tetrafluoro-6- (1-adamantane carbonyloxy) -hexane-1-sulfonate and the like.

Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoro Lomethanesulfonate, 1- (6-n-butoxynaphthalene) 2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxy) Naphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4- Hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) Tetrahydrothiophenium perfluoro-n-octa 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate Can be mentioned.

Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-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-te Etc. La tetrafluoroethane sulfonates.

Examples of the halogen-containing compound include phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.
Examples of the diazoketone compound include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphthoquinonediazide of 2,3,4,4′-tetrabenzophenone. Examples include 4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester.
Examples of the sulfonic acid compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene- Examples include 2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate, and the like. It is done.

Among these, the latent photoacid generator compound is preferably a tetrahydrothiophenium salt, and more preferably a 1- (4-n-butoxynaphthalen-1-yl) among tetrahydrothiophenium salts. Tetrahydrothiophenium nonafluoro-n-butanesulfonate.

These (C) acid generating compounds may be used alone or in combination of two or more.

In the present embodiment, the amount of the (C) acid generating compound used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the solid content of the composition for forming a silicon-containing film according to the present embodiment. More preferably, the content is 0.01 to 2 parts by mass.

<(D) Solvent>
The composition for forming a silicon-containing film according to this embodiment contains (D) a solvent for the purpose of dissolving or dispersing (A) polysiloxane and (A ′) polysiloxane unless the effects of the present invention are impaired. It may be.

Examples of the solvent (D) include n-pentane, iso-pentane, n-hexane, i-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso Aromatic hydrocarbon solvents such as propyl benzene, n-amyl naphthalene, trimethylbenzene; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, te t-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2- Ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethyl Nonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl Monoalcohol solvents such as carbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, Polyhydric alcohol solvents such as 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin;

Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso- Ketone solvents such as butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, iso-propyl ether, n-butyl ether, n- Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, -Ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2- (2-ethylbutoxy) ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol , 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene Recall monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, ether solvents such as 2-methyltetrahydrofuran;

Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec -Pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl acetate Ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol acetate Ether monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, propion Ethyl acetate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate Ester solvents such as diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, etc. Can be mentioned.

Among these, as the solvent (D), ether solvents and ester solvents are preferable, and among ether solvents and ester solvents, glycol solvents are more preferable because of their excellent film formability.
Examples of the glycol solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
In addition, these (D) solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present embodiment, the amount of the solvent (D) used is preferably 88.0 to 99.88 parts by mass with respect to 100 parts by mass of the silicon-containing film forming composition according to the present embodiment. More preferably, it is 5 to 99.8 parts by mass.

<(E) Other copolymer, other polysiloxane>
The composition for forming a silicon-containing film according to the present embodiment may contain (E) another copolymer or another polysiloxane as necessary, as long as the effects of the present invention are not impaired.

When the composition for forming a silicon-containing film according to this embodiment contains (E) another copolymer or another polysiloxane, the amount used thereof is the composition for forming a silicon-containing film according to this embodiment. The amount is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the solid content.

(E) Other copolymers and other polysiloxanes may be contained in the silicon-containing film-forming composition according to the present embodiment, or may be contained in two or more kinds.

<Other ingredients>
The composition for forming a silicon-containing film according to the present embodiment may contain other components as necessary as long as the effects of the present invention are not impaired.

[Β-diketone]
The composition for forming a silicon-containing film according to this embodiment may contain a β-diketone from the viewpoint of improving the uniformity of the formed coating film and the storage stability.
Examples of β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, and 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 and the like.
These β-diketones may be used alone or in combination of two or more.

[Colloidal silica]
The composition for forming a silicon-containing film according to this embodiment may contain colloidal silica.
Colloidal silica is a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 10 to 40% by mass. Is.
Examples of colloidal silica include methanol silica sol, isopropanol silica sol [manufactured by Nissan Chemical Industries, Ltd.];
In addition, these colloidal silica may be used individually by 1 type, and may be used in combination of 2 or more type.

[Colloidal alumina]
The silicon-containing film forming composition according to the present embodiment may contain colloidal alumina.
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.);
In addition, these colloidal aluminas may be used alone or in combination of two or more.

[Organic polymer]
The silicon-containing film forming composition according to the present embodiment may contain an organic polymer.
Examples of organic polymers include compounds having a polyalkylene oxide structure, compounds having a sugar chain structure, vinylamide polymers, acrylate compounds, methacrylate compounds, aromatic vinyl compounds, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, Examples thereof include polyquinoxaline, polyoxadiazole, and a fluorine polymer.
In addition, these organic polymers may be used individually by 1 type, and may be used in combination of 2 or more type.

[Surfactant]
The composition for forming a silicon-containing film according to this embodiment may contain a surfactant for the purpose of improving applicability, striation, and the like.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, the following trade names are KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 [above, manufactured by Kyoeisha Chemical Co., Ltd.], F-top EF301, EF303, EF352 [above, manufactured by Tochem Products Co., Ltd.], MegaFac F171, F173 [above, manufactured by Dainippon Ink & Chemicals, Inc.], Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 [ As described above, manufactured by Asahi Glass Co., Ltd.).
In addition, these surfactants may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the compounding quantity of surfactant can be suitably determined according to the objective.

<Method for preparing composition for forming silicon-containing film>
The method for preparing the composition for forming a silicon-containing film according to the present embodiment is not particularly limited, and for example, it can be prepared by mixing the above-described components at a predetermined ratio.

<Silicon-containing film>
The composition for forming a silicon-containing film according to this embodiment can be suitably used in a multilayer resist process. Among the multi-layer resist process, finer region than 90 nm (ArF, ArF in immersion exposure, F 2, _EUV, nanoimprint) in the pattern formation using a multilayer resist process in, it can be particularly preferably used .

Specifically, the silicon-containing film forms a coating film of the composition for forming a silicon-containing film by, for example, applying it to the surface of a resist film or other lower layer film (antireflection film). Can be cured by heat treatment to form a silicon-containing film.

As a method for applying the silicon-containing film forming composition according to this embodiment, a spin coating method, a roll coating method, a dip method, or the like can be used.

The heating temperature of the coating film to be formed is usually 50 to 450 ° C., and the film thickness after the heat treatment is usually 10 to 1000 nm, preferably 10 to 500 nm.

2. Pattern Forming Method The pattern forming method according to the present embodiment includes (1) a step of forming a silicon-containing film on the upper surface side of the substrate using the silicon-containing film forming composition (hereinafter also referred to as “step (1)”). (2) a step of forming a resist pattern on the upper surface side of the silicon-containing film (hereinafter also referred to as “step (2)”), (3) the silicon by one or more etchings using the resist pattern as a mask. A step of forming a pattern on the containing film (hereinafter also referred to as “step (3)”), and (4) forming a pattern on the substrate by one or more etchings using the pattern formed on the silicon-containing film as a mask. And (5) a step of peeling the silicon-containing film with a basic liquid (hereinafter also referred to as “step (5)”). Do it at least.

Further, if necessary, (6) a step of forming a resist underlayer film on the substrate (hereinafter referred to as “step (6)”) is further performed. In step (1), the silicon layer is formed on the resist underlayer film. A silicon-containing film may be formed using the composition for forming a containing film.

In the pattern forming method according to the present embodiment, since the silicon-containing film forming composition according to the present embodiment is used, the basic stripping performance is excellent in wet stripping, and a good resist pattern can be formed. .

<Process (1)>
Step (1) is a step of forming a silicon-containing film on the upper surface side of the substrate using the silicon-containing film forming composition. Thereby, a substrate with a silicon-containing film in which a silicon-containing film is formed on the upper surface side of the substrate is obtained.

In the pattern forming method according to this embodiment, the silicon-containing film forming composition includes: It is preferable to use those described in the silicon-containing film forming composition.

Examples of the substrate include conventionally known substrates such as a silicon wafer and a wafer coated with aluminum.
Further, as the substrate, a patterned substrate such as a wiring groove (trench) or a plug groove (via) may be used.

The substrate is preliminarily formed with a resist underlayer film (another film different from the silicon-containing film obtained by using the silicon-containing film-forming composition according to the present embodiment) through the step (6) described later. May be.

As the composition for forming a silicon-containing film, a composition filtered with a filter having a pore diameter of about 0.2 μm can be suitably used.
The solid content concentration of the silicon-containing film forming composition is not particularly limited, but is preferably 0.1 to 10% by mass.

The silicon-containing film is obtained by baking the coating film formed by applying the silicon-containing film forming composition according to this embodiment, so that the solvent in the coating film (that is, in the silicon-containing film forming composition). It can be formed by volatilizing the solvent contained.
The baking temperature can be appropriately set depending on the type of the silicon-containing film forming composition used, but is preferably 30 to 450 ° C., more preferably 50 to 350 ° C. .

In addition, since the formation method and film thickness of the silicon-containing film in the step (1) are the same as those described above, the description is omitted here.

<Step (2)>
Step (2) is a step of forming a resist pattern on the upper surface side of the silicon-containing film obtained in step (1).

In step (2), the method for forming the resist pattern is not particularly limited, and examples thereof include a method using photolithography. Details will be described below.

As a method using photolithography, for example,
(2-1) using a resist composition, forming a resist film on the upper surface side of the silicon-containing film;
(2-2) a step of selectively irradiating the resist film with radiation and subjecting the resist film to immersion exposure;
(2-3) a step of developing the resist film subjected to immersion exposure to form a resist pattern;
Have

[Step (2-1)]
Step (2-1) is a step of forming a resist film on the upper surface side of the silicon-containing film using a resist composition.
Specifically, after applying the resist composition so that the resulting resist film has a predetermined thickness, the solvent in the film is volatilized by pre-baking to form a resist film.

Examples of the resist composition include a positive chemically amplified resist composition, a positive resist composition containing an alkali-soluble resin, a negative chemically amplified resist composition, and a negative resist composition containing an alkali-soluble resin. Is mentioned.

As the resist composition, a resist composition filtered with a filter having a pore diameter of about 0.2 μm can be suitably used.
Further, the solid content concentration of the resist composition is not particularly limited, but is preferably 5 to 50% by mass.
In the step (2-1), a commercially available resist composition can be used as it is.

The coating method of the resist composition is not particularly limited, and can be performed by, for example, a spin coating method.

The pre-baking temperature can be appropriately set according to the type of resist composition to be used, but is usually about 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.

[Step (2-2)]
Step (2-2) is a step of subjecting the resist film to immersion exposure by selectively irradiating the resist film with radiation.
Specifically, a reduction projection type exposure apparatus called a stepper is usually used, and an immersion exposure liquid is disposed between the projection lens of the apparatus and the silicon-containing film obtained in step (1). Then, the reticle (photomask) pattern is reduced by the projection lens, and projection exposure is performed while moving on the wafer.

Examples of the liquid for immersion exposure include water, long-chain or cyclic aliphatic compounds, and the like. The immersion exposure liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as low as possible so as to minimize distortion of the optical image projected onto the film.
When the exposure light source is ArF excimer laser light, it is preferable to use water from the viewpoints of availability and easy handling in addition to the above-described viewpoints. When water is used, an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens. As water to be used, distilled water and ultrapure water are preferable.

As exposure light used for immersion exposure, electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, and X-rays; charging such as electron beam and α-ray, depending on the type of the silicon-containing film forming composition used. It can select suitably from particle beam etc.
Among these, as the exposure light used for immersion exposure, far ultraviolet rays are preferable, ArF excimer laser light and KrF excimer laser light (wavelength 248 nm) are more preferable, and ArF excimer laser light is more preferable. Further, the exposure conditions such as the exposure amount can be appropriately selected as necessary.

[Step (2-3)]
Step (2-3) is a step of developing the exposed resist film to form a resist pattern.
Specifically, a predetermined resist pattern is formed by developing the exposed resist film with a developing solution, followed by washing and drying.

The developer can be appropriately selected depending on the type of resist composition used.
In the case of a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin, 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, alkaline aqueous solution such as 1,5-diazabicyclo [4.3.0] -5-nonene, and the like.

The alkaline aqueous solution may be one to which a suitable amount of a water-soluble organic solvent, a surfactant or the like is added.
Examples of the water-soluble organic solvent include methanol, ethanol, n-propropanol, i-propanol, n-butanol, t-butanol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanediol. Examples include alcohols such as methanol.
In addition, these water-soluble organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the water-soluble organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution so that the developability does not deteriorate and the development residue in the exposed part does not increase.

When an alkaline aqueous solution is used as the developer, it is preferable to wash and dry with a rinse after development. As this rinse liquid, water is preferable and ultrapure water is more preferable.

In the case of negative-type chemically amplified resist compositions and negative-type resist compositions containing alkali-soluble resins, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine , Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and aqueous alkali solutions such as cyclic amines such as pyrrole and piperidine.

The concentration of the developer is preferably 10% by mass or less from the viewpoint of dissolving the exposed area and not dissolving the unexposed area.

In the pattern forming method according to the present embodiment, the silicon-containing film is formed on the upper surface side of the substrate using the silicon-containing film forming composition according to the present embodiment by passing through the step (1). Damage to the substrate by the developer can be suppressed.

In step (2-3), post-baking is preferably performed before development (that is, after step (2-2)) in order to improve resolution, pattern profile, developability, and the like.

The post-baking temperature can be appropriately set according to the type of resist composition used, but is preferably 50 to 200 ° C, more preferably 80 to 150 ° C.

<Step (3)>
Step (3) is a step of forming a pattern on the silicon-containing film by one or more etchings using the resist pattern obtained in step (2) as a mask.

In the step (3), either dry etching or wet etching can be employed as the etching, but dry etching is preferable.

Dry etching can be performed using a known dry etching apparatus.
Further, the source gas at the time of dry etching can be appropriately selected depending on the elemental composition of the silicon-containing film to be etched, for example, CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , SF _6. Fluorine gas such as Cl ₂ , chlorine gas such as Cl ₂ and BCl ₃ , oxygen gas such as O ₂ , O ₃ and H ₂ O, H ₂ , NH ₃ , CO, CO ₂ , CH ₄ and C ₂ H ₂ Reducing gases such as C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , BCl ₃ , He, N _2. An inert gas such as Ar is used, and these gases may be mixed and used. For dry etching of a silicon-containing film, a fluorine-based gas is usually used, and a mixture of an oxygen-based gas and an inert gas is preferably used.

<Process (4)>
Step (4) is a step of forming a pattern on the substrate by one or more etchings using the pattern formed on the silicon-containing film obtained in step (3) as a mask.

In the step (4), as the etching, both dry etching and wet etching can be adopted, but dry etching is preferable.
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.
In addition, these gas may be used individually by 1 type, and may be used in combination of 2 or more type. For example, such as a gas that combines _{N 2} and _{H 2} and the like.

In step (4), when a substrate on which a resist underlayer film was formed was used through step (6) described later, the resist underlayer film portion in the substrate was etched to form a pattern. The pattern is preferably formed by etching the substrate using the pattern as a mask.

Note that the etching in the step (4) is the same as that described in the step (3), and therefore the description is omitted here.

<Step (5)>
Step (5) is a step of peeling the silicon-containing film remaining on the upper surface side of the substrate after performing step (4) with a basic liquid. This makes it possible to remove the resist reliably.

The basic liquid used for wet stripping is not particularly limited as long as it is basic. 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 (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4 0.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, and the like.

Among these, an aqueous ammonia solution is particularly preferable from the viewpoint of avoiding damage to the substrate.
Further, the basic aqueous solution may be one in which an appropriate amount of a water-soluble organic solvent, a surfactant or the like is added. Furthermore, a solution containing an organic solvent other than water may be used as long as it is a basic solution.
The water-soluble organic solvent is the same as that described in the step (2-3), and therefore the description thereof is omitted here.

The pH of the basic solution is preferably 7.5 or more, and more preferably 8.0 or more. If the pH is less than 7.5, the silicon-containing film may not be sufficiently removed.

The silicon-containing film formed by the composition for forming a silicon-containing film according to this embodiment does not use a fluorine compound that is frequently used as a peeling liquid at the time of wet peeling, and other basic liquid that causes little damage to the substrate. Even when the substrate is used, the residue on the substrate can be surely removed. Therefore, by using the pattern forming method according to this embodiment, damage to the substrate can be avoided.

The wet stripping method is not particularly limited as long as the silicon-containing film and the basic solution can be in contact with each other for a certain period of time. For example, a method of immersing a substrate on which a pattern is formed in a basic solution, a basic solution The method of spraying, the method of apply | coating a basic solution, etc. are mentioned. After each of these methods, the substrate may be washed with water and dried.

The immersion time in the immersion method can be set to, for example, about 0.2 to 30 minutes. However, if the immersion time is increased, damage to the substrate may occur, so it is preferable to set it within 20 minutes, and more preferably within 5 minutes.

The set temperature in step (5) is not particularly limited, but is preferably 20 to 90 ° C. This is because if the temperature is less than 20 ° C., the effect of the present invention may not be sufficiently exhibited, and if it exceeds 90 ° C., the substrate may be damaged.

Since the silicon-containing film formed by the silicon-containing film forming composition according to the present embodiment does not need to be set to a high temperature condition when wet-peeling, the pattern forming method according to the present embodiment is used. Thus, damage to the substrate due to heat can be reduced.

<Step (6)>
Step (6) is a step of forming a resist underlayer film on the substrate. In this invention, a process (6) can be performed as needed.
When the step (6) is performed, the step (1) described above is performed after the step (6). In the step (1), the silicon-containing film forming composition is used on the resist underlayer film. A film will be formed.

As the resist underlayer film, for example, a material commercially available under a trade name such as “NFC HM8005” (manufactured by JSR Corporation) can be used.

The method for forming the resist underlayer film is not particularly limited. For example, a coating film formed by applying a material for forming the resist underlayer film on the substrate by a known method such as a spin coat 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.

The temperature at which the coating film is heated is not particularly limited, but is preferably 90 to 550 ° C., more preferably 90 to 450 ° C., and still more preferably 90 to 300 ° C.

The thickness of the resist underlayer film is not particularly limited, but is preferably 50 to 20000 nm.

Hereinafter, examples will be described. In addition, the Example shown below shows an example of the typical Example of this embodiment, and, thereby, the range of this invention is not interpreted narrowly.

1-1. (A) Synthesis of Polysiloxane In each of the synthesis examples shown below, (A) polysiloxane was synthesized using compounds represented by the following chemical formulas (M-1) to (M-9) as monomers. .

Note that the compound represented by the chemical formula (M-1) is a compound that gives the structural unit (III) in this specification, and the compounds represented by the chemical formulas (M-2) and (M-9) are structural units (IV). The compounds represented by the chemical formulas (M-3) to (M-8) are compounds that give the structural unit (I).

<Synthesis Example 1: (A-1) Polysiloxane>
An aqueous oxalic acid solution was prepared by dissolving 0.45 g of oxalic acid in 21.6 g of water by heating. Thereafter, 10.65 g of the compound represented by the chemical formula (M-1), 3.41 g of the compound represented by the chemical formula (M-2), 2.01 g of the compound represented by the chemical formula (M-3), and 53 of propylene glycol-1-ethyl ether 53 A flask containing .5 g was set with a condenser and a dropping funnel containing the prepared aqueous oxalic acid solution. 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 produced by the reaction was removed to obtain 45.4 g of a resin solution.
The solid content in this resin solution was (A-1) polysiloxane.

The content ratio of the solid content in the obtained resin solution was 7.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 2000.

In addition, the solid content concentration and the weight average molecular weight (Mw) of the polysiloxane in this example were measured by the following methods.

[Measurement of solid content of polysiloxane]
By baking 0.5 g of the resin solution for 30 minutes at 250 ° C., the weight of the solid content with respect to 0.5 g of the resin solution was measured to obtain the solid content concentration (% by mass) of the polysiloxane.

[Measurement of polystyrene equivalent weight average molecular weight (Mw)]
GPC column [manufactured by Tosoh Corporation] (2 product names “G2000HXL”, 1 product name “G3000HXL”, 1 product name “G4000HXL”), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column Temperature: Polystyrene-converted weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

<Synthesis Examples 2 to 7: (A-2) to (A-7) Polysiloxane, (E-1) Copolymer>
The (A-2) to (A-7) polysiloxane and (E-1) copolymer were the same as those in Synthesis Example 1 except that the monomers shown in Table 1 were used in the amounts shown in Table 1. Synthesized by the same method.

<Comparative Synthesis Examples 1 and 2: (AR-1) and (AR-2) polysiloxane>
The (AR-1) and (AR-2) polysiloxanes were synthesized by the same method as in Synthesis Example 1 except that the monomers shown in Table 1 were used in the amounts shown in Table 1.

The amount of monomer used, the solid content concentration, and the weight average molecular weight (Mw) in the resin solutions obtained in Synthesis Examples 2 to 7 and Comparative Synthesis Examples 1 and 2 were the same as in Synthesis Example 1. It was measured.

<Result>
Table 1 shows the amount of monomer used, the solid content concentration, and the weight average molecular weight (Mw) of the solid content in the resin solutions obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 and 2.
In Tables 1 and 2, the resin composition (theoretical value, unit: mol%) determined by the amount of each monomer used is also shown.

1-2. Preparation of silicon-containing film-forming composition (A-1) to (A-6) polysiloxane, (E-1) copolymer obtained in each of the above synthesis examples, and each of the above comparative synthesis examples Using the resulting (AR-1) and (AR-2) polysiloxanes and (D) solvent, the silicon-containing film forming compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were used as shown below. Prepared.
In this example, “parts” means all parts by mass.

<Example 1>
As shown in Table 2, 1.10 parts of (A-1) polysiloxane obtained in Synthesis Example 1 was dissolved in 69.16 parts of (D-1) solvent, and then this solution was added with a pore size of 0.2 μm. The composition for forming a silicon-containing film of Example 1 was obtained.

<Examples 2 to 8 and Comparative Examples 1 and 2>
Except for using each component in the ratio shown in Table 2, compositions for forming silicon-containing films of Examples 2 to 8 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1. In Table 2, propylene glycol ethyl ether was used as the (E-2) copolymer of Comparative Examples 1 and 2.

1-3. Evaluation of composition for forming silicon-containing film A substrate with a silicon-containing film was formed using each of the positive-type silicon-containing film-forming compositions of Examples 1 to 8 and Comparative Examples 1 and 2 obtained as described above. The following various evaluations were performed.

The method for forming the substrate will be described below.
Each composition for forming a silicon-containing film obtained as described above was applied onto a silicon wafer (substrate) by spin coating.
Thereafter, baking is performed in an air atmosphere under baking conditions of a temperature of 220 ° C. and a time of 60 seconds to form a silicon-containing film having a thickness of 30 nm, and a “substrate with silicon-containing film” in which a silicon-containing film is formed on the substrate. Obtained.

<Solvent resistance>
The substrate obtained as described above was immersed in cyclohexanone (room temperature) for 10 seconds.
Spectral ellipsometer UV1280E [manufactured by KLA-TENCOR, the same applies hereinafter] The film thickness change rate was calculated from the measured value.
The solvent resistance was evaluated as “A” (good) when the film thickness change rate was less than 1%, and “B” (bad) when the film thickness change rate was 1% or more.

<TMAH phenomenon liquid resistance>
The substrate obtained as described above was immersed in a 2.38% TMAH developer (room temperature) for 60 seconds.
The film thickness before and after immersion was measured using a spectroscopic ellipsometer UV1280E, and the film thickness change rate was calculated from the measured value.
The TMAH phenomenon liquid resistance was evaluated as “A” (good) when the film thickness change rate was less than 1%, and “B” (bad) when the film thickness change rate was 1% or more.

<Basic liquid peeling performance>
The substrate obtained as described above was heated to 65 ° C. (a) basic solution (25% aqueous ammonia solution: 30% aqueous hydrogen peroxide solution: water = 1: 1: 5 mixed aqueous solution), (b) It was immersed in a basic liquid (9% aqueous ammonia solution) for 5 minutes.
The film thickness before and after the immersion was measured using a spectroscopic ellipsometer UV1280E.
Basic liquid peeling performance is "A" when the silicon-containing film formed on the substrate can be peeled within 3 minutes, "B" when peelable within 3 to 5 minutes, and peelable after 5 minutes or more The case was evaluated as “C”.

<Result>
Table 3 shows the evaluation results of the respective items of solvent resistance, TMAH developer resistance, and basic liquid peeling performance for each of the positive silicon-containing film forming compositions of Examples 1 to 8 and Comparative Examples 1 and 2.

<Discussion>
As is clear from Table 3, it was found that the silicon-containing film forming composition according to this embodiment is excellent in solvent resistance and TMAH developer resistance.
It has also been found that the composition for forming a silicon-containing film according to this embodiment has excellent basic liquid peeling performance.

2-1. (A) Synthesis of Polysiloxane In each of the synthesis examples shown below, (A) polysiloxane was synthesized using compounds represented by the following chemical formulas (M-10) to (M-21) as monomers. .

Note that the compound represented by the chemical formula (M-10) is a compound that gives the structural unit (III) in this specification, and the compounds represented by the chemical formulas (M-11) and (M-12) are structural units (IV). The compounds represented by the chemical formulas (M-13) to (M-21) are compounds that give the structural unit (II).

<Synthesis Example 8: (A-7) Polysiloxane>
An aqueous oxalic acid solution was prepared by dissolving 0.45 g of oxalic acid in 21.6 g of water by heating. Thereafter, 10.65 g of the compound represented by the chemical formula (M-10), 3.41 g of the compound represented by the chemical formula (M-11), 2.01 g of the compound represented by the chemical formula (M-13), and propylene glycol-1-ethyl ether 53 A flask containing .5 g was set with a condenser and a dropping funnel containing the prepared aqueous oxalic acid solution. 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 produced by the reaction was removed to obtain 45.4 g of a resin solution.
The solid content in this resin solution was (A-7) polysiloxane.

In addition, the measurement of the solid content concentration and the weight average molecular weight (Mw) of the polysiloxane in this example is 1-1. (A) The same method as described in the synthesis of polysiloxane was performed.

<Synthesis Example 9: (A-8) Polysiloxane>
An aqueous oxalic acid solution was prepared by dissolving 1.31 g of oxalic acid in 11.88 g of water by heating. Thereafter, a flask containing 28.87 g of the compound represented by the chemical formula (M-10), 3.93 g of the compound represented by the chemical formula (M-11), 12.85 g of the compound represented by the chemical formula (M-13), and 33.28 g of methanol. The dropping tube containing the cooling tube and the prepared oxalic acid aqueous solution was 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 223.00 g of propylene glycol monomethyl ether acetate was added and set in an evaporator, and methanol was removed to obtain 105.0 g of a resin solution.
The solid content in this resin solution was (A-8) polysiloxane.

<Synthesis Examples 10 to 25: (A-9) to (A-24) Polysiloxane>
(A-9), (A-11), (A-13), (A-15), (A-17), and (A-19) polysiloxanes are prepared from the monomers shown in Tables 4 and 5. The compounds were synthesized in the same manner as in Synthesis Example 8 except that the blending amounts shown in Tables 4 and 5 were used.
(A-10), (A-12), (A-14), (A-16), (A-18), (A-20), (A-21), (A-22), (A The -23) and (A-24) polysiloxanes were synthesized by the same method as in Synthesis Example 9 except that the monomers shown in Tables 4 and 5 were used in the amounts shown in Tables 4 and 5.

<Comparative Synthesis Examples 3 and 4: (AR-3) and (AR-4) polysiloxane>
(AR-3) Polysiloxane was synthesized by the same method as in Synthesis Example 1 except that the monomers shown in Table 5 were used in the blending amounts shown in Table 5.
(AR-4) Polysiloxane was synthesized by the same method as in Synthesis Example 9 except that the monomers shown in Table 5 were used in the blending amounts shown in Table 5.

The amount of monomer used, the solid content concentration, and the weight average molecular weight (Mw) in the resin solutions obtained in Synthesis Examples 9 to 25 and Comparative Synthesis Examples 3 and 4 were the same as in Synthesis Example 8. It was measured.

<Result>
Tables 4 and 5 show the amount of monomer used, the solid content concentration, and the weight average molecular weight (Mw) of the solid content in the resin solutions obtained in Synthesis Examples 8 to 25 and Comparative Synthesis Examples 3 and 4.
In Tables 4 and 5, the resin composition (theoretical value, unit: mol%) determined by the amount of each monomer used is also shown.

2-2. Preparation of silicon-containing film-forming composition (1) Preparation of silicon-containing film-forming composition 1
(A-7) to (A-24) polysiloxanes obtained in each of the above synthesis examples, (AR-3) and (AR-4) polysiloxanes obtained in each of the above comparative synthesis examples, and (E ) Using other polysiloxane, (C) acid generating compound and (D) solvent, the compositions for forming silicon-containing films of Examples 9 to 26 and Comparative Examples 3 and 4 were prepared as shown below. did.
In this example, “parts” means all parts by mass.

<Example 9>
As shown in Table 6, 1.10 parts of (A-7) polysiloxane obtained in Synthesis Example 8; 0.10 parts of (E-3) other polysiloxane and 0. After dissolving 01 parts in 69.16 parts of (D-2) solvent and 29.63 parts of (D-3) solvent, the solution was filtered through a filter having a pore size of 0.2 μm to obtain the silicon of Example 1. A composition for forming a containing film was obtained.

As the other polysiloxane (E-3) in Table 6, a polymer represented by the following chemical formula was used.

In Table 6, the following compounds were used as the (C-1) acid generating compound, the (D-2) solvent, and the (D-3) solvent.
C-1: 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate D-2: Propylene glycol monomethyl ether acetate D-3: Propylene glycol monoethyl ether

<Examples 10 to 26 and Comparative Examples 3 and 4>
Except for using each component in the ratio shown in Table 6, compositions for forming silicon-containing films of Examples 10 to 26 and Comparative Examples 3 and 4 were prepared in the same manner as in Example 9.

(2) Preparation 2 of silicon-containing film forming composition
(A-7) to (A-24) polysiloxanes obtained in each of the above synthesis examples, (AR-3) and (AR-4) polysiloxanes obtained in each of the above comparative synthesis examples, and (C The compositions for forming silicon-containing films of Examples 27 to 44 and Comparative Examples 5 and 6 were prepared using the acid generating compound and (D) solvent as shown below.

<Example 27>
As shown in Table 7, 1.20 parts of (A-7) polysiloxane obtained in Synthesis Example 1 and 0.01 part of (C-1) acid generating compound were added to 69.16 parts of (D-2) solvent. (D-3) After being dissolved in 29.60 parts of the solvent, this solution was filtered through a filter having a pore size of 0.2 μm to obtain a silicon-containing film forming composition of Example 23.

The (C-1) acid generating compound, the (D-2) solvent and the (D-3) solvent in Table 7 are the (C-1) acid generating compound, the (D-2) solvent and the (D-3) in Table 6. -3) The same solvent was used.

<Examples 28 to 44 and Comparative Examples 5 and 6>
Except for using each component in the ratio shown in Table 7, compositions for forming silicon-containing films of Examples 28 to 44 and Comparative Examples 5 and 6 were prepared in the same manner as in Example 27.

2-3. Evaluation of composition for forming silicon-containing film A substrate with a silicon-containing film was formed using each of the compositions for forming a silicon-containing film of Examples 9 to 44 and Comparative Examples 3 to 6 obtained as described above. Various evaluations were performed.

Solvent resistance, TMAH phenomenon liquid resistance, and basic liquid peeling performance are 1-3. The evaluation was performed by the same method as described in the evaluation of the silicon-containing film forming composition.

<Organic phenomenon solution resistance>
The substrate obtained as described above was immersed in an organic developer (butyl acetate, room temperature) for 60 seconds.
The film thickness before and after immersion was measured using a spectroscopic ellipsometer UV1280E, and the film thickness change rate was calculated from the measured value.
The organic phenomenon solution resistance was evaluated as “A” (good) when the film thickness change rate was less than 1%, and “B” (poor) when it was 1% or more.

<Result>
Table 8 shows the evaluation results of the respective items of solvent resistance, TMAH developer resistance, and basic liquid peeling performance for the silicon-containing film forming compositions of Examples 9 to 26 and Comparative Examples 3 and 4.

Table 9 shows the evaluation results of the respective items of solvent resistance, organic developer resistance, and basic liquid peeling performance for each of the silicon-containing film forming compositions of Examples 27 to 44 and Comparative Examples 5 and 6.

<Discussion>
As is apparent from Tables 8 and 9, it was found that the silicon-containing film forming composition according to this embodiment is excellent in solvent resistance, TMAH developer resistance, or organic developer resistance.
Furthermore, it was also found that the composition for forming a silicon-containing film according to this embodiment has an excellent basic liquid peeling performance.

3-1. (A) Synthesis of polysiloxane [A] Polysiloxane was synthesized using the following silane compound.
M-22: Tetramethoxysilane M-23: Phenyltrimethoxysilane M-24: 4-Methylphenyltrimethoxysilane M-25: Methyltrimethoxysilane

[Synthesis Example 26: Polysiloxane (A-25)]
1.28 g of oxalic acid was dissolved in 12.85 g of water by heating to prepare an aqueous oxalic acid solution. Thereafter, a condenser tube and the above oxalic acid aqueous solution were placed in a flask containing (M-22) 25.05 g (90 mol%), (M-23) 3.63 g (10 mol%) and methanol 43.21 g. A dropping funnel was set. Subsequently, after heating the said flask to 60 degreeC with an oil bath, the said 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 is allowed to cool, and 129.00 g of propylene glycol monomethyl ether acetate is added to the reaction solution and set in an evaporator, and the remaining water and generated methanol are removed to obtain a solid content. As a result, 86.0 g of a solution containing the polysiloxane (A-25) was obtained.
The solid content concentration of the polysiloxane (A-25) in the solution was 18.0% by mass, and the Mw of the polysiloxane (A-25) was 2,000.

[Synthesis Example 27: Polysiloxane (A-26)]
2.92 g of tetramethylammonium hydroxide was dissolved by heating in 8.75 g of water to prepare an aqueous solution of tetraammonium hydroxide. Thereafter, a cooling tube and 10.66 g (70 mol%) and 2.12 g of (M-24) were added to a flask containing 11.67 g of the tetraammonium hydroxide aqueous solution, 4.53 g of water and 20 g of methanol. A dropping funnel containing a methanol solution consisting of (10 mol%), (M-25) 2.72 g (20 mol%) and methanol 20 g was set. Subsequently, after heating the said flask to 50 degreeC with an oil bath, the said methanol solution was dripped slowly and it was made to react at 50 degreeC for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool. Then, the reaction solution cooled as described above was added dropwise to 36.67 g of a maleic acid methanol solution prepared separately by dissolving 4.39 g of maleic anhydride in 16.14 g of water and 16.14 g of methanol. Stir for minutes. Subsequently, 50 g of 4-methyl-2-pentenone was added and then set in an evaporator, and the remaining water, reaction solvent and methanol produced by the reaction were removed to obtain a 4-methyl-2-pentenone resin solution. After the resin solution was transferred to the separatory funnel, 80 g of water was added to perform the first water wash, and 40 g of water was added to perform the second water wash. Thereafter, 50 g of propylene glycol monomethyl ether acetate is 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 to obtain a solid content. As a result, 51 g of a propylene glycol monomethyl ether acetate solution containing polysiloxane (A-26) was obtained.
The solid content concentration of the polysiloxane (A-26) in the solution was 14.5% by mass, and the Mw of the polysiloxane (A-26) was 4,000.

[Synthesis Examples 28 to 30: Polysiloxane (A-27) to (A-29)]
[A] A solution containing polysiloxanes (A-27) to (A-29) in the same manner as in Synthesis Example 26, except that each monomer giving polysiloxane was used in the amount shown in Table 1. Was synthesized.
Table 10 shows the solid content concentration of [A] polysiloxane and the Mw of [A] polysiloxane in the obtained solution containing each [A] polysiloxane.

[Synthesis Example 31: Polysiloxane (A-30)]
1.28 g of oxalic acid was dissolved in 12.85 g of water by heating to prepare an aqueous oxalic acid solution. Thereafter, 13.92 g (50 mol%) of (M-22), 18.15 g (50 mol%) of (M-25) and 57.19 g of 2,6-dimethyl-7-octen-2-ol were placed in the flask. A dropping funnel containing the cooling tube and the oxalic acid aqueous solution was set. Subsequently, after heating the said flask to 60 degreeC with an oil bath, the said 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 is allowed to cool and then set in an evaporator to remove the remaining water and the generated methanol, to obtain 97.3 g of a solution containing polysiloxane (A-30) as a solid content. Obtained.
The solid content concentration of the polysiloxane (A-30) in the solution was 18.0% by mass, and the Mw of the polysiloxane (A-30) was 2,000.

<Result>
Table 10 shows the amount of the monomer used in the resin solutions obtained in Synthesis Examples 26 to 31, the solid content concentration, and the weight average molecular weight (Mw) of the solid content.
In Table 10, the resin composition (theoretical value, unit: mol%) determined by the amount of each monomer used is also shown.

3-2. (B) Compound As the (B) compound, compounds represented by the following chemical formulas (B-1) to (B-5) were used. Compound (B-4) (also referred to as “polymer (B-4)”) was synthesized by the following method.

[Synthesis of Polymer B-4]
The following compound (M-26) 3.49 g (50 mol%) and compound (M-27) 7.03 g (50 mol%) were dissolved in 10.49 g of acetonitrile, and 0.23 g of AIBN as a radical polymerization initiator (total A monomer solution was prepared by adding 5 mol%) to the monomer. Next, a 100 mL three-necked flask containing 20 g of acetonitrile was purged with nitrogen for 30 minutes, and then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower. Thereafter, extraction and washing were performed using a mixed solution of hexane / acetonitrile / isopropyl alcohol = 105 g / 5.25 g / 39.38 g, and further a mixed solution of hexane / acetonitrile / isopropyl alcohol = 105 g / 13.13 g / 19.69 g was used. Extraction washing was performed twice. 74.67 g of propylene glycol monoethyl ether was added and concentrated under reduced pressure to synthesize a polymer (B-4) solution having a solid content concentration of 13% (37.3 g, yield 64%). Mw of the polymer (B-4) was 10,000.

3-3. Preparation of silicon-containing film-forming composition (A-25) to (A-30) polysiloxane, (B-1) to (B-5) compound and (D) solvent obtained in each of the above synthesis examples Using the compositions for forming silicon-containing films of Examples 37 to 47 and Comparative Examples 7 and 8, as shown below.
In this example, “parts” means all parts by mass.

<Example 37>
As shown in Table 11, 1.0 part of (A-25) polysiloxane and 0.3 part of (B-1) compound obtained in Synthesis Example 22 were dissolved in 98.7 parts of (D-4) solvent. Then, this solution was filtered with a filter having a pore size of 0.2 μm to obtain the silicon-containing film forming composition of Example 1.

<Examples 46 to 55 and Comparative Examples 7 and 8>
Except for using each component in the ratio shown in Table 11, compositions for forming silicon-containing films of Examples 46 to 55 and Comparative Examples 7 and 8 were prepared in the same manner as in Example 45.

3-4. Evaluation of composition for forming silicon-containing film A substrate with a silicon-containing film was formed using each of the positive-type silicon-containing film-forming compositions of Examples 45 to 55 and Comparative Examples 7 and 8 obtained as described above. The following various evaluations were performed.

<Result>
Table 12 shows the evaluation results of the respective items of solvent resistance, TMAH developer resistance, and basic liquid peeling performance for each of the positive silicon-containing film forming compositions of Examples 45 to 55 and Comparative Examples 7 and 8.

<Discussion>
As is clear from Table 12, the silicon-containing film forming composition according to this embodiment was found to be excellent in solvent resistance and TMAH developer resistance.
It has also been found that the composition for forming a silicon-containing film according to this embodiment has excellent basic liquid peeling performance.

The silicon-containing film forming composition and the pattern forming method using the composition according to this embodiment can be suitably used for a multilayer resist process. It can be suitably used in a multilayer resist process. Among the multi-layer resist process, finer region than 90 nm (ArF, ArF in immersion exposure, F 2, _EUV, nanoimprint) in the pattern formation using a multilayer resist process in, it can be particularly preferably used .

In addition, the silicon-containing film formed by the silicon-containing film forming composition according to this embodiment exhibits excellent basic liquid peeling performance. Therefore, the silicon-containing film forming composition and the pattern forming method using the composition according to the present embodiment use a multilayer resist process including a step of performing wet stripping with a basic solution, among stripping solutions. It can be suitably used in the pattern formation.

Furthermore, the silicon-containing film formed by the composition for forming a silicon-containing film according to the present embodiment uses another base that causes little damage to the substrate without using a fluorine compound that is frequently used as a stripping solution during wet stripping. Even when an adhesive stripping solution is used, the residue on the substrate can be reliably removed, so that damage to the substrate can be avoided. In addition, when the silicon-containing film is wet-peeled, it is not necessary to set the temperature condition to a high temperature, and damage to the substrate due to heat can be reduced.

Claims

A composition for forming a silicon-containing film used in a multilayer resist process including a step of forming a silicon-containing film on the resist underlayer film surface and peeling the silicon-containing film with a basic liquid,
A silicon-containing film-forming composition comprising a compound having one or more selected from the group consisting of a partial structure represented by the following general formula (1) and a partial structure represented by the following general formula (2) object.

(In the formula (1), when L, —SO 2 —O— * and X 1 do not form a ring, L is a single bond or a divalent organic group, and X 1 is a hydrogen atom or a monovalent organic group. It is.
When L, —SO 2 —O— * and X form a ring, L is a trivalent organic group and X 1 is a divalent organic group. (Note, * represents a bonding position between the O and X 1.))

(In Formula (2), X 2 is a hydrogen atom or a monovalent organic group.)
A compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is represented by (A) the general formula (1). 2. The composition for forming a silicon-containing film according to claim 1, comprising a polysiloxane having at least one selected from the group consisting of a partial structure represented by formula (2) and a partial structure represented by the general formula (2).
The polysiloxane (A) is a structural unit derived from at least one compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The composition for forming a silicon-containing film according to claim 2, which is a polysiloxane having (I).

(In Formulas (3) and (4), p is an integer of 1 or more, R 1 is a single bond or a (p + 1) -valent group. R 2 and R 3 are each independently a hydrogen atom or a fluorine atom. Or R 2 and R 3 may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, and l is an integer of 0 to 2. And m + 1 + n is 4.
In formula (3), Y is a hydrogen atom or a monovalent organic group.
In the formula (4), q and r are each independently an integer of 0 to 3. )
The composition for forming a silicon-containing film according to claim 3, wherein Y in the general formula (3) is an alkyl group.
The composition for forming a silicon-containing film according to claim 3 or 4, wherein the ratio of the structural unit (I) in the (A) polysiloxane is 1 to 60 mol% based on the raw material monomer.
3. The composition for forming a silicon-containing film according to claim 2, wherein the (A) polysiloxane is a polysiloxane having at least a structural unit (II) derived from a compound represented by the following general formula (5).

(In the formula (5), p is an integer of 1 or more, R 1 is a single bond or a (p + 1) -valent group. R 2 and R 3 are each independently a hydrogen atom, a fluorine atom or a monovalent group. An organic group, R 2 and R 3 may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, l is an integer of 0 to 2, and m + 1 + n Is 4. X 2 is a hydrogen atom or a monovalent organic group.)
The composition for forming a silicon-containing film according to claim 6, wherein R 1 in the general formula (5) is a single bond, a sulfur atom or a group containing a sulfur atom.
The silicon-containing film-forming composition according to claim 6 or 7, wherein X 2 in the general formula (5) is an alkyl group.
In Formula (5), X 2 is a monovalent acid-dissociable group, a silicon-containing film-forming composition according to any one of claims 6 to 8.
The composition for forming a silicon-containing film according to any one of claims 6 to 9, wherein a ratio of the structural unit (II) in the (A) polysiloxane is 5 to 30 mol% based on a raw material monomer.
The compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is selected from (B) a sulfo group and a sulfonate group. The composition for forming a silicon-containing film according to any one of claims 1 to 10, comprising a compound having at least one selected from the above (excluding the (A) polysiloxane).
The silicon-containing film according to claim 11, further comprising (A ′) polysiloxane having neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2). Forming composition.
The composition for forming a silicon-containing film according to claim 11 or 12, wherein the compound (B) is a vinyl polymer.
The silicon-containing composition according to any one of claims 11 to 13, wherein the content of the compound (B) is 0.1 to 80 parts by weight with respect to 100 parts by weight of the (A ') polysiloxane. Film forming composition.
(1) forming a silicon-containing film on the upper surface side of the substrate using the silicon-containing film-forming composition;
(2) forming a resist pattern on the upper surface side of the silicon-containing film;
(3) forming a pattern on the silicon-containing film by one or more etchings using the resist pattern as a mask;
(4) forming a pattern on the substrate by one or more etchings using the pattern formed on the silicon-containing film as a mask; and
(5) a step of peeling the silicon-containing film with a basic liquid;
A pattern forming method for performing
The composition for forming a silicon-containing film includes a compound having at least one selected from the group consisting of a partial structure represented by the following general formula (1) and a partial structure represented by the following general formula (2). A pattern forming method characterized by this.

(In the formula (1), when L, —SO 2 —O— * and X 1 do not form a ring, L is a single bond or a divalent organic group, and X 1 is a hydrogen atom or a monovalent organic group. It is.
When L, —SO 2 —O— * and X form a ring, L is a trivalent organic group and X 1 is a divalent organic group. (Note, * represents a bonding position between the O and X 1.))

(In Formula (2), X 2 is a hydrogen atom or a monovalent organic group.)
A compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is represented by (A) the general formula (1). The pattern formation method of Claim 15 which contains the polysiloxane which has 1 or more types chosen from the group which consists of the partial structure represented by the partial structure represented by said general formula (2), and said partial structure.
The polysiloxane (A) is a structural unit derived from at least one compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The pattern formation method of Claim 16 which is polysiloxane which has (I).

(In Formulas (3) and (4), p is an integer of 1 or more, R 1 is a single bond or a (p + 1) -valent group. R 2 and R 3 are each independently a hydrogen atom or a fluorine atom. Or R 2 and R 3 may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, and l is an integer of 0 to 2. And m + 1 + n is 4.
In formula (3), Y is a hydrogen atom or a monovalent organic group.
In the formula (4), q and r are each independently an integer of 0 to 3. )
The pattern formation method according to claim 17, wherein Y in the general formula (3) is an alkyl group.
The pattern forming method according to claim 17 or 18, wherein a ratio of the structural unit (I) in the (A) polysiloxane is 1 to 60 mol% based on a raw material monomer.
The pattern forming method according to claim 16, wherein the (A) polysiloxane is a polysiloxane having a structural unit (II) derived from at least a compound represented by the following general formula (5).

(In the formula (5), p is an integer of 1 or more, R 1 is a single bond or a (p + 1) -valent group. R 2 and R 3 are each independently a hydrogen atom, a fluorine atom or a monovalent group. An organic group, R 2 and R 3 may be the same or different, n is an integer of 1 to 3, m is an integer of 1 to 3, l is an integer of 0 to 2, and m + 1 + n Is 4. X 2 is a hydrogen atom or a monovalent organic group.)
21. The pattern forming method according to claim 20, wherein R 1 in the general formula (5) is a single bond, a sulfur atom or a group containing a sulfur atom.
The pattern formation method according to claim 20, wherein X 2 in the general formula (5) is an alkyl group.
In Formula (5), X 2 is a monovalent acid-dissociable groups, a pattern forming method according to any one of claims 20 22.
The pattern forming method according to any one of claims 20 to 23, wherein a ratio of the structural unit (II) in the (A) polysiloxane is 5 to 30 mol% based on a raw material monomer.
The compound having at least one selected from the group consisting of the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is selected from (B) a sulfo group and a sulfonate group. The pattern formation method as described in any one of Claims 15-24 which contains the compound (however, except the said (A) polysiloxane) which has at least 1 type.
The composition for forming a silicon-containing film further includes (A ′) a polysiloxane having neither the partial structure represented by the general formula (1) nor the partial structure represented by the general formula (2). The pattern forming method according to claim 25.
27. The pattern forming method according to claim 25 or 26, wherein the compound (B) is a vinyl polymer.
The pattern formation according to any one of claims 25 to 27, wherein the content of the compound (B) is 0.1 to 80 parts by weight with respect to 100 parts by weight of the (A ') polysiloxane. Method.
(6) forming a resist underlayer film on the substrate;
And further
29. The pattern forming method according to any one of claims 15 to 28, wherein in the step (1), a silicon-containing film is formed on the resist underlayer film using the silicon-containing film forming composition.