JP6516459B2 - Method of producing structure including base agent and phase separation structure - Google Patents

Description

  The present invention relates to a method for producing a structure including a base agent and a phase separation structure.

  In recent years, with the further miniaturization of large-scale integrated circuits (LSI), techniques for processing more delicate structures are required. In response to such demands, technological development is being carried out to form finer structures using the phase separation structure formed by the self-assembly of block copolymers in which mutually incompatible blocks are bonded to each other. .

In order to utilize phase separation of the block copolymer, it is essential to form the self-assembled nanostructures formed by microphase separation only in specific regions and to align them in a desired direction.
In order to realize position control and orientation control of such self-assembled nanostructures, methods such as graphoepitaxy that controls phase separation patterns by guide patterns, and chemical epitaxy that controls phase separation patterns by differences in substrate chemical states It is proposed (for example, refer nonpatent literature 1).

  As a method of phase separation of block copolymers to form a fine pattern, for example, a method of forming a neutral layer having a surface free energy of an intermediate value of surface free energies of two block chains on a substrate Are disclosed (see, for example, Patent Document 1). By forming such a neutral layer on the substrate, the surface on which the block copolymer contacts on the substrate has a surface free energy of an intermediate value of the surface free energy of the two block chains. Become. This forms patterns of various shapes having smaller dimensions than existing lithography techniques.

JP, 2008-36491, A

Proceedings of SPIE, Volume 7637, 76370 G-1 (2010).

However, in the method described in Patent Document 1, it is necessary to select a neutral layer material having a desired value of surface free energy depending on the type of block copolymer to be used and to control the surface free energy of the neutral layer. . For this reason, there has been a demand for a primer which can be used conveniently.
Moreover, in the conventional neutral layer material (base agent), there is a problem that control of the surface state of the base agent layer formed using this is insufficient and phase separation failure of the block copolymer tends to occur.
This invention is made in view of the said situation, Comprising: The phase separation performance of a block copolymer is improved, the base agent which can be used conveniently, and the manufacturing method of the structure containing a phase separation structure using the same. To provide the problem.

  The inventors of the present invention have examined, when forming a fine structure by a directed self assembly (DSA) technique of block copolymer, a substrate, and a layer containing the block copolymer formed on the substrate, It has been found that the phase separation of the block copolymer is promoted by enhancing the adhesion of Then, as a result of further examination, it is found that the adhesion can be enhanced and the above-mentioned problems can be solved by adopting a specific resin component as the base agent material, and the present invention has been completed.

A first aspect of the present invention was formed on a substrate, the hydrophobic polymer block (b11) and the hydrophilic polymer block (b21) and is bonded to block copolymer layer comprising a polymer, undercoat agent used in order to phase separation A resin component, the resin component comprising a polymer compound represented by Formula (A1-1) described later and a polymer compound represented by Formula (A2-1) described later It is a base agent containing at least one selected from the group .
According to a second aspect of the present invention, in the step of applying the base agent of the first aspect on a substrate to form a base agent layer, and on the base agent layer, a hydrophobic polymer block (b11) and A structure comprising a phase separation structure, comprising the steps of: forming a layer containing a block copolymer in which it is bonded to a hydrophilic polymer block (b21); and separating the layer containing the block copolymer Manufacturing method.

In the present specification and claims, “aliphatic” is a concept relative to an aromatic and is defined to mean a group, a compound or the like having no aromaticity.
The term "alkyl group" is intended to include linear, branched and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified.
The "alkylene group" is intended to include a linear, branched and cyclic divalent saturated hydrocarbon group unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
The “halogenated alkyl group” is a group in which part or all of hydrogen atoms of an alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of the hydrogen atoms of the alkyl group or the alkylene group are substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
The “constituent unit derived from acrylic acid ester” means a constitutional unit formed by cleavage of the ethylenic double bond of acrylic acid ester.
The “acrylic ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ = CH—COOH) is substituted with an organic group.
In the acrylic ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted by a substituent. The substituent (R ^α ) for substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or a group other than a hydrogen atom, and is, for example, an alkyl group of 1 to 5 carbon atoms, a halogenation of 1 to 5 carbon atoms Alkyl groups, hydroxyalkyl groups and the like can be mentioned. In addition, the carbon atom of alpha-position of acrylic acid ester is a carbon atom which the carbonyl group has couple | bonded, unless there is particular notice.
Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α position is substituted with a substituent may be referred to as an α-substituted acrylic acid ester. Moreover, an acrylic ester and an alpha substituted acrylic ester may be included and it may be called "(alpha substituted) acrylic ester."
The “structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
The term "hydroxystyrene derivative" is a concept including those in which a hydrogen atom at the alpha position of hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As their derivatives, those in which the hydrogen atom of hydroxystyrene which may be substituted with a hydrogen atom at the alpha position is substituted with an organic group, or even if the hydrogen atom at the alpha position is substituted with a substituent What has substituents other than a hydroxyl group couple | bonded with the benzene ring of good hydroxystyrene, etc. are mentioned. The alpha position (carbon atom at the alpha position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.
As a substituent which substitutes the hydrogen atom of alpha position of hydroxystyrene, the thing similar to what was mentioned as a substituent of alpha position in the above-mentioned alpha substitution acrylic acid ester is mentioned.
The “constituent unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative” means a constitutional unit formed by cleavage of an ethylenic double bond of vinylbenzoic acid or a vinylbenzoic acid derivative.
The "vinyl benzoic acid derivative" is a concept including those in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with an alkyl group, another substituent such as a halogenated alkyl group, and derivatives thereof. As their derivatives, those in which the hydrogen atom in the alpha position is substituted with an organic group and the hydrogen atom in the carboxy group of vinyl benzoic acid which may be substituted with a substituent, or the hydrogen atom in the alpha position is substituted with a substituent And those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid which may be mentioned. The alpha position (carbon atom at the alpha position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.
The "styrene derivative" means that the hydrogen atom at the alpha position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
The “structural unit derived from styrene” and the “structural unit derived from a styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (a methyl group, an ethyl group, a propyl group, an isopropyl group) , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
In addition, specific examples of the halogenated alkyl group as a substituent at the α-position include groups in which part or all of the hydrogen atoms of the above “alkyl group as a substituent at the α-position” are substituted with a halogen atom Be Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Further, specific examples of the hydroxyalkyl group as a substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as a substituent at the α-position” are substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.
When it is described that "it may have a substituent", when substituting a hydrogen atom (-H) with a monovalent group and when substituting a methylene group (-CH _2- ) with a divalent group Including both.
"Exposure" is a concept that includes general radiation irradiation.

According to the base agent of the present invention, the phase separation performance of the block copolymer can be enhanced and it can be used conveniently.
According to the method for producing a structure including the phase separation structure of the present invention, the phase separation performance of the block copolymer is enhanced, and a finer structure can be formed in a better shape as compared with the existing lithography technology.

It is a schematic process drawing explaining one embodiment of a manufacturing method of a structure containing phase separation structure concerning the present invention. It is a figure explaining one example of an embodiment of an arbitrary process.

<Base agent>
The undercoating agent of the present invention is used to phase-separate a layer formed on a substrate and containing a block copolymer in which a hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) are bonded.
Such an undercoating agent is useful as a surface-modifying material of a substrate when forming a fine structure by block copolymer induced self-assembly (DSA) technology. By applying such an undercoating agent on a substrate and providing an undercoating agent layer, the substrate surface is compatible with either the hydrophobic polymer block (b11) or the hydrophilic polymer block (b21) constituting the block copolymer. And promote phase separation of the block copolymer.

(Block copolymer)
A block copolymer is a polymer compound in which a plurality of partial components (blocks) in which structural units of the same type are repeatedly bonded are bonded. The block copolymer in the present invention is a polymer compound in which a hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) are bonded.
With the hydrophobic polymer block (b11) (hereinafter, also simply referred to as "block (b11)"), a plurality of monomers having relatively different affinities with water are used, and among these monomers, the affinity with water It refers to a block consisting of a polymer (hydrophobic polymer) obtained by polymerizing a monomer having a relatively lower property. The hydrophilic polymer block (b21) (hereinafter, also simply referred to as “block (b21)”) is a polymer obtained by polymerizing one of the plurality of monomers having a relatively higher affinity to water (hydrophilic polymer) Say a block consisting of

The block (b11) and the block (b21) are not particularly limited as long as phase separation occurs, but it is preferable that they be a combination of mutually incompatible blocks.
In addition, in the block (b11) and the block (b21), the phase composed of at least one block in the blocks composed of the block copolymer can be removed more easily than the phase composed of other blocks. It is preferable that it is a combination.
The number of types of blocks constituting the block copolymer may be two or three or more.
In the block copolymer of the present invention, partial components (blocks) other than the block (b11) and the block (b21) may be bonded.

  As the block (b11) and the block (b21), for example, a block in which structural units derived from styrene or a styrene derivative are repeatedly bonded, and a hydrogen atom bonded to a carbon atom at the α position may be substituted by a substituent A block to which a structural unit derived from an acrylic acid ester (a structural unit derived from an (α-substituted) acrylic acid ester) is repeatedly bonded, and a hydrogen atom bonded to a carbon atom at the α position may be substituted by a substituent A block in which structural units derived from acrylic acid (structural units derived from (α-substituted) acrylic acid) are repeatedly bonded, a block in which structural units derived from siloxane or its derivative are repeatedly bonded, and alkylene oxide are derived Block in which structural units are repeatedly bonded, silsesquioxane structure-containing structural units are repeated Bound block, and the like.

Examples of the styrene derivative include those in which a hydrogen atom at the alpha position of styrene is substituted with a substituent such as an alkyl group or a halogenated alkyl group, or derivatives of these. Examples of these derivatives include those in which a substituent is bonded to the benzene ring of styrene in which the hydrogen atom at the α-position may be substituted by a substituent. As said substituent, a C1-C5 alkyl group, a C1-C5 halogenated alkyl group, a hydroxyalkyl group etc. are mentioned, for example.
Specifically as the styrene derivative, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, 4-vinylbenzyl chloride and the like Can be mentioned.

Examples of (α-substituted) acrylic acid esters include acrylic acid esters and acrylic acid esters in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent. As said substituent, a C1-C5 alkyl group, a C1-C5 halogenated alkyl group, a hydroxyalkyl group etc. are mentioned, for example.
Specific examples of (α-substituted) acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, propyltrimethoxysilane acrylate; methyl methacrylate, ethyl methacrylate , Propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, methacrylic acid methacrylate Rokishipuropiru, benzyl methacrylate, anthracene, glycidyl methacrylate, 3,4-epoxycyclohexyl methane, and the like methacrylic acid esters such as methacrylic acid propyl trimethoxy silane.

Examples of (α-substituted) acrylic acid include acrylic acid and acrylic acid in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent. As said substituent, a C1-C5 alkyl group, a C1-C5 halogenated alkyl group, a hydroxyalkyl group etc. are mentioned, for example.
Specific examples of the (α-substituted) acrylic acid include acrylic acid and methacrylic acid.

Examples of siloxane or derivatives thereof include dimethylsiloxane, diethylsiloxane, diphenylsiloxane, methylphenylsiloxane and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, isopropylene oxide, butylene oxide and the like.
As a silsesquioxane structure containing structural unit, cage silsesquioxane structure containing structural unit is preferable. As a monomer which provides cage type silsesquioxane structure containing structural unit, the compound which has cage type silsesquioxane structure and a polymeric group is mentioned.

  As a block copolymer in the present invention, for example, a block in which structural units derived from styrene or a styrene derivative are repeatedly bonded, and a block in which structural units derived from an (α-substituted) acrylic acid ester are repeatedly bonded Polymer compound; polymer compound in which a block in which structural units derived from styrene or a styrene derivative are repeatedly bonded and a block in which structural units derived from (α-substituted) acrylic acid are repeatedly bonded; styrene or styrene A polymer compound in which a block in which structural units derived from a derivative are repeatedly bonded and a block in which structural units derived from a siloxane or its derivative are repeatedly bonded; a structural unit derived from an alkylene oxide is repeatedly bonded Block and (α substitution) A polymer compound in which a structural unit derived from luic acid ester is repeatedly bonded; and a block in which a structural unit derived from alkylene oxide is repeatedly bonded; and a structural unit derived from (α-substituted) acrylic acid And a block in which the structural unit derived from the cage-type silsesquioxane structure is repeatedly bonded, and the block in which the structural unit derived from (α-substituted) acrylic acid ester is repeatedly bonded A polymer compound in which: a block in which a cage-type silsesquioxane structure-containing constituent unit is repeatedly bonded; and a block in which a constituent unit derived from (α-substituted) acrylic acid is repeatedly bonded A block in which a cage-type silsesquioxane structure-containing constitutional unit is repeatedly bonded; And block structural units are repeatedly linkages derived from hexane or a derivative thereof, include polymeric compounds bound.

Among the above, as the block copolymer, a block in which a structural unit derived from styrene or a styrene derivative is repeatedly bonded and a block in which a structural unit derived from an (α-substituted) acrylic ester is repeatedly bonded are bonded Molecular compound; a polymer compound in which a block in which a structural unit derived from styrene or a styrene derivative is repeatedly bonded and a block in which a structural unit derived from (α-substituted) acrylic acid is repeatedly bonded is preferable, styrene or More preferred is a polymer compound in which a block in which structural units derived from styrene derivatives are repeatedly bonded and a block in which structural units derived from (α-substituted) acrylic acid esters are repeatedly bonded are bonded, from styrene or styrene derivatives Constituting structural units combine repeatedly And the block, (meth) polymeric compound and block structural units are repeatedly bound derived from an acrylate ester, it is bonded are more preferable.
Specifically, polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer, polystyrene-polyethyl methacrylate block copolymer, polystyrene- (poly-t-butyl methacrylate) block copolymer, polystyrene-polymethacrylic acid block copolymer, polystyrene-poly Examples include methyl acrylate block copolymer, polystyrene-polyethyl acrylate block copolymer, polystyrene- (poly-t-butyl acrylate) block copolymer, polystyrene-polyacrylic acid block copolymer and the like. Among these, PS-PMMA block copolymers are particularly preferred.

  The mass average molecular weight (Mw) (based on polystyrene conversion by gel permeation chromatography) of each polymer constituting the block copolymer is not particularly limited as long as it can cause phase separation, but it is not particularly limited. 500,000 are preferable, 5,000-40000 are more preferable, and 5,000-300,000 are more preferable.

The Mw of the block copolymer is not particularly limited as long as it is a size capable of causing phase separation, but 5000 to 100000 is preferable, 20000 to 60000 is more preferable, and 3000 to 50000 is more preferable.
The molecular weight dispersity (Mw / Mn) of the block copolymer is preferably 1.0 to 3.0, more preferably 1.0 to 1.5, and still more preferably 1.0 to 1.2. In addition, Mn shows a number average molecular weight.
The period of the block copolymer (the length of one molecule of the block copolymer) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and still more preferably 20 to 30 nm.

«Resin component (A)»
The base agent which is the first aspect of the present invention contains a resin component (hereinafter sometimes referred to as "resin component (A)" or "(A) component").
The resin component (A) has a constituent unit of the hydrophobic polymer block (b12) or a constituent unit of the hydrophilic polymer block (b22), and has a carboxy group at at least one end of the main chain.

The hydrophobic polymer block (b12) (hereinafter, also simply referred to as "block (b12)") is different from the monomer which provides the constituent unit of the hydrophilic polymer block (b21) constituting the above block copolymer with water. It is a block consisting of a polymer (hydrophobic polymer) in which monomers having relatively low affinity are polymerized. The structural unit of the block (b12) and the structural unit of the block (b11) may have the same or different structures. Above all, the adhesion between the substrate and the layer containing the block copolymer is further enhanced through the undercoating layer, so that the structural unit of the block (b12) and the structural unit of the block (b11) have the same structure. Is preferred.
The hydrophilic polymer block (b22) (hereinafter, also simply referred to as "block (b22)") is different from the monomer which provides the constituent unit of the hydrophobic polymer block (b11) constituting the above block copolymer with water. It is a block consisting of a polymer (hydrophilic polymer) in which a monomer having a relatively high affinity is polymerized. The structural unit of the block (b22) and the structural unit of the block (b21) may have the same or different structures. Above all, the adhesion between the substrate and the layer containing the block copolymer is further enhanced through the undercoating layer, so that the structural unit of the block (b22) and the structural unit of the block (b21) have the same structure. Is preferred.

As the block (b12) and the block (b22), for example, a block in which structural units derived from styrene or a styrene derivative are repeatedly bonded, a block in which structural units derived from an (α-substituted) acrylic ester are repeatedly bonded, α-substituted) a block in which structural units derived from acrylic acid are repeatedly bonded, a block in which structural units derived from siloxane or a derivative thereof are repeatedly bonded, a block in which structural units derived from alkylene oxide are repeatedly bonded, silsesquioxane The block etc. which the sun structure containing structural unit couple | bonded repeatedly are mentioned.
Styrene or styrene derivative in block (b12) and block (b22), (.alpha.-substituted) acrylic ester, (.alpha.-substituted) acrylic acid, siloxane or derivatives thereof, alkylene oxide, monomer providing silsesquioxane structure-containing constitutional unit As the compound, the same compounds as the compounds exemplified in the description of the block (b11) and the block (b21) described above can be mentioned.

The carboxy group possessed by the component (A) is bonded to at least one end of the main chain of one or more polymer compounds contained in the component (A).
As a preferable component (A), for example, a polymer compound having a constituent unit of a hydrophobic polymer block (b12) and having a carboxy group at at least one end of the main chain (hereinafter, “component (A1)”) A high molecular weight compound having a constituent unit of the hydrophilic polymer block (b22) and having a carboxy group at at least one end of the main chain (hereinafter referred to as “component (A2)”). .
In the present invention, although either the component (A1) or the component (A2) can achieve the effects of the present invention, the component (A1) can be suitably adopted from the viewpoint of easy availability.

[(A1) component]
The component (A1) is a polymer compound having a constituent unit of the hydrophobic polymer block (b12) and having a carboxy group at at least one end of the main chain (main chain end).
As the constituent unit of the block (b12), a constituent unit derived from styrene or a styrene derivative is preferable because the surface of the primer layer is easily stabilized. That is, the structural unit (u1) containing a styrene skeleton which may have a substituent is more preferable.

Structural Unit (u1) The structural unit (u1) is a structural unit containing a styrene skeleton which may have a substituent.
The styrene skeleton having a substituent means one in which part or all of hydrogen atoms in the alpha position of benzene or a benzene ring are substituted by a substituent.
As a substituent in the structural unit (u1), carbon atomized by a halogen atom, or an oxygen atom, a halogen atom or a silicon atom may be linear, branched or cyclic or a combination thereof having 1 to 20 carbon atoms A hydrogen group is mentioned.

  As for the substituent in the structural unit (u1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom is more preferable.

As for the substituent in the structural unit (u1), the hydrocarbon group has 1 to 20 carbon atoms. In addition, such a hydrocarbon group is a linear, branched or cyclic hydrocarbon group or a combination thereof, and may contain an oxygen atom, a halogen atom or a silicon atom.
As such a hydrocarbon group, for example, a linear, branched or cyclic alkyl group or an aryl group can be mentioned.

The alkyl group as such a hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.
The alkyl group here is a partially or completely halogenated alkyl group (halogenated alkyl group), an alkylsilyl group in which a carbon atom constituting the alkyl group is substituted with a silicon atom or an oxygen atom, an alkylsilyloxy It may be a group or an alkoxy group.
A partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms bonded to the alkyl group is substituted with a halogen atom, and a completely halogenated alkyl group is bonded to an alkyl group It means an alkyl group in which all hydrogen atoms are substituted by halogen atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are mentioned, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom is more preferable (that is, a fluorinated alkyl group is preferable).
As said alkyl silyl group, a trialkyl silyl group or a trialkyl silyl alkyl group is preferable, for example, a trimethyl silyl group, a trimethyl silyl methyl group, a trimethyl silyl ethyl group, a trimethyl silyl n-propyl group etc. are mentioned suitably.
As the above alkylsilyloxy group, a trialkylsilyloxy group or a trialkylsilyloxyalkyl group is preferable. For example, a trimethylsilyloxy group, a trimethylsilyloxymethyl group, a trimethylsilyloxyethyl group, a trimethylsilyloxy-n-propyl group and the like are preferable. It can be mentioned.
The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

  The aryl group as such a hydrocarbon group has 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

  As a preferable thing of a structural unit (u1), the structural unit represented by the following general formula (u1-1) is mentioned, for example.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｒ^１は、ハロゲン原子、又は酸素原子、ハロゲン原子若しくはケイ素原子を含んでいてもよい炭素数１〜２０の直鎖状、分岐鎖状若しくは環状又はこれらの組み合わせによる炭化水素基である。ｐは、０〜５の整数である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ¹ is a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, a halogen atom or a silicon atom, and which is linear, branched or cyclic or a combination thereof. p is an integer of 0 to 5; ]

In said Formula (u1-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.
The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like can be mentioned.
The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a fluorinated alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom or an alkyl group of 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is preferable. More preferred is a hydrogen atom.

In the above formula (u1-1), R ¹ is a halogen atom, or an oxygen atom, a halogen atom or a silicon atom, and may be linear, branched or cyclic, having 1 to 20 carbon atoms, or a combination thereof Are hydrocarbon groups according to
A layer containing a block copolymer formed on the undercoating agent layer by adjusting the free energy of the surface of the undercoating agent layer by bonding the R ¹ as a substituent to the benzene ring in the structural unit (u1) Can be well phase separated in a vertical cylinder pattern or the like.
R ¹ in the above-mentioned formula (u1-1) is a substituent in the above-mentioned constituent unit (u1) (a halogen atom, or an oxygen atom, a halogen atom or a silicon atom); , Branched or cyclic, or a combination of these hydrocarbon groups).
Among these, as R ¹ , a layer containing a block copolymer formed on the undercoating agent layer can be well phase separated, so that it may have an oxygen atom, a halogen atom or a silicon atom, and may have 1 to 1 carbon atoms 20 linear, branched or cyclic hydrocarbon groups or combinations thereof are preferred.
Among them, an alkyl group having 1 to 20 carbon atoms which may contain an oxygen atom or a halogen atom is more preferable,
An alkyl group of 1 to 6 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms is more preferable,
Particularly preferred is an alkyl group having 1 to 6 carbon atoms.

R number of carbon atoms in the alkyl group in ¹ to 6, more preferably 3 to 6, more preferably 3 or 4, 4 being particularly preferred. The alkyl group in R ¹ is preferably a linear alkyl group or a branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group. Group is preferably mentioned, more preferably n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group, more preferably n-butyl group, isobutyl group or tert-butyl group, tert-butyl group Groups are particularly preferred.
Halogenated alkyl group for R ¹ is, some or all of the hydrogen atoms of the alkyl group for R ¹ above, are substituted with a halogen atom. Especially as this halogen atom, a fluorine atom is preferable. R number of carbon atoms in the halogenated alkyl group for ^1, preferably 1 to 6, more preferably 3 to 6, more preferably 3 or 4.
R number of carbon atoms of the alkoxy group in ¹ is preferably 1 to 6, more preferably 1 to 4, 2 is particularly preferred. The alkoxy group in R ¹ is preferably a linear alkoxy group or a branched alkoxy group, and examples thereof preferably include a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group, and an ethoxy group is particularly preferable. .

  In said Formula (u1-1), p is an integer of 0-5, The integer of 0-3 is preferable, The integer of 0-2 is more preferable, 0 or 1 is more preferable, 1 is especially preferable.

In the above formula (u1-1), the bonding position of R ^{1 in} the benzene ring is preferably the para position because the phase separation performance of the layer containing the block copolymer is further enhanced.

Below, the specific example of the structural unit of a block (b12) is given. In the formula, R ^α is a hydrogen atom or a methyl group.

As the structural unit of the block (b12) contained in the component (A1), one type may be used alone, or two or more types may be used in combination.
The constituent unit of the block (b12) preferably contains a constituent unit (u1).
As such a structural unit (u1), at least one selected from the group consisting of structural units represented by chemical formulas (u1-1-1) to (u1-1-22) is preferable, and a chemical formula (u1-1-1) is preferable. 1) to (u1-1-14) is more preferably at least one selected from the group consisting of the structural units respectively represented by chemical formulas (u1-1-1) to (u1-1-11) At least one selected from the group consisting of structural units is more preferable, and a group consisting of structural units represented by chemical formulas (u1-1-1) to (u1-1-6) and (u1-1-11) Particularly preferred is at least one selected from the group consisting of structural units represented by chemical formulas (u1-1-1) to (u1-1-3) and (u1-1-11), respectively. Is the most Masui.

In the component (A1), the proportion of the constituent unit of the block (b12) is preferably 25 mol% or more, more preferably 50 mol% or more, based on the total of all the constituent units constituting the component (A1). More preferably, it is 100 mol%.
If the proportion of the constituent units of the block (b12) is at least the preferable lower limit value, the surface of the primer layer can be more stabilized, and the layer containing the block copolymer formed on the primer layer can be well phase separated.

The component (A1) has a carboxy group at at least one end of the main chain.
The number of carboxy groups possessed by the end of the main chain is preferably 1 to 3, more preferably 1 or 2, since the phase separation performance of the layer containing the block copolymer formed on the primer layer is further enhanced. Is particularly preferred.
Below, the specific example of the principal chain terminal part which has a carboxy group is given. In the chemical formulae, "*" indicates a bond.

-Arbitrary structural unit (structural unit (u3)) The component (A1) is an arbitrary structural unit (structural unit (u3)) in addition to the structural unit of the block (b12) as long as the effects of the present invention are not impaired. May be included. As a structural unit (u3), the structural unit derived from the monomer which can be copolymerized with the monomer which provides a structural unit (u1) is mentioned, for example.
When the component (A1) has a structural unit (u3), the proportion of the structural unit (u3) in the component (A1) is more than 0 mol 25 with respect to the total of all structural units constituting the component (A1). Mol% or less is preferable.

  Among the above, as the component (A1), the phase separation performance of the layer containing the block copolymer formed on the undercoating layer can be further enhanced, and thus the structural unit (u1) is included, and The high molecular compound which has a carboxy group only in any one terminal part is preferable, and among these, the high molecular compound which has a structural unit (u1) and which a carboxy group has couple | bonded with the principal chain is especially preferable.

  As a preferable thing of a component (A1), the high molecular compound represented by the following general formula (A1-1) is mentioned. In addition, "x" in a chemical formula shows the number of repetition of a structural unit (following same).

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｒ^１０及びＲ^２０は、それぞれ独立に、水素原子、炭素数１〜５の炭化水素基、又はカルボキシ基を有する炭素数１〜５の炭化水素基である。但し、Ｒ^１０及びＲ^２０の少なくとも一方は、カルボキシ基を有する炭素数１〜５の炭化水素基である。Ｒ^１及びｐは、前記式（ｕ１−１）におけるＲ^１及びｐとそれぞれ同様である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ¹⁰ and R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a hydrocarbon group having 1 to 5 carbon atoms having a carboxy group. However, at least one of R ¹⁰ and R ²⁰ is a hydrocarbon group of 1 to 5 carbon atoms having a carboxy group. R ¹ and p are respectively the same as R ¹ and p in the formula (u1-1). ]

In said formula (A1-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R in the formula (A1-1) is the same as R in the formula (u1-1) described above.
As R, a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a fluorinated alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom or an alkyl group of 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is preferable. More preferred is a hydrogen atom.

The hydrocarbon group in R ¹⁰ and R ²⁰ in the formula (A1-1) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group at R ¹⁰ and R ²⁰ may be saturated or unsaturated, and is preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure, and the like, and among them, linear or branched chains Aliphatic hydrocarbon groups are preferred. Among these, a linear or branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable.
The aromatic hydrocarbon group in R ¹⁰ and R ²⁰ is a hydrocarbon group having an aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) π electrons, and may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include benzene and naphthalene. Examples of the aromatic hydrocarbon group for R ¹⁰ and R ²⁰ include a group obtained by removing one or more hydrogen atoms from the above aromatic ring, and a hydrogen atom from an aromatic compound containing two or more aromatic rings (eg, biphenyl, fluorene, etc.) A group in which one or more groups are removed, or a group in which one of the aromatic ring or the hydrogen atom of the aromatic compound is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1 Arylalkyl group such as -naphthylethyl group, 2-naphthylethyl group etc., or a group in which at least one hydrogen atom of the linear or branched alkyl group is substituted with an aromatic ring, etc. Be It is preferable that carbon number of the alkylene group couple | bonded with said aromatic ring or aromatic compound is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is 1.

In at least one of R ¹⁰ and R ^{20 in} the above formula (A1-1), the number of carboxy groups contained in the hydrocarbon group is higher in the phase separation performance of the layer containing the block copolymer formed on the undercoating layer. 1 to 3 is preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

The specific example of (A1) component is given to the following. In the formula, R ^α is a hydrogen atom or a methyl group. R ²¹ in the chemical formula (A1-1-5) is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ²² in the chemical formula (A1-1-6) is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

Among the above, the component (A1) is
At least one selected from the group consisting of polymer compounds represented by chemical formulas (A1-1-1) to (A1-1-6), respectively, is preferable,
More preferably, at least one selected from the group consisting of the polymer compounds represented by chemical formulas (A1-1-1) to (A1-1-4), respectively.

As the component (A), the layer containing the block copolymer formed on the undercoating agent layer can be more favorably phase separated, so the polymer compound represented by the above-mentioned chemical formula (A1-1-1) It is also possible to simultaneously have “(A1-1-1) component” and the polymer compound represented by the chemical formula (A1-1-3) (hereinafter referred to as “(A1-1-3) component”). preferable.
When both the (A1-1-1) component and the (A1-1-3) component are included, the ratio (mass ratio) of the both is (A1) component / (A2) component = 10/90 to 90/10. Preferably, 15/85 to 85/15 are more preferable. When the ratio (mass ratio) is within the above-mentioned preferred range, the surface of the primer layer is more stabilized, and the layer containing the block copolymer formed on the primer layer can be well phase separated.

The content of the component (A1) in the component (A) is preferably 15% by mass or more, more preferably 50% by mass or more, and may be 100% by mass.
If the content of the component (A1) is equal to or more than the above-mentioned preferable lower limit value, the surface of the base agent layer is more stabilized, and the layer containing the block copolymer formed on the base agent layer is easily phase separated easily. Become.

[(A2) component]
The component (A2) is a polymer compound having a constituent unit of the hydrophilic polymer block (b22) and having a carboxy group (—COOH) at at least one end of the main chain.
As the constituent unit of the block (b22), a constituent unit derived from (α-substituted) acrylic acid ester or a constituent unit derived from (α-substituted) acrylic acid because the surface of the primer layer is easily stabilized (That is, a structural unit (u2) derived from acrylic acid or an ester thereof in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent) is preferable.

Structural Unit (u2) The structural unit (u2) is a structural unit derived from acrylic acid or an ester thereof in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted by a substituent.
As a preferable thing of a structural unit (u2), the structural unit represented by the following general formula (u2-1) is mentioned, for example.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｒ^２は、炭素数１〜２０の直鎖状若しくは分岐鎖状のヒドロキシアルキル基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ² is a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. ]

R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group in said Formula (u2-1). R in the formula (u2-1) is the same as R in the formula (u1-1) described above.
As R, a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a fluorinated alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom or an alkyl group of 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is preferable. More preferred is a hydrogen atom.

In formula (u2-1), R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms .
The hydroxyalkyl group in R ² has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms. Particularly preferred is a group obtained by substituting a part or all of hydrogen atoms of an alkyl group having 1 to 4 carbon atoms with a hydroxy group. The number of hydroxy groups is preferably 1 to 3, more preferably 1 or 2.
The hydroxyalkyl group in R ² may be linear or branched.

Below, the specific example of the structural unit of a block (b22) is given. In the formula, R ^α is a hydrogen atom or a methyl group.

As the structural unit of the block (b22) contained in the component (A2), one type may be used alone, or two or more types may be used in combination.
The constituent unit of the block (b22) preferably contains a constituent unit (u2).
As the structural unit (u2), at least one selected from the group consisting of structural units represented by chemical formulas (u2-1-1) to (u2-1-3) is preferable, and The structural unit represented by 1) is particularly preferred.

In the component (A2), the proportion of the constituent unit of the block (b22) is preferably 25 mol% or more, more preferably 50 mol% or more, based on the total of all constituent units constituting the component (A2), More preferably, it is 100 mol%.
If the proportion of the constituent units of the block (b22) is at least the preferable lower limit value, the surface of the primer layer can be more stabilized, and the layer containing the block copolymer formed on the primer layer can be well phase separated.

The component (A2) has a carboxy group (—COOH) at at least one end of the main chain.
The number of carboxy groups possessed by the end of the main chain is preferably 1 to 3, more preferably 1 or 2, since the phase separation performance of the layer containing the block copolymer formed on the primer layer is further enhanced. Is particularly preferred.
Examples of the main chain terminal part having a carboxy group include groups represented by the above chemical formulas (mc-1), (mc-2) and (mc-3), respectively.

-Arbitrary structural unit (structural unit (u4)) The component (A2) is an arbitrary structural unit (structural unit (u4)) in addition to the structural unit of the block (b22) as long as the effects of the present invention are not impaired. May be included. As a structural unit (u4), the structural unit derived from the monomer which can be copolymerized with the monomer which provides a structural unit (u2) is mentioned, for example.
When the component (A2) has the structural unit (u4), the proportion of the structural unit (u4) in the component (A2) is more than 0 mol 25 with respect to the total of all structural units constituting the component (A2). Mol% or less is preferable.

  Among the above, as the component (A2), the phase separation performance of the layer containing the block copolymer formed on the undercoating layer can be further enhanced, and thus the structural unit (u2) is included, and The high molecular compound which has a carboxy group only in any one terminal part is preferable, and, among these, the high molecular compound which has a structural unit (u2) and which a carboxy group has couple | bonded with the principal chain is especially preferable.

  As a preferable thing of a component (A2), the high molecular compound represented by the following general formula (A2-1) is mentioned.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｒ^３０及びＲ^４０は、それぞれ独立に、水素原子、炭素数１〜５の炭化水素基、又はカルボキシ基を有する炭素数１〜５の炭化水素基である。但し、Ｒ^３０及びＲ^４０の少なくとも一方は、カルボキシ基を有する炭素数１〜５の炭化水素基である。Ｒ^２は、前記式（ｕ２−１）におけるＲ^２と同様である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ³⁰ and ^{R 40} are independently a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms having a hydrocarbon group, or a carboxy group having 1 to 5 carbon atoms. However, at least one of R ³⁰ and R ⁴⁰ is a hydrocarbon group of 1 to 5 carbon atoms having a carboxy group. R ² is the same as ^{R 2} in the formula (U2-1). ]

In said formula (A2-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R in the formula (A2-1) is the same as R in the formula (u2-1) described above.
As R, a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a fluorinated alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom or an alkyl group of 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is preferable. More preferred is a hydrogen atom.
In said formula (A2-1), R ³⁰ and R ⁴⁰ are respectively the same as R ¹⁰ and R ²⁰ in said formula (A1-1).

The specific example of (A2) component is given to the following. In the formula, R ^α is a hydrogen atom or a methyl group. R ⁴¹ in the chemical formula (A2-0-1) is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

Among the above, the component (A2) is
At least one selected from the group consisting of polymer compounds represented by chemical formulas (A2-1-1) and (A2-1-2) is preferable, and a polymer represented by chemical formula (A2-1-1) Compounds are more preferred.
The content of the component (A2) in the component (A) is preferably 15% by mass or more, more preferably 50% by mass or more, and may be 100% by mass. If the content of the component (A2) is not less than the above-mentioned preferable lower limit value, the surface of the base agent layer is more stabilized, and the layer containing the block copolymer formed on the base agent layer is easily phase separated easily. Become.

In the primer according to the present invention, as the component (A), one type of polymer compound may be used alone, or two or more types of polymer compounds may be used in combination.
The component (A) preferably contains at least one polymer compound selected from the group consisting of the components (A1) and (A2) described above.

  If component (A) has a constituent unit of hydrophobic polymer block (b12) or a constituent unit of hydrophilic polymer block (b22) and a carboxy group at at least one end of the main chain, You may contain high molecular compounds other than the above-mentioned (A1) component or (A2) component.

The mass average molecular weight (Mw) (based on polystyrene conversion by gel permeation chromatography (GPC)) of the component (A) is not particularly limited, and 1000 to 200,000 is preferable, 1500 to 200,000 is more preferable, and 2000 to 20000. More preferably 150000.
Since it melt | dissolves in the below-mentioned organic solvent fully as it is below the upper limit of this preferable range, it is excellent in the coating property to a board | substrate. On the other hand, when it is not less than the lower limit value of this preferable range, the primer composition is excellent in the production stability of the polymer compound and excellent in the coating property to the substrate.
The molecular weight dispersion degree (Mw / Mn) of the component (A) is not particularly limited, and is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and still more preferably 1.0 to 2.5. preferable. In addition, Mn shows a number average molecular weight.

The component (A) can be obtained, for example, by polymerizing a monomer for deriving each constitutional unit by known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN). In addition, for the component (A), an initiator such as CH ₃ -CH ₂ -CH (CH ₃ ) -Li may be used during the above polymerization.
Furthermore, for the component (A), an end modifier such as isobutylene sulfide may be used during the above polymerization.
The monomer which derives each structural unit may use a commercially available thing, and may use what was synthesize | combined using the well-known method.

In the base agent according to the present invention, the content of the component (A) may be appropriately adjusted according to the desired film thickness and the like of the base agent layer.
The content of the component (A) in the base agent according to the present invention is preferably 70% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more based on the total solid content. Is more preferred.

«Optional component»
The base agent according to the present invention may further contain components (optional components) other than the component (A) in addition to the component (A) described above.

Acid Generator Component (B) The primer according to the present invention may further contain an acid generator component (B) (hereinafter also referred to as “component (B)”). The component (B) generates an acid upon heating or exposure. The component (B) does not have to be acidic per se, and may be one which is decomposed by heat or light to function as an acid.

The component (B) is not particularly limited, and an acid generator component for a chemically amplified resist which has been used in photolithography can be used.
As such an acid generator component, a thermal acid generator which generates an acid by heating, a photoacid generator which generates an acid by exposure, etc. may be mentioned. For example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes, diazomethane-based acid generators such as poly (bissulfonyl) diazomethanes, nitrobenzyl sulfonate A wide variety of systems are known, such as a system acid generator, an iminosulfonate system acid generator, and a disulfone system acid generator.
In addition, "the thermal acid generator which generate | occur | produces an acid by heating" means the component which generate | occur | produces an acid by the heating of 200 degrees C or less specifically. When the heating temperature is 200 ° C. or less, control of the generation of the acid becomes easy. Preferably, a component that generates an acid upon heating at 50 to 150 ° C. is used. When the preferable heating temperature is 50 ° C. or more, the stability in the base agent is good.

  As the onium salt-based acid generator of component (B), a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methide anion, and a fluorinated antimonic acid in the anion part Those having at least one anionic group selected from the group consisting of ions are preferred.

  Moreover, the cation represented by the following general formula (b-c1) or general formula (b-c2) is mentioned to the cation part of the onium salt type acid generator of (B) component.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”はそれぞれ独立に置換基を有していてもよいアリール基、アルキル基又はアルケニル基を表す。式（ｂ−ｃ１）におけるＲ^１”〜Ｒ^３”のうち、いずれか二つが相互に結合して式中のイオウ原子と共に環を形成してもよい。］

[Wherein, R ^{1 ′} ′ to R ^{3 ′} ′ and R ^{5 ′} ′ to R ⁶ ′ ′ each independently represents an aryl group, alkyl group or alkenyl group which may have a substituent. Any two of R ^{1 ′} ′ to R ³ ′ ′ in formula (b-c1) may be bonded to each other to form a ring with the sulfur atom in the formula. ]

In formula (b-c1), R ^{1 ′} ′ to R ^{3 ′} ′ each independently represents an aryl group which may have a substituent, an alkyl group or an alkenyl group. Any two of R ^{1 ′} ′ to R ³ ′ ′ may be bonded to each other to form a ring with the sulfur atom in the formula.

The aryl group of R ^{1 ′} ′ to R ³ ′ ′ is a C 6-20 unsubstituted aryl group; part or all of the hydrogen atoms of the unsubstituted aryl group are an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group , Oxo group (= O), aryl group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, —C (= O) —O—R ⁶ ′, —O—C (= O) —R ⁷ ′, —O A substituted aryl group substituted by -R ⁸ 'and the like can be mentioned. R ⁶ ′, R ⁷ ′ and R ⁸ ′ each represents a linear, branched or cyclic 3 to 20 carbon saturated hydrocarbon group having 1 to 25 carbon atoms, or a 2 to 5 carbon atoms It is a linear or branched aliphatic unsaturated hydrocarbon group.

In R ^{1 ′} ′ to R ^{3 ′} ′, an unsubstituted aryl group is preferably an aryl group having a carbon number of 6 to 10 because it can be synthesized inexpensively. Specifically, examples include a phenyl group and a naphthyl group.

As an alkyl group as a substituent in the substituted aryl group of R ^{1 ′} ′ to R ³ ′ ′, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group It is more preferable that
The alkoxy group as a substituent in the substituted aryl group is preferably an alkoxy group having a carbon number of 1 to 5, and is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group It is more preferable that
As a halogen atom as a substituent in the substituted aryl group, a fluorine atom is preferable.
Examples of the aryl group as a substituent in the substituted aryl group include the same as the aryl groups of R ¹ ′ ′ to R ³ ′ ′.

As an alkoxyalkyloxy group in a substituted aryl group, for example,
General formula: -O-C (R <^47> ) (R < ⁴⁸ >)-O-R < ⁴⁹ >
[Wherein, R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom, or a linear or branched alkyl group, and R ⁴⁹ is an alkyl group. ] The group represented by these is mentioned.
In R ⁴⁷ and R ⁴⁸ , the carbon number of the alkyl group is preferably 1 to 5, and may be linear or branched, an ethyl group or a methyl group is preferable, and a methyl group is most preferable.
At least one of R ⁴⁷ and R ⁴⁸ is preferably a hydrogen atom. In particular, it is more preferable that one is a hydrogen atom and the other is a hydrogen atom or a methyl group.
The alkyl group for R ⁴⁹ preferably has 1 to 15 carbon atoms, and may be linear, branched or cyclic.
The linear or branched alkyl group for R ⁴⁹ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group It can be mentioned.
The cyclic alkyl group for R ⁴⁹ preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane or the like which may or may not be substituted with an alkyl group of 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group Groups obtained by removing one or more hydrogen atoms from the polycycloalkanes of Examples of monocycloalkanes include cyclopentane and cyclohexane. Examples of polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. Among them, a group in which one or more hydrogen atoms have been removed from adamantane is preferable.

As the alkoxycarbonylalkyloxy group in the substituted aryl group, for example,
General ^{formula: -O-R 50 -C (=} O) -O-R 56
[Wherein, R ⁵⁰ is a linear or branched alkylene group, and R ⁵⁶ is a tertiary alkyl group. ] The group represented by these is mentioned.
The linear or branched alkylene group for R ⁵⁰ preferably has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a 1,1-dimethylethylene group. Etc.
As a tertiary alkyl group in R ⁵⁶ , 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl -1-cyclohexyl, 1-ethyl-1-cyclohexyl, 1- (1-adamantyl) -1-methylethyl, 1- (1-adamantyl) -1-methylpropyl, 1- (1-adamantyl) -1-methylbutyl group, 1- (1-adamantyl) -1-methylpentyl group; 1- (1-cyclopentyl) -1-methylethyl group, 1- (1-cyclopentyl) -1-methylpropyl group, 1- (1-cyclopentyl) -1-methylbutyl group, 1- (1-cyclopentyl) -1-methylpentyl group; 1- (1-cyclohexyl) -1-methylethyene Group, 1- (1-cyclohexyl) -1-methylpropyl group, 1- (1-cyclohexyl) -1-methylbutyl group, 1- (1-cyclohexyl) -1-methylpentyl group, tert-butyl group, tert -A pentyl group, a tert- hexyl group, etc. are mentioned.

Moreover, the general ^formula: the ^{R 56} in the -O-R 50 -C (= O ) -O-R 56, also include groups replaced by ^{R 56} '. R ⁵⁶ ′ is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or an aliphatic cyclic group which may contain a hetero atom.
^Examples of the alkyl group for R ⁵⁶ ′ include the same as the alkyl group for R ⁴⁹ described above.
The fluorinated alkyl group for R ⁵⁶ ′ includes a group in which part or all of the hydrogen atoms in the alkyl group for R ⁴⁹ are substituted with a fluorine atom.
The aliphatic cyclic group which may contain a hetero atom in R ⁵⁶ ′ includes an aliphatic cyclic group not containing a hetero atom, an aliphatic cyclic group containing a hetero atom in the ring structure, and an aliphatic cyclic group Those in which a hydrogen atom in a group is substituted with a hetero atom are listed.
As R ⁵⁶ ′, as an aliphatic cyclic group containing no hetero atom, a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane or the like It can be mentioned. Examples of monocycloalkanes include cyclopentane and cyclohexane. Examples of polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. Among them, a group in which one or more hydrogen atoms have been removed from adamantane is preferable.
Specific examples of the aliphatic cyclic group containing a hetero atom in the ring structure for R ⁵⁶ ′ include, for example, aliphatic rings represented by the following formulas (L1) to (L6) and (S1) to (S4), respectively. Formula group etc. are mentioned.

［式中、Ｑ”は炭素数１〜５のアルキレン基、−Ｏ−、−Ｓ−、−Ｏ−Ｒ^９４−または−Ｓ−Ｒ^９５−であり、Ｒ^９４およびＲ^９５はそれぞれ独立に炭素数１〜５のアルキレン基であり、ｍは０または１の整数である。］

[Wherein, Q "is an alkylene group of 1 to 5 carbon atoms, -O-, -S-, -O-R ⁹⁴ -or -S-R ^95- , and R ⁹⁴ and R ⁹⁵ are each independently carbon It is an alkylene group of the number 1-5, and m is an integer of 0 or 1.]

In the above formula, the alkylene group in Q ′ ′, R ⁹⁴ and R ⁹⁵ preferably has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a 1,1-dimethyl group. Ethylene group etc. are mentioned.
In these aliphatic cyclic groups, a part of hydrogen atoms bonded to carbon atoms constituting the ring structure may be substituted by substituents. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O) and the like.
As said alkyl group, a C1-C5 alkyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having a carbon number of 1 to 5, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, methoxy And ethoxy groups are most preferred.
As a halogen atom as the said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.

Specifically, in R ⁵⁶ ′, as a hydrogen atom in an aliphatic cyclic group being substituted by a hetero atom, a hydrogen atom in an aliphatic cyclic group being substituted by an oxygen atom (= O), etc. Can be mentioned.

^{-C (= O) -O-R} 6 ', -O-C (= O) -R 7', 'R 6 ^{in' -O-R 8, R 7} ', R 8' are each carbon atoms 1 to 25 linear, branched or cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or linear or branched aliphatic unsaturated hydrocarbon group having 2 to 5 carbon atoms .

The linear or branched saturated hydrocarbon group has 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.
Examples of the linear saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
As a branched saturated hydrocarbon group, except for tertiary alkyl group, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3 And -methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.
The linear or branched saturated hydrocarbon group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O), a cyano group and a carboxy group.
The alkoxy group as a substituent of the linear or branched saturated hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, and is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, An n-butoxy group and a tert-butoxy group are preferable, and a methoxy group and an ethoxy group are most preferable.
A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom as a substituent of the said linear or branched saturated hydrocarbon group, A fluorine atom is preferable.
As a halogenated alkyl group as a substituent of the linear or branched saturated hydrocarbon group, part or all of hydrogen atoms of the linear or branched saturated hydrocarbon group may be the halogen atom And groups substituted by

The cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in R ⁶ ′, R ⁷ ′ and R ⁸ ′ may be either a polycyclic group or a monocyclic group, for example, one from monocycloalkanes Groups in which a hydrogen atom has been removed; and groups in which one hydrogen atom has been removed from a polycycloalkane such as bicycloalkane, tricycloalkane or tetracycloalkane. More specifically, one hydrogen atom is removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, cyclooctane or the like, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane Groups and the like.
The cyclic saturated hydrocarbon group may have a substituent. For example, part of carbon atoms constituting a ring of the cyclic alkyl group may be substituted with a hetero atom, and even if a hydrogen atom bonded to the ring of the cyclic alkyl group is substituted by a substituent Good.
As an example of the former, one or more hydrogens from a heterocycloalkane in which a part of carbon atoms constituting the ring of the monocycloalkane or polycycloalkane is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom Groups in which atoms have been removed can be mentioned. Moreover, you may have an ester bond (-C (= O) -O-) in the structure of the said ring. Specifically, a lactone-containing monocyclic group such as a group in which one hydrogen atom is removed from γ-butyrolactone, or a group in which one hydrogen atom is removed from a bicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane And lactone-containing polycyclic groups, and the like.
Examples of the substituent in the latter example include the same as those exemplified as the substituent which the linear or branched alkyl group may have, and an alkyl group having 1 to 5 carbon atoms. .

R ⁶ ′, R ⁷ ′ and R ⁸ ′ may be a combination of a linear or branched alkyl group and a cyclic alkyl group.
As a combination of a linear or branched alkyl group and a cyclic alkyl group, a group in which a cyclic alkyl group is bonded to a linear or branched alkyl group as a substituent, or a cyclic alkyl group And groups in which a linear or branched alkyl group is bonded, and the like.

R ⁶ The ', R ^7', linear aliphatic unsaturated hydrocarbon group in R 8 ^', for example, vinyl group, propenyl group (allyl group) and a butynyl group.
R ⁶ The ', R ^7', branch in R 8 ^'chain aliphatic unsaturated hydrocarbon group, for example, 1-methyl propenyl group, and 2-methyl-propenyl group.
The linear or branched aliphatic unsaturated hydrocarbon group may have a substituent. Examples of the substituent include the same as those listed as the substituent which the linear or branched alkyl group may have.

Among R ⁶ ′, R ⁷ ′ and R ⁸ ′, among the above, a linear or branched saturated hydrocarbon group having 1 to 15 carbon atoms, or a cyclic saturated hydrocarbon having 3 to 20 carbon atoms Groups are preferred.

Examples of the alkyl group of R ^{1 ′} ′ to R ³ ′ ′ include, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Especially, it is preferable that it is C1-C5 from the point which is excellent in resolution. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decyl group and the like can be mentioned. Preferred are methyl groups because they are excellent in resolution and can be synthesized inexpensively.
In the alkyl group of R ^{1 ′} ′ to R ³ ′ ′, part or all of the hydrogen atoms thereof are an alkoxy group, a halogen atom, a hydroxyl group, an oxo group (= O), an aryl group, an alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group , -C (= O) -O- R 6 ', -O-C (= O) -R 7', which may be substituted by ^{-O-R 8} 'and the like. Alkoxy group, a halogen atom, an aryl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, -C (= O) -O- R 6 ', -O-C (= O) -R 7', -O-R ⁸ ′ is the same as the substituent of the aryl group of R ¹ ′ ′ to R ³ ′ ′.

The alkenyl group of R ^{1 ′} ′ to R ³ ′ ′ preferably has, for example, 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 to 4 carbon atoms. Specifically, a vinyl group, propenyl group (allyl group), butynyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like can be mentioned.

When any two of R ^{1 ′} ′ to R ³ ′ ′ are mutually bonded to form a ring with a sulfur atom in the formula, it is preferable that a sulfur atom is included to form a 3- to 10-membered ring, It is particularly preferable to form a 5- to 7-membered ring.

  As a preferable thing among the cation part in the compound represented by said Formula (b-c1), the thing specifically shown below is mentioned.

［式中、ｇ１、ｇ２、ｇ３は繰返し数を示し、ｇ１は１〜５の整数であり、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[In the formula, g1, g2 and g3 represent the number of repetitions, g1 is an integer of 1 to 5; ]

In the formula (ca-1-47), R ^d is a substituent. Examples of the substituent include the substituents exemplified in the description of the substituted aryl group above (alkyl group, alkoxy group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, halogen atom, hydroxyl group, oxo group (= O), aryl ^{groups, -C (= O) -O-} R 6 ", -O-C (= O) -R 7", -O-R 8 ") can be mentioned.

In formula (b-c2), each of R ^{5 ′} ′ to R ^{6 ′} ′ independently represents an aryl group which may have a substituent, an alkyl group or an alkenyl group.
Examples of the aryl group of R ^{5 ′} ′ to R ⁶ ′ ′ include the same as the aryl groups of R ¹ ′ ′ to R ³ ′ ′. Examples of the alkyl group of R ^{5 ′} ′ to R ⁶ ′ ′ include the same as the alkyl group of R ¹ ′ ′ to R ³ ′ ′. Examples of the alkenyl group of R ^{5 ′} ′ to R ⁶ ′ ′ include the same as the alkenyl groups of R ¹ ′ ′ to R ³ ′ ′.
Specific examples of the cation moiety in the compound represented by the above formula (b-c2) include diphenyliodonium, bis (4-tert-butylphenyl) iodonium and the like.

  In the present specification, the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation (exposure) with radiation. It is possessed. Such an oxime sulfonate-based acid generator can be selected arbitrarily from among those commonly used for chemically amplified resist compositions.

［式（Ｂ−１）中、Ｒ^３１、Ｒ^３２は、それぞれ独立に有機基を表す。］

[In formula (B-1), R ³¹ and R ³² each independently represent an organic group. ]

The organic group of R ³¹ and R ^{32 is} a group containing a carbon atom, and is an atom other than a carbon atom (for example, hydrogen atom, oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom, etc.), etc. You may have.
As the organic group of R ^31, a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Here, "having a substituent" means that some or all of the hydrogen atoms of the alkyl group or the aryl group are substituted with a substituent.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. As the alkyl group, particularly preferred is a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group). The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted by a halogen atom, and the completely halogenated alkyl group means that all hydrogen atoms are halogen atoms Means an alkyl group substituted by As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, Especially a fluorine atom is preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. Particularly preferred aryl groups are partially or completely halogenated aryl groups. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted by a halogen atom, and the completely halogenated aryl group means that all hydrogen atoms are halogen atoms Means an aryl group substituted by
As R ³¹ , an alkyl group having 1 to 4 carbon atoms which does not have a substituent or a fluorinated alkyl group having 1 to 4 carbon atoms is particularly preferable.
As the organic group of R ^32, a linear, branched or cyclic alkyl group, an aryl group or a cyano group is preferable. ^Examples of the alkyl group and aryl group of R ³² include the same alkyl groups and aryl groups as mentioned for R ³¹ above.
In particular, R ³² is preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  Preferred examples of the oxime sulfonate-based acid generator include compounds represented by general formula (B-2) or (B-3) shown below.

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４は、アリール基を含む基である。Ｒ^３４のアルキル基又はハロゲン化アルキル基と、Ｒ^３５とが結合して環を形成していていもよい。Ｒ^３５は、置換基を有さないアルキル基又はハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is a group containing an aryl group. The alkyl group of R ³⁴ or the halogenated alkyl group may be combined with R ³⁵ to form a ring. R ³⁵ is an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は、２または３価の芳香族炭化水素基である。Ｒ^３８は、置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は、２又は３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a di- or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group having no substituent or a halogenated alkyl group. p ′ ′ is 2 or 3.]

In the general formula (B-2), the alkyl group having no substituent of R ³³ or the halogenated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, The numbers 1 to 6 are most preferable.
As R ³³ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.
In the fluorinated alkyl group for R ³³ , the hydrogen atom of the alkyl group is preferably 50% or more, preferably 70% or more, and more preferably 90% or more. Particularly preferred.
As a group containing an aryl group of R ^34, a hydrogen atom is selected from the ring of an aromatic hydrocarbon such as phenyl group, biphenyl group, fluorenyl group, naphthyl group, anthryl group, phenanthryl group and the like. There may be mentioned a group in which one group is excluded and a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is substituted by a hetero atom such as oxygen atom, sulfur atom or nitrogen atom. Among these, a fluorenyl group is preferable.
The group containing an aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxy group and the like. The alkyl group or the halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.
The substituted or unsubstituted alkyl or halogenated alkyl group of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
As R ³⁵ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.
In the fluorinated alkyl group for R ³⁵ , the hydrogen atom of the alkyl group is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more. Especially preferred because the strength of the generated acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorinated.

In the general formula (B-3), as the alkyl group having no substituent of R ³⁶ or the halogenated alkyl group, the same as the alkyl group having no substituent of the above R ³³ or a halogenated alkyl group Can be mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group of R ³⁷ include groups in which one or two hydrogen atoms have been further removed from the aryl group of R ³⁴ described above.
Examples of the alkyl group having no substituent of R ³⁸ or the halogenated alkyl group include the same as the alkyl group having no substituent of the above R ³⁵ or the halogenated alkyl group.
p ′ ′ is preferably 2.

Specific examples of the oxime sulfonate-based acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzene sulfonyloxy Imino) -benzyl cyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzyl cyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzyl cyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-Methoxybenzyl cyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide, α-[(p-toluenesulfonyloxyimino) -4-Methoxyphenyl! Acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl) Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope Entenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenyl acetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenyl acetonitrile Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro) Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Moreover, the oxime sulfonate-based acid generator disclosed in JP-A-9-208554 ([Chemical formula 18] to [chemical formula 19] of paragraphs [0012] to [0014], WO 04/074242 (65 The oxime sulfonate-based acid generator disclosed in Examples 1 to 40) on page 85 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

Among the diazomethane-based acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and the like can be mentioned.
In addition, diazomethane-based acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
Also, as poly (bissulfonyl) diazomethanes, for example, 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane and the like Door can be.

In the base agent according to the present invention, as the component (B), one type of acid generator may be used alone, or two or more types of acid generator may be used in combination.
When a base agent contains the (B) component, 0.5-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of the (B) component in a base agent, 1-20 mass Part is more preferred. If the content of the component (B) is within the above range, the effects of the present invention can be sufficiently obtained.

  The primer according to the present invention further improves miscible additives, for example, an additional resin for improving the performance of the primer layer, and coating properties, as long as the effects of the present invention are not impaired. For the purpose of appropriately containing a surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base multiplication agent, a basic compound (nitrogen-containing compound such as imidazole, etc.) be able to.

Organic Solvent (S) The base agent according to the present invention dissolves each component such as the component (A) and, if necessary, the component (B) in an organic solvent (hereinafter also referred to as "component (S)"). It can be manufactured.
Any component can be used as the component (S) as long as it can dissolve each component to be used to form a uniform solution, and any conventional solvent for a film composition containing a resin as a main component can be used. One or two or more kinds can be appropriately selected and used.
Examples of the component (S) include lactones such as γ-butyrolactone; acetones such as methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol, diethylene glycol and propylene glycol A polyhydric alcohol such as dipropylene glycol; a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the polyhydric alcohol or a compound having the ester bond Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether etc. or monophenyl ether etc. Derivatives of polyhydric alcohols such as compounds having a ether bond [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; methyl lactate Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether , Dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene etc And organic solvents and the like.
The component (S) may be used alone or as a mixed solvent of two or more.
Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and EL are preferable as the (S) component.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, etc., but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is considered within the range. For example, in the case of blending EL as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, mass ratio of PGMEA: PGME becomes like this. Preferably 1: 9-9: 1, More preferably, 2: 8-8: 2, More preferably, 3: 7-7: 3 It is. Moreover, when mix | blending PGME and cyclohexanone as a polar solvent, mass ratio of PGMEA: (PGME + cyclohexanone) becomes like this. Preferably 1: 9-9: 1, More preferably, 2: 8-8: 2, More preferably 3: 7 to 7: 3.
Moreover, as (S) component, mixed solvent of PGMEA, EL, or a mixed solvent of the above PGMEA and a polar solvent, and γ-butyrolactone is also preferable. In this case, as the mixing ratio, the mass ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of the component (S) used is not particularly limited, and is a concentration that can be applied to a substrate etc. and appropriately set according to the applied film thickness, but generally the solid concentration of the base agent is 0 .1 to 20% by mass, preferably 0.2 to 15% by mass.

(Contact angle of water on the surface of the base agent layer formed on the substrate)
When the undercoating agent according to the present invention contains a resin component having a constituent unit of the hydrophobic polymer block (b12), the contact angle of water on the surface of the undercoating agent layer formed on the substrate using this is preferred. Is 80 ° or more, more preferably 90 ° or more.
Moreover, when the base agent concerning this invention contains the resin component which has a structural unit of a hydrophilic polymer block (b22), the contact angle of the water in the surface of the base agent layer formed on a board | substrate using this is Preferably, it becomes 30 to 80 degrees.
If the value of the contact angle is within the above-mentioned preferable range, the adhesion between the substrate and the layer containing the block copolymer is enhanced through the undercoating layer. Along with this, the phase separation performance of the layer containing the block copolymer formed on the primer layer is enhanced.

The contact angle of water is measured by the following procedure.
Procedure (1): A PGMEA solution of the component (A) is applied on a substrate to form a base agent layer having a thickness of less than 10 nm.
Procedure (2): 2 μL of water is dropped on the surface of the base agent layer, and the contact angle (static contact angle) is measured by a contact angle meter.

The undercoating agent according to the present invention described above has a constituent unit of the hydrophobic polymer block (b12) or a constituent unit of the hydrophilic polymer block (b22), and a carboxy group at at least one end of the main chain Containing a resin component.
When such an undercoating agent is used as a surface modifying material of a substrate, which is used for phase separation of a layer containing a block copolymer formed on the substrate, the substrate through the undercoating agent layer formed by the undercoating agent The adhesion between the layer and the layer containing the block copolymer formed on the substrate is enhanced. Along with this, it is considered that the phase separation performance of the block copolymer is improved.
In addition, since the surface state of the base agent layer is stable, it is necessary to select a neutral layer material in which the free energy of the surface of the base agent layer becomes a desired value depending on the type of block copolymer used. Absent. Thus, such a base agent can be used conveniently.

<Method of manufacturing structure including phase separation structure>
The method for producing a structure including a phase separation structure according to a second aspect of the present invention comprises the steps of applying the base agent of the first aspect of the present invention described above onto a substrate to form a base agent layer ( (Hereinafter referred to as “step (i)”) and a step of forming a layer containing a block copolymer in which a hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) are bonded on the undercoating layer And a step of phase-separating a layer containing the block copolymer (hereinafter referred to as "step (iii)").
Hereinafter, a method for producing a structure including such a phase separation structure will be specifically described with reference to FIG. However, the present invention is not limited to this.

FIG. 1 shows one embodiment of a method of manufacturing a structure including a phase separation structure according to the present invention.
First, the above-mentioned base agent according to the present invention is applied onto the substrate 1 to form the base agent layer 2 (FIG. 1 (I); step (i)).
Next, a composition containing a block copolymer in which a hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) are bonded is applied onto the primer layer 2 (hereinafter also referred to as "BCP composition"). To form a layer 3 containing the block copolymer (FIG. 1 (II); step (ii)).
Next, heating is performed to perform annealing, and the layer 3 containing the block copolymer is phase-separated into the phase 3a and the phase 3b (FIG. 1 (III); step (iii)).
According to the manufacturing method of the present embodiment described above, that is, the manufacturing method having steps (i) to (iii), the structure 3 ′ including the phase separation structure is formed on the substrate 1 on which the base agent layer 2 is formed. Manufactured.

[Step (i)]
In the step (i), the base agent is applied onto the substrate 1 to form the base agent layer 2.
By providing the base agent layer 2 on the substrate 1, the hydrophilic / hydrophobic balance of the surface of the substrate 1 and the layer 3 containing the block copolymer can be achieved.
That is, when the undercoating agent layer 2 contains a resin component having a constituent unit of the hydrophobic polymer block (b12), the phase composed of the hydrophobic polymer block (b11) in the layer 3 containing the block copolymer Adhesion is increased. When the primer layer 2 contains a resin component having a constituent unit of the hydrophilic polymer block (b22), the adhesion between the phase consisting of the hydrophilic polymer block (b21) of the layer 3 containing the block copolymer and the substrate Increase.
Along with this, the phase separation of the layer 3 containing the block copolymer facilitates the formation of a cylinder structure oriented in the direction perpendicular to the surface of the substrate 1.

The type of the substrate 1 is not particularly limited as long as the substrate can apply the BCP composition on its surface. For example, a substrate made of an inorganic substance such as metal (silicon, copper, chromium, iron, aluminum etc.), glass, titanium oxide, silica, mica etc .; And substrates made of organic substances such as polystyrene, cellulose, cellulose acetate, and phenol resin.
The size and shape of the substrate 1 are not particularly limited. The substrate 1 does not necessarily have to have a smooth surface, and substrates of various shapes can be appropriately selected. For example, a substrate having a curved surface, a flat plate having a concavo-convex shape on the surface, a thin plate or the like may be mentioned.

An inorganic and / or organic film may be provided on the surface of the substrate 1.
Examples of inorganic films include inorganic antireflective films (inorganic BARCs). An organic antireflective film (organic BARC) may be mentioned as the organic film.
The inorganic film can be formed, for example, by applying an inorganic antireflective film composition such as a silicon material on the substrate and baking it.
The organic film is formed, for example, by applying a material for forming an organic film, in which a resin component or the like constituting the film is dissolved in an organic solvent, on a substrate by a spinner or the like, preferably 200 to 300 ° C., preferably 30 to 300. It can be formed by baking treatment under heating conditions for a second, more preferably for 60 to 180 seconds. The material for forming an organic film does not necessarily need to be sensitive to light or an electron beam like a resist film, and may or may not have sensitivity. Specifically, a resist or a resin generally used in the manufacture of a semiconductor element or a liquid crystal display element can be used.
In addition, by etching an organic film using a pattern made of a block copolymer, which is formed by processing the layer 3, the pattern can be transferred to the organic film to form an organic film pattern. Thus, the material for forming an organic film is preferably a material capable of forming an organic film which can be etched, particularly dry-etched. Among them, a material capable of forming an organic film capable of etching such as oxygen plasma etching is preferable. Such an organic film forming material may be a material conventionally used to form an organic film such as an organic BARC. For example, ARC series manufactured by Nissan Chemical Industries, Ltd., AR series manufactured by Rohm and Haas, SWK series manufactured by Tokyo Ohka Kogyo Co., Ltd., etc. may be mentioned.

It does not specifically limit as a method to apply | coat the base agent which concerns on this invention on the board | substrate 1, and forms the base agent layer 2, It can form by a conventionally well-known method.
For example, the base agent layer 2 can be formed by applying a base agent on the substrate 1 by a conventionally known method such as spin coating or using a spinner to form a coating and drying.
As a method of drying the coating film, it is sufficient if the solvent contained in the base agent can be volatilized, and examples thereof include a baking method and the like. At this time, the baking temperature is preferably 80 to 300 ° C., more preferably 180 to 300 ° C., and still more preferably 210 to 280 ° C. The baking time is preferably 30 to 500 seconds, more preferably 60 to 400 seconds.
The above-mentioned bake time and the bake temperature can be arbitrarily combined.
About 10-100 nm is preferable, and, as for the thickness of the base agent layer 2 after drying of a coating film, about 40-90 nm is more preferable.

Before forming the base agent layer 2 on the substrate 1, the surface of the substrate 1 may be cleaned in advance. By cleaning the surface of the substrate 1, the coatability of the base agent is improved.
As the cleaning treatment method, a conventionally known method can be used, and examples thereof include oxygen plasma treatment, ozone oxidation treatment, acid alkali treatment, chemical modification treatment and the like.

After forming the base agent layer 2, the base agent layer 2 may be rinsed using a rinse liquid such as a solvent, if necessary. The rinse removes non-crosslinked parts and the like in the primer layer 2 and thus improves the affinity to at least one polymer (block) constituting the block copolymer and orients vertically to the surface of the substrate 1 It becomes easy to form the phase-separation structure which consists of the cylinder structure which was carried out.
The rinse solution is only required to dissolve the uncrosslinked portion, and a solvent such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), or a commercially available thinner solution Etc. can be used.
In addition, after the cleaning, post-baking may be performed to evaporate the rinse solution. 80-300 degreeC is preferable, as for the temperature conditions of this post-baking, 100-270 degreeC is more preferable, and 120-250 degreeC is further more preferable. The baking time is preferably 30 to 500 seconds, more preferably 60 to 240 seconds. About 1-10 nm is preferable, and, as for the thickness of the base agent layer 2 after this post-baking, about 2-7 nm is more preferable.

[Step (ii)]
In the step (ii), a layer 3 containing a block copolymer in which a plurality of types of blocks are combined is formed on the undercoating layer 2.
The method for forming the layer 3 on the base agent layer 2 is not particularly limited. For example, the BCP composition is coated on the base agent layer 2 by a conventionally known method such as spin coating or using a spinner. And a method of forming a coating film and drying it. Details of the BCP composition will be described later.

The thickness of the layer 3 may be a thickness sufficient for phase separation to occur, and in consideration of the type of the substrate 1 or the structural periodic size of the phase separation structure to be formed or the uniformity of the nanostructure, etc. 20 to 100 nm is preferable, and 30 to 80 nm is more preferable.
For example, when the substrate 1 is a Cu substrate, the thickness of the layer 3 is preferably 10 to 100 nm, and more preferably 30 to 80 nm.

[Step (iii)]
In step (iii), the layer 3 containing the block copolymer is phase separated.
By annealing the substrate 1 after the step (ii) by heating, a phase separation structure is formed such that at least a part of the surface of the substrate 1 is exposed by selective removal of the block copolymer. That is, a structure 3 'including a phase separation structure in which the phases 3a and 3b are separated on the substrate 1 is manufactured.
The temperature conditions for the annealing treatment are preferably above the glass transition temperature of the block copolymer used and below the thermal decomposition temperature. For example, in the case where the block copolymer is a polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer (weight average molecular weight 5000 to 100,000), 180 to 270 ° C. is preferable. The heating time is preferably 30 to 3600 seconds.
The annealing treatment is preferably performed in a low reactive gas such as nitrogen.

  According to the method of manufacturing a structure including a phase separation structure according to the present invention described above, the phase separation performance of the block copolymer is enhanced, and the finer structure is formed in a better shape as compared with the existing lithography technology. It can be formed. In addition, it is possible to manufacture a substrate provided with nanostructures whose position and orientation are more freely designed on the substrate surface. For example, the structure to be formed has high adhesion to the substrate and tends to have a phase separation structure composed of a cylinder structure oriented in the direction perpendicular to the substrate surface.

[Optional process]
The manufacturing method of the structure containing phase-separation structure based on this invention is not limited to embodiment mentioned above, You may have processes (arbitrary processes) other than process (i)-(iii).
As such an optional step, a step of selectively removing a phase composed of at least one of a plurality of types of blocks constituting the block copolymer out of the layer containing the block copolymer (hereinafter referred to as “step (iv)” And guide pattern formation steps.

Step (iv) In the step (iv), the layer comprising the block copolymer formed on the undercoating layer comprises at least one block of the plurality of types of blocks constituting the block copolymer. Selectively remove the phases. Thereby, a fine pattern (polymer nanostructure is formed.

As a method of selectively removing the phase consisting of blocks, a method of performing oxygen plasma treatment on a layer containing a block copolymer, a method of performing hydrogen plasma treatment, and the like can be mentioned.
In the following, among the blocks constituting the block copolymer, P _A block blocks that are not selectively removed, the blocks are selectively removed as P _B block. For example, after phase separation of the layer containing the PS-PMMA block copolymer, the phase consisting of PMMA is selectively removed by performing oxygen plasma treatment, hydrogen plasma treatment or the like on the layer. In this case, PS moiety is a block _{P A,} PMMA moiety is _{P B} block.

FIG. 2 shows an example embodiment of step (iv).
In the embodiment shown in FIG. 2, the structure 3 ′ produced on the substrate 1 in the step (iii) is subjected to oxygen plasma treatment to selectively remove the phase 3 a and consist of the separated phases 3 b. A pattern (polymer nanostructure) is formed. In this case, phase 3b is a phase consisting of _{P A} block is a phase-phase 3a consists _{P B} block.

As described above, the substrate 1 on which a pattern is formed by phase separation of the block copolymer layer 3 can be used as it is, but the pattern on the substrate 1 (polymer nanostructures can be further heated The shape of) can also be changed.
The temperature conditions of heating are above the glass transition temperature of the block copolymer used and preferably below the thermal decomposition temperature. Further, the heating is preferably performed in a low reactive gas such as nitrogen.

-Guide pattern forming step In the method of manufacturing a structure including a phase separation structure according to the present invention, a step of providing a guide pattern on the undercoating layer between the step (i) and the step (ii) (guide It may have a pattern formation process). This makes it possible to control the array structure of the phase separation structure.
For example, even in the case of a block copolymer in which a random fingerprint-like phase separation structure is formed without providing a guide pattern, alignment is performed along the grooves by providing a groove structure of a resist film on the surface of the primer layer The phase separation structure is obtained. A guide pattern may be provided on the base agent layer 2 on such a principle. In addition, when the surface of the guide pattern has affinity with any of the polymers constituting the block copolymer, a phase separation structure composed of a cylinder structure oriented in the direction perpendicular to the substrate surface is easily formed.

The guide pattern can be formed, for example, using a resist composition.
As the resist composition for forming the guide pattern, one having an affinity to any of the polymers constituting the block copolymer is appropriately selected from the resist composition generally used for forming a resist pattern and its modified products. Can be used. As the resist composition, a positive resist composition forming a positive pattern in which a resist film exposed portion is dissolved and removed, a negative resist composition forming a negative pattern in which a resist film unexposed portion is dissolved and removed Although any may be sufficient, it is preferable that it is a negative resist composition. The negative resist composition contains, for example, an acid generator and a base component such that the solubility in a developer containing an organic solvent is reduced by the action of an acid, and the base component is A resist composition containing a resin component having a structural unit which is decomposed by the action of an acid to increase polarity is preferable.
After the BCP composition is cast on the base agent layer on which the guide pattern is formed, annealing is performed to cause phase separation. Therefore, as a resist composition for forming a guide pattern, it is preferable to be able to form a resist film excellent in solvent resistance and heat resistance.

Regarding Composition Containing Block Copolymer (BCP Composition) The BCP composition can be prepared by dissolving the above-described block copolymer in an organic solvent. Examples of the organic solvent include the same as the component (S) described above as the organic solvent that can be used for the base agent.
The organic solvent contained in the BCP composition is not particularly limited, and the concentration which can be applied is appropriately set according to the applied film thickness, and generally, the solid content concentration of the block copolymer is 0.2 to 70. It is used so that it becomes mass%, preferably 0.2 to 50 mass%.

  In addition to the above-mentioned block copolymers and organic solvents, the BCP composition may, if desired, additionally contain compatible additives, such as additional resins for improving the performance of the primer layer, to improve the coatability. A surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base multiplication agent, a basic compound and the like can be appropriately contained.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

<Example of synthesis of polymer compound>
<< Synthesis of Polymer Compound 3 >>
180 mg of lithium chloride was put into a dried 50 mL Schlenk tube, 39 g of low oxygen and low moisture grade tetrahydrofuran was put under an argon atmosphere, and cooled to -78 ° C.
After the above cooling, 0.34 g of a 1 M solution of sec-butyllithium in cyclohexane and 0.83 g of dehydrated and degassed styrene were injected by a syringe and reacted for 30 minutes.
Subsequently, 0.25 g of tert-butyl chloroacetate which had been subjected to a degassing treatment was injected by a syringe as an end modifier for the polymer compound, and reacted for 15 minutes to obtain a reaction liquid.
The reaction solution was then warmed to room temperature, concentrated and diluted with 26 g of tert-butyl methyl ether. Subsequently, the organic layer was washed three times with 17 g of a 1% by mass aqueous hydrochloric acid solution and four times with 17 g of ultrapure water.
The organic layer after washing was concentrated to dryness to obtain 0.66 g of a precursor of polymer compound 3 in a yield of 80%.
0.66 g of the precursor of the obtained polymer compound 3 is dissolved in 6 g of propylene glycol monomethyl ether (PGME), 0.52 g of p-toluenesulfonic acid monohydrate is added, and reacted at 40 ° C. for 10 hours I got
Next, the reaction solution was warmed to room temperature, concentrated, diluted with 13 g of dichloromethane, and then the organic layer was washed three times with 13 g of a 1% by mass aqueous hydrochloric acid solution and four times with 13 g of ultrapure water.
The organic layer after washing was concentrated to dryness to obtain 0.53 g of the target polymer compound (polymer compound 3) in a yield of 80%.
With respect to the obtained polymer compound 3, as a result of GPC analysis, Mn was 1900, Mw was 2000, and Mw / Mn was 1.05. As a result of ¹³ C-NMR analysis, a peak of a primary carbon atom to which a COOH group is bound was confirmed at around 170 to 172 ppm. From the ratio of the integral value with the initiator end (18 to 20 ppm of CH ₃ ), the OH introduction rate to the end of the main chain was 77.0% (0.035 / 0.046 × 100 = 77.0) %).

<< Synthesis of Polymer Compound 4 >>
180 mg of lithium chloride was put into a dried 50 mL Schlenk tube, 39 g of low oxygen and low moisture grade tetrahydrofuran was put under an argon atmosphere, and cooled to -78 ° C.
After the above cooling, 0.34 g of a 1 M solution of sec-butyllithium in cyclohexane and 0.83 g of dehydrated and degassed styrene were injected by a syringe and reacted for 30 minutes.
Subsequently, 0.91 g of degassed 1,2-butylene oxide was injected by a syringe as an end modifier for the polymer compound, and reacted for 15 minutes to obtain a reaction liquid.
The reaction solution was then warmed to room temperature, concentrated and diluted with 26 g of tert-butyl methyl ether. Subsequently, the organic layer was washed three times with 17 g of a 1% by mass aqueous hydrochloric acid solution and four times with 17 g of ultrapure water.
The organic layer after washing was concentrated to dryness to obtain 0.62 g of the target polymer compound (polymer compound 3) in a yield of 75%.
With respect to the obtained polymer compound 4, as a result of GPC analysis, Mn was 1900, Mw was 2000, and Mw / Mn was 1.15. As a result of ¹³ C-NMR analysis, a peak of a quaternary carbon atom to which an OH group was bonded was confirmed at 69 to 70 ppm. From the ratio of the integral value with the initiator end (18 to 20 ppm of CH ₃ ), the OH introduction rate to the main chain end was 93.8% (0.061 / 0.065 × 100 = 93.8) %).

<Preparation of base agent>
(Examples 1 to 7, Comparative Examples 1 to 3)
Polymer compounds 3 to 4 were synthesized as described above. Moreover, the following high molecular compounds 1-2 were each synthesize | combined by well-known radical polymerization.
Subsequently, each of the polymer compounds 1 to 4 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare an undercoating agent (solid content concentration: 1.20% by mass) of each example.

In Tables 1 and 2, each abbreviation has the following meaning. The numerical values in [] are compounding amounts (parts by mass).
(A) -1: the following polymer compound 1. Copolymer composition ratio of said polymer compound (ratio of each constituent unit in polymer compound (molar ratio)) determined by ¹³ C-NMR, x / y = 93/7, standard polystyrene conversion determined by GPC measurement Mass average molecular weight (Mw) 5000, molecular weight dispersion degree (Mw / Mn) 1.05.
(A) -2: the following polymer compound 2. Copolymer composition ratio (ratio of constituent units in the polymer compound (molar ratio)) x / y / z = 80/14/6, as determined by ¹³ C-NMR Mass average molecular weight (Mw) 5000 in standard polystyrene conversion, molecular weight dispersion degree (Mw / Mn) 1.05.
(A) -3: the following polymer compound 3. Copolymer composition ratio of the polymer compound (proportion of each constitutional unit in the polymer compound (molar ratio)) determined by ¹³ C-NMR n = 100, mass average molecular weight in terms of standard polystyrene as determined by GPC ( Mw) 2000, molecular weight dispersity (Mw / Mn) 1.05.
(A) -4: the following polymer compound 4 Copolymer composition ratio of the polymer compound determined by ¹³ C-NMR (proportion of each constitutional unit in the polymer compound (molar ratio)) x = 100, mass average molecular weight in terms of standard polystyrene determined by GPC measurement Mw) 2000, molecular weight dispersity (Mw / Mn) 1.05.
(S) -1: propylene glycol monomethyl ether acetate (PGMEA).

<Manufacture of structure including phase separation structure>
[Step (i)]
Next, the base material of each example shown in Tables 1 and 2 is applied onto an 8-inch silicon wafer using a spinner, and baking is performed at a baking temperature and baking time shown in Tables 3 and 4 to dry the table. An undercoating layer was formed to a thickness as shown in 3-4.
The primer layer was rinsed with OK 73 thinner (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove random copolymer such as uncrosslinked portion. After this, it was baked at 250 ° C. for 60 seconds. After baking, the film thickness of the base agent layer formed on the organic antireflective film was 2 nm.

[Measurement of water contact angle on the surface of the base coat layer]
Water was dropped on the surface of the base layer, and contact angle (static contact angle) was measured using DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.) (measurement of contact angle: 2 μL of water). This measured value is shown in Tables 3 to 4 as "contact angle (°)".

[Step (ii)]
Next, a PS-PMMA block copolymer (PS / PMMA composition ratio (molar ratio) 55/45, Mw 42400, Mw / Mn 1.07, period 26 nm) so as to cover the undercoating layer formed on the organic antireflective film. The PGMEA solution (block copolymer concentration: 2% by mass) was spin-coated (rotational speed 1,500 rpm, 60 seconds).
Next, the substrate coated with the PGMEA solution of PS-PMMA block copolymer was baked at 90 ° C. for 60 seconds to be dried to form a PS-PMMA block copolymer layer with a film thickness of 30 nm.

[Step (iii)]
Next, the PS-PMMA block copolymer layer was phase-separated into a phase consisting of PS and a phase consisting of PMMA by annealing by heating at 210 ° C. for 300 seconds under a nitrogen stream to form a phase separation structure.

  As a result of the above, in any of the examples, a structure including a phase separation structure was produced on the base agent layer. When the foundation | coating agent of Examples 1-9 was used, the pattern in which the vertical cylinder shape and the horizontal cylinder shape were mixed all was formed. When the base agents of Comparative Examples 1 to 4 were used, vertical cylinder patterns were all formed.

[Step (iv)]
Perform oxygen plasma treatment (200 mL / min, 40 Pa, 40 ° C., 200 W, 20 seconds) on a silicon (Si) wafer with a phase separation structure formed using TCA-3822 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) The phase consisting of PMMA was selectively removed.

[Evaluation of phase separation performance]
Thereafter, the surface (phase separation state) of the obtained substrate was observed with a scanning electron microscope SEM (SU 8000, manufactured by Hitachi High-Technologies Corporation).
As a result of this observation, when a pattern in which the vertical cylinder shape and the horizontal cylinder shape were mixed was observed as ◎, and when only the vertical cylinder pattern was observed as x, the result is shown as “phase separation performance” in Tables 3 to 3. It showed to 4.
In this specification, the formation of the horizontal cylinder pattern indicates that it is an undercoating agent having higher affinity to the hydrophobic polymer block.

From the results shown in Tables 3 to 4, in the case of using the undercoating materials of Examples 1 to 9 to which the present invention is applied, the blocks are compared with the case of using the undercoating agents of Comparative Examples 1 to 3 outside the scope of the present invention. It can be confirmed that the phase separation performance of the copolymer is further enhanced.
In addition, in the production of a structure including a phase separation structure, the undercoating agents of Examples 1 to 9 are more compatible with the hydrophobic polymer block because the contact angle to water was large and the formation of a horizontal cylinder pattern was also confirmed. It was confirmed that it is a highly basic substrate.
In this Example, the base agent of the present invention is applied on a substrate, and the phase separation performance is tested when the block copolymer is applied on the base agent. The test is intended to test the affinity to the block copolymer, and does not impose any limitation on other uses of the primer. For example, the base agent of the present invention is coated on a substrate to form a base agent layer, a guide pattern is formed on the base agent layer using a resist composition or the like, and the base agent layer on which the guide pattern is formed. Also in the above, it is considered that the phase separation performance of the block copolymer can be improved as compared with the case of using the base material of Comparative Examples 1 to 4 outside the scope of the present invention.

DESCRIPTION OF SYMBOLS 1 ... board | substrate, 2 ... foundation | substrate agent layer, 3 ... layer, 3a ... phase, 3b ... phase.

Claims (3)

Formed on the substrate, a layer containing the block copolymer with the hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) is bonded to a base material which is used to phase separation,
A resin component is contained, and the resin component is at least selected from the group consisting of a polymer compound represented by the following general formula (A1-1) and a polymer compound represented by the following general formula (A2-1) Base agents , including one kind .

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ¹⁰ and R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a hydrocarbon group having 1 to 5 carbon atoms having a carboxy group. However, at least one of R ¹⁰ and R ²⁰ is a hydrocarbon group of 1 to 5 carbon atoms having a carboxy group. R ¹ is a halogen atom, or a hydrocarbon group of 1 to 20 carbon atoms which may contain an oxygen atom, a halogen atom or a silicon atom, and which is linear, branched or cyclic or a combination thereof. p is an integer of 0 to 5; x represents the number of repetitions of the constituent unit. ]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. R ³⁰ and ^{R 40} are independently a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms having a hydrocarbon group, or a carboxy group having 1 to 5 carbon atoms. However, at least one of R ³⁰ and R ⁴⁰ is a hydrocarbon group of 1 to 5 carbon atoms having a carboxy group. R ² is a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms. x represents the number of repetitions of the constituent unit. ] Applying the base agent according to claim 1 on a substrate to form a base agent layer;
Forming a layer comprising a block copolymer in which a hydrophobic polymer block (b11) and a hydrophilic polymer block (b21) are bonded on the undercoating layer;
Phase separating a layer containing the block copolymer;
A method for producing a structure including a phase separation structure, comprising: Wherein in the step of forming the base material layer, a substrate coated with undercoat agent, comprising the step of baking 6 0 seconds at 210 ° C. or higher, a manufacturing method of a structure that contains a phase separation structure according to claim 2 .

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