JP6325320B2 - Method for manufacturing structure including phase separation structure and method for forming topcoat film - Google Patents

Description

  The present invention relates to a method for manufacturing a structure including a phase separation structure and a method for forming a topcoat film.

In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), a technique for processing more delicate structures is required. In response to such a demand, attempts have been made to form a finer pattern using a phase separation structure formed by self-assembly of block copolymers in which incompatible blocks are bonded to each other. (For example, refer to Patent Document 1).
In order to utilize the phase-separated structure of the block copolymer, it is essential that the self-assembled nanostructure formed by microphase separation is formed only in a specific region and arranged in a desired direction. In order to realize these position control and orientation control, processes such as graphoepitaxy for controlling the phase separation pattern by the guide pattern and chemical epitaxy for controlling the phase separation pattern by the difference in the chemical state of the substrate have been proposed. (For example, refer nonpatent literature 1).

JP 2008-36491 A

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

Recently, a method of forming a layer containing a block copolymer and forming a topcoat film on the layer containing the block copolymer (hereinafter sometimes referred to as “TC process”) has been attempted.
In the TC process, a solvent in which the block copolymer is not dissolved, for example, a solvent containing water, is used as a solvent for the top coat material in order to prevent the underlying block copolymer from being dissolved during the formation of the top coat. .

In the case of forming a guide pattern, the surface of the top coat film is reduced in hydrophobicity because the surface of the guide pattern having low hydrophobicity and the surface of the block copolymer having high hydrophobicity are alternately present. The film formability is rarely a problem.
However, when the phase separation structure of the block copolymer is formed without forming the guide pattern, the top coat film is formed on the surface of the layer containing the highly hydrophobic block copolymer, and a solvent containing water is used. When used, a top coat film may not be formed. As described above, there has been a demand for a topcoat material having excellent film formability even when a guide pattern is not used.
This invention is made | formed in view of the said situation, and makes it a subject to provide the manufacturing method of the structure containing a phase-separation structure using the topcoat material excellent in film forming property.

The first aspect of the present invention includes a step of forming a layer containing a block copolymer on a support, a step of applying a topcoat material on the layer containing the block copolymer, and forming a topcoat film; A step of phase-separating the layer including the block copolymer on which the topcoat film is formed by thermal annealing, wherein the topcoat material includes a polymer compound including dicarboxylic acid or a salt of dicarboxylic acid, and an organic solvent component ( S), the organic solvent component (S) contains water and an alcohol, and the amount of the water is 0.5 to 3 times the amount of the alcohol. This is a method for manufacturing a structure including a phase separation structure.
The second aspect of the present invention includes a step of forming a layer containing a block copolymer on a support, a step of applying a topcoat material on the layer containing the block copolymer, and forming a topcoat film; The top coat material contains a polymer compound containing dicarboxylic acid or a salt of dicarboxylic acid, and an organic solvent component (S), and the organic solvent component (S) contains water and alcohol, The method for forming a topcoat film is characterized in that the amount of water is 0.5 to 3 times the amount of alcohol.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the structure containing a phase-separation structure using the topcoat material excellent in film forming property can be provided.

It is a general | schematic process drawing explaining one Embodiment of the manufacturing method of the structure containing the phase-separation structure which concerns on this invention. It is a schematic process drawing explaining one embodiment of the present invention.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are 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.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group And both.
“Exposure” is a concept including general irradiation of radiation.

“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid 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 acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) for substituting the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. An alkyl group etc. are mentioned. In addition, itaconic acid diesters in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group with a modified hydroxyl group thereof Shall be included. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group of acrylic acid is bonded unless otherwise specified.
Hereinafter, an acrylate 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 acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.

“Structural unit derived from acrylamide” means a structural unit formed by cleavage of the ethylenic double bond of acrylamide.
In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. The α-position carbon atom of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom bonded to the α-position carbon atom of acrylamide are the same as those described as the α-position substituent (substituent (R ^α0 )) in the α-substituted acrylic ester. Can be mentioned.

“A 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.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxy styrene of the hydroxystyrene which may be substituted with a substituent at the α-position is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent The thing etc. which the substituents other than a hydroxyl group couple | bonded with the benzene ring of good hydroxystyrene are mentioned. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.

The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The “vinyl benzoic acid derivative” is a concept including a compound in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom at the carboxy group of vinyl benzoic acid, which may be substituted with a hydrogen atom at the α-position, is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.

The “styrene derivative” is a concept including those in which a hydrogen atom at the α-position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from 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, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. 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.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

≪Method for producing structure including phase separation structure≫
The present invention includes a step of forming a layer containing a block copolymer on a support, a step of applying a topcoat material on the layer containing the block copolymer to form a topcoat film, and the topcoat film comprising: A step of phase-separating the formed layer containing the block copolymer by thermal annealing, and the top coat material contains a polymer compound containing dicarboxylic acid or a salt of dicarboxylic acid, and an organic solvent component (S). The organic solvent component (S) contains water and alcohol, and the amount of the water is 0.5 times or more of the amount of the alcohol, and the structure including a phase separation structure It is a manufacturing method of a body.

[Step of forming a layer containing a block copolymer on a support]
<Support>
First, the support body 1 is prepared (FIG. 1 (a)).
If the support body 1 can apply | coat the solution containing a photosensitive resin film or a block copolymer on the surface, the kind will not be specifically limited. For example, metals such as silicon, copper, chromium, iron, and aluminum, substrates made of inorganic materials such as glass, titanium oxide, silica, and mica, substrates made of organic compounds such as acrylic plates, polystyrene, cellulose, cellulose acetate, and phenol resins Is mentioned.
Moreover, the magnitude | size and shape of the support body 1 used in this invention are not specifically limited. The support 1 does not necessarily have a smooth surface, and substrates of various materials and shapes can be appropriately selected. For example, a substrate having a curved surface, a flat plate having an uneven surface, and a substrate having various shapes such as a flake shape can be used.

  In addition, an inorganic and / or organic film may be provided on the surface of the support 1. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC).

When forming a neutralization film (not shown) on the support 1, the surface of the support may be washed. By washing the surface of the support, the subsequent neutralization film forming step may be performed satisfactorily.
As the cleaning treatment, conventionally known methods can be used, and examples thereof include oxygen plasma treatment, hydrogen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment. For example, the substrate is immersed in an acid solution such as sulfuric acid / hydrogen peroxide solution, washed with water, and dried. Thereafter, a layer containing a block copolymer can be formed on the surface of the substrate.

<Block copolymer>
Block copolymer In the present invention, the block copolymer is a polymer in which a plurality of partial constituent components (blocks) in which only structural units of the same kind are bonded. In the present invention, it is preferable to use one containing a Si-containing block. There may be two types of blocks constituting the block copolymer, or three or more types. In the present invention, the plurality of types of blocks constituting the block copolymer are not particularly limited as long as they are combinations that cause phase separation, but are preferably combinations of Si-containing blocks and non-Si-containing blocks. A combination of blocks that are incompatible with each other is preferable. Moreover, it is preferable that the phase which consists of at least 1 type block in the multiple types of block which comprises a block copolymer is a combination which can be selectively removed easily rather than the phase which consists of other types of block. Combinations that can be easily and selectively removed include block copolymers in which one or more blocks having an etching selectivity ratio of greater than 1 are combined.

In the present invention, the “period of the block copolymer” means the period of the phase structure observed when the phase-separated structure is formed, and is the sum of the lengths of the phases that are incompatible with each other. The period of the block copolymer corresponds to the length of one molecule of the block copolymer.
The period of the block copolymer depends on the intrinsic polymerization characteristics such as the degree of polymerization N and the Flory-Huggins interaction parameter χ. That is, the greater the “χN”, the greater the repulsion between different blocks in the block copolymer. For this reason, when χN> 10 (hereinafter referred to as “strength separation limit point”), the repulsion between different types of blocks in the block copolymer is large, and the tendency of phase separation to increase. At the intensity separation limit point, the period of the block copolymer is approximately N ^2/3 χ ^1/6 . That is, the period of the block copolymer is proportional to the degree of polymerization N that correlates with the molecular weight Mn and the molecular weight ratio between different blocks. Therefore, the period of the block copolymer can be easily adjusted by adjusting the composition and the total molecular weight of the block copolymer used.

[Si-containing block]
The Si-containing block that is preferably used in the present invention will be described.
The Si-containing block is not particularly limited as long as it is a block of a structural unit having Si. For example, it is derived from a structural unit represented by the following general formula (a00-1) or (a00-2), siloxane, or a derivative thereof. And a cage-type silsesquioxane (POSS) structure-containing structural unit described later.

［式（ａ００−１）又は（ａ００−２）中、Ｌａ^１は単結合又はヘテロ原子を有していてもよい２価の連結基であり、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立に、水素原子又は炭素数１〜５のアルキル基であり、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り、Ｙａ^１は単結合又は２価の連結基である。］

[In Formula (a00-1) or (a00-2), La ¹ is a divalent linking group optionally having a single bond or a hetero atom, and R ¹ , R ² , and R ³ are each independently , A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya ¹ is a single bond or a divalent group. The linking group of ]

In Formula (a00-1), La ¹ is a divalent linking group that may have a single bond or a hetero atom.

(Divalent linking group optionally having a hetero atom in La ¹ )
The hetero atom in the divalent linking group which may have a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

When La ¹ is a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, —O—C. (═O) —O—, —C (═O) —NH—, —NH—, —NH—C (═NH) — (H may be substituted with a substituent such as an alkyl group or an acyl group). _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - C (═O) —O—, —C (═O) —O—Y ²¹ , — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (= O) a group represented by —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, m 'is an integer of 0-3. ] Etc. are mentioned.
When the divalent linking group containing a hetero atom is —C (═O) —NH—, —NH—, —NH—C (═NH) —, H is a substituent such as an alkyl group or acyl. May be substituted. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² each independently have a substituent. It is also a good divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group optionally having substituent (s)” mentioned in the description of the divalent linking group.
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² —, m ′ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.
In La ¹ , the hetero atom is preferably an oxygen atom. In the present invention, La ¹ is a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. Preferably there is.

In formula (a00-1) or (a00-2), R ¹ , R ² , and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. In the present invention, R ¹ , R ² and R ³ are preferably methyl groups.

In formula (a00-2), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, Examples include propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms 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 halogen atoms. 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.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

In formula (a00-2), Ya ¹ is a single bond or a divalent linking group. Although it does not specifically limit as a bivalent coupling group, The bivalent hydrocarbon group which may have a substituent, the bivalent coupling group containing a hetero atom, etc. are mentioned as a suitable thing.

(Divalent hydrocarbon group optionally having a substituent in Ya ¹ )
The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in the structure.

  The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (excluding two hydrogen atoms from the aliphatic hydrocarbon ring) Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a linear or branched chain fatty acid. Group intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O— are preferable.

Specifically, the aromatic hydrocarbon group as the divalent hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, more preferably 5 to 20, 6 to 15 is particularly preferable, and 6 to 10 is most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are heterogeneous. Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) ) In which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) Group in which one hydrogen atom is further removed from the aryl group in the group); and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

(Divalent linking group containing a hetero atom)
The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

When Ya ¹ is a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, and —O—C. (═O) —O—, —C (═O) —NH—, —NH—, —NH—C (═NH) — (H may be substituted with a substituent such as an alkyl group or an acyl group). _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - C (═O) —O—, —C (═O) —O—Y ²¹ , — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (= O) a group represented by —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, m 'is an integer of 0-3. ] Etc. are mentioned.
When the divalent linking group containing a hetero atom is —C (═O) —NH—, —NH—, —NH—C (═NH) —, H is a substituent such as an alkyl group or acyl. May be substituted. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² each independently have a substituent. It is also a good divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group optionally having substituent (s)” mentioned in the description of the divalent linking group.
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² —, m ′ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

Ya ¹ in the present invention is a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. It is preferable.

  Specific examples of the structural unit represented by the formula (a00-1) or (a00-2) are shown below.

  As the block copolymer, for example, a block copolymer in which a block of a structural unit not containing Si and a block of a structural unit containing Si are combined: a block of a structural unit derived from an (α-substituted) acrylate ester; A block copolymer in which a block of a structural unit containing Si is bonded; a block copolymer in which a block of a structural unit derived from (α-substituted) acrylic acid and a block of a structural unit containing Si are combined A block copolymer obtained by combining a block of a structural unit containing Si and a block of a structural unit derived from polyethylene oxide; a block of a structural unit containing Si and a block of a structural unit derived from polypropylene oxide; And a block copolymer in which Si is contained. A block copolymer obtained by bonding a block of a constituent unit and a block of a constituent unit derived from polylactic acid; a block of a constituent unit having an aromatic group; and a block of a constituent unit derived from siloxane or a derivative thereof; A block copolymer in which a block of a cage-type silsesquioxane structure-containing structural unit and a block of a structural unit derived from an (α-substituted) acrylate ester are combined; a cage-type silsesquioxy A block copolymer comprising a block of a sun structure-containing structural unit and a block of a structural unit derived from (α-substituted) acrylic acid; a block of a cage-type silsesquioxane structure-containing structural unit and a siloxane or a derivative thereof Block copolymer obtained by combining a block of a structural unit derived from I can get lost.

  In the present invention, the block copolymer preferably includes a structural unit having an aromatic group and a structural unit containing Si among the above.

Examples of the structural unit having an aromatic group include structural units having an aromatic group such as a phenyl group and a naphthyl group. In the present invention, a structural unit derived from styrene or a derivative thereof is preferable.
Examples of styrene or derivatives thereof include α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethyl. Styrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, 4-vinylbenzyl chloride 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, vinylpyridine and the like.

The (α-substituted) acrylic acid means one or both of acrylic acid or one in which a hydrogen atom bonded to a carbon atom at the α-position in acrylic acid is substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
Examples of (α-substituted) acrylic acid include acrylic acid and methacrylic acid.

The (α-substituted) acrylate ester means one or both of the acrylate ester or the hydrogen atom bonded to the α-position carbon atom in the acrylate ester substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
Examples of (α-substituted) acrylate esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, and acrylic acid. Acrylic acid esters such as hydroxyethyl, 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 Mud propyl, benzyl methacrylate, anthracene, glycidyl methacrylate, 3,4-epoxycyclohexyl methane, and the like methacrylic acid esters such as methacrylic acid propyl trimethoxy silane.
Among these, methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and t-butyl methacrylate are preferable.

Examples of siloxane or derivatives thereof include dimethylsiloxane, diethylsiloxane, diphenylsiloxane, and methylphenylsiloxane.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, isopropylene oxide, butylene oxide and the like.

  Examples of the cage-type silsesquioxane (POSS) structure-containing structural unit include structural units represented by the following general formula (a0-1).

［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を表す。Ｖ^０は置換基を有していてもよい２価の炭化水素基を表す。Ｒ^０は置換基を有していてもよい１価の炭化水素基を表し、複数のＲ^０はそれぞれ同じであってもよく異なっていてもよい。］

[Wherein, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. V ⁰ represents a divalent hydrocarbon group which may have a substituent. R ⁰ represents a monovalent hydrocarbon group which may have a substituent, and a plurality of R ⁰ may be the same or different. ]

In the formula (a0-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically a methyl group or an ethyl group. Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms 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 halogen atoms. 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.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

In the formula (a0-1), the monovalent hydrocarbon group for R ⁰ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. However, the carbon number does not include the carbon number in the substituent described later.
The monovalent hydrocarbon group for R ⁰ may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and particularly preferably an aliphatic hydrocarbon group. It is more preferably an aliphatic saturated hydrocarbon group (alkyl group).
More specifically, examples of the alkyl group include a chain aliphatic hydrocarbon group (a linear or branched alkyl group) and an aliphatic hydrocarbon group having a ring in the structure.
The linear alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, and an n-propyl group are preferable, a methyl group, an ethyl group, or an isobutyl group is more preferable, an ethyl group or an isobutyl group is further preferable, and an ethyl group is particularly preferable.
The branched alkyl group preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and the like, and an isopropyl group or a tert-butyl group is most preferable.
Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group is the chain described above. Examples thereof include a group bonded to the terminal of a chain-like aliphatic hydrocarbon group or a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of the chain-like aliphatic hydrocarbon group described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, more preferably 4 to 6 carbon atoms, and may be a polycyclic group or a monocyclic group. . As the monocyclic group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, And tetracyclododecane.

The chain-like aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).
The cyclic aliphatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, and an oxygen atom (= O).

When the monovalent hydrocarbon group in R ⁰ is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a monovalent hydrocarbon group having at least one 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. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent described later.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); an aromatic compound containing two or more aromatic rings A group in which one hydrogen atom is removed from (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl groups such as 2-naphthylethyl group) and the like.
The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

In the formula (a0-1), the divalent hydrocarbon group for V ⁰ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
The aliphatic hydrocarbon group as the divalent hydrocarbon group for V ⁰ may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group 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. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent described later.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); 1 of the hydrogen atoms of a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring A group substituted with an alkylene group (for example, an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) A group in which one atom is further removed).
The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Specific examples of the structural unit represented by the formula (a0-1) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

In the present invention, the molar ratio between the structural unit not containing Si and the structural unit containing Si is preferably 50:50 to 70:30, and more preferably 60:40 to 65:35. .
When the proportion of the structural unit derived from the structural unit having an aromatic group, (α-substituted) acrylic acid, or (α-substituted) acrylic ester is within the above preferred range, it is perpendicular to the support surface. An oriented cylindrical phase separation structure is easily obtained.

  Specific examples of such a block copolymer include a block copolymer having a styrene block and a Si-containing block, a block copolymer having a cage-type silsesquioxane (POSS) structure-containing structural unit block and an acrylic acid block, and a cage. And block copolymers having a block of a structural unit containing a silsesquioxane (POSS) structure and a block of methyl acrylate.

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of each polymer constituting the block copolymer is not particularly limited as long as it is a size capable of causing phase separation. To 50,000,000 are preferable, 5,000 to 400,000 are more preferable, and 5,000 to 300,000 are more preferable.
Further, the 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 1.3. In addition, Mn shows a number average molecular weight.

  In addition to the block copolymer described above, the composition containing the block copolymer may further contain, if desired, miscible additives, for example, an additional resin for improving the performance of the layer made of the neutralized film, and coatability. A surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base proliferating agent, a basic compound, and the like can be added and contained as appropriate.

-Organic solvent The composition containing a block copolymer can be prepared by dissolving the block copolymer in an organic solvent. Any organic solvent may be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, an arbitrary solvent can be selected from among known solvents for resin-based film compositions. One or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Monohydric alcohols; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl of the polyhydric alcohols or compound having the ester bond Ether alkyl such as ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having a propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) among these]; 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, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, Aromatic organics such as dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene A solvent etc. can be mentioned.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and EL are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Within range. For example, when EL is blended 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, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3. Further, when PGME and cyclohexanone are blended as polar solvents, the mass ratio of PGMEA: (PGME + cyclohexanone) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3. : 7 to 7: 3.

In addition, as the organic solvent in the composition containing the block copolymer, PGMEA, EL, or a mixed solvent of PGMEA and a polar solvent and a mixed solvent of γ-butyrolactone are also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of the organic solvent used in the composition containing the block copolymer is not particularly limited, and can be appropriately set according to the coating film thickness at a coatable concentration. Is used in such a manner that the solid content concentration is 0.2 to 70% by mass, preferably 0.2 to 50% by mass.

In the following, among the blocks constituting the block copolymer, P _A block (Fig optional step the blocks that are not selectively removed in block P _B (2b in FIG. 1), a block that is selectively removed after 2a) in 1. For example, after phase-separating a layer containing a PS-Si-containing block copolymer, the phase composed of the Si-containing block is selectively removed by performing oxygen plasma treatment, hydrogen plasma treatment, or the like on the layer. In this case, PS is a block _{P B} is a Si-containing block _{P A} block.

In the present invention, the shape and size of the phases is selectively removed (i.e., phase consisting block P _A), the volume fraction of each block constituting the block copolymer and is defined by the molecular weight of the block copolymer. For example, by a relatively small volume fraction of P _A block occupied in the block copolymer, it is possible to form a cylindrical structure phase consisting P _A block phase in consisting of P _B block is present in the cylindrical . On the other hand, by the volume fraction of the block P _A and P _B blocks occupying the block copolymer to the same extent, the lamellar structure in which a phase of phase and P _A block consisting of block P _B are alternately laminated Can be formed. In addition, the size of each phase can be increased by increasing the molecular weight of the block copolymer.

[Step of applying top coat material on layer containing block copolymer to form top coat film]
The present invention provides a top coat film forming step of forming a top coat film by applying a top coat material on the layer containing a block copolymer after the above [step of forming a layer containing a block copolymer on a support]. Have
In the top coat film forming step, for example, as shown in FIG. 1C, a top coat material 3 may be formed by applying a top coat material on the layer 2 containing a block copolymer to form a top coat film. .

In the topcoat film formation step, a topcoat film is formed by applying a polymer compound containing dicarboxylic acid or a salt of dicarboxylic acid and a topcoat material containing an organic solvent component (S) on the layer containing the block copolymer. To do.
By providing the topcoat film 3 using the topcoat material on the layer 2 containing the block copolymer, the surface state of the layer can be well controlled and phase separation can be performed more stably.
In the present invention, the top coat film 3 can be formed, for example, by applying the top coat material onto the layer 2 containing the block copolymer using a spinner or the like. After the application, a baking process may be performed. At that time, the heating temperature is preferably 80 to 280 ° C., and the heating time is preferably 10 to 600 seconds.
The thickness of the topcoat film 3 formed on the layer 2 containing the block copolymer is preferably 2 to 500 nm, more preferably 5 to 200 nm, and still more preferably 10 to 100 nm. . When the thickness of the top coat film 3 is within the above preferable range, the influence of the external environment can be sufficiently blocked, and phase separation is more likely to occur.

  As the top coat material, the following top coat material can be used. In the present invention, as will be described later, the topcoat material contains a polymer compound containing dicarboxylic acid or a salt of dicarboxylic acid, and an organic solvent component (S), and the organic solvent component (S) contains water and It contains alcohol, and the compounding quantity of the water is 0.5 times or more of the compounding quantity of the alcohol.

≪Topcoat material≫
The topcoat material used in the method for producing a structure including the phase separation structure of the present invention and the topcoat material preferably used will be described.
In the present invention, the topcoat material contains a polymer compound having a structural unit (Tc1) containing dicarboxylic acid or a salt of dicarboxylic acid, and an organic solvent component (S), and the organic solvent component (S) contains water and It contains alcohol and the amount of the water is 0.5 times or more the amount of the alcohol (hereinafter also referred to as “topcoat material (1)”).
The topcoat material of the present invention includes a polymer compound having a structural unit (Tc1) containing dicarboxylic acid or a salt of dicarboxylic acid and a structural unit (Tc2) for controlling the surface energy of the layer containing the block copolymer. And the organic solvent component (S) contains water and an alcohol, and the amount of the water is 0.5 times or more the amount of the alcohol (hereinafter referred to as “topcoat material (2)”. ) ")).
Furthermore, the polymer compound which has the structural unit (Tc1) containing dicarboxylic acid or the salt of dicarboxylic acid, the surface energy control agent which controls the surface energy of the layer containing the said block copolymer, and an organic solvent component (S) are contained. It may be a top coat material.

"Topcoat material (1)"
(Polymer compound)
The polymer compound used for the topcoat material (1) has a structural unit (Tc1) containing dicarboxylic acid or a salt of dicarboxylic acid.
By having the structural unit (Tc1), the surface energy of the layer containing the block copolymer can be maintained at an appropriate height during phase separation.
Examples of the “structural unit containing dicarboxylic acid or dicarboxylic acid” include structural units represented by the following chemical formulas.
The structural unit represented by the chemical formula (Tc1-1) is a structural unit whose polarity increases in the presence of a basic component. The structural units represented by the chemical formulas (Tc1-2) and (Tc1-3) are structural units whose polarity decreases by heating.

The structural unit (Tc1) possessed by the polymer compound may be one type or two or more types.
As to which of the structural units represented by (Tc1-1) to (Tc1-3) should be selected as the structural unit (Tc1), the type of block copolymer and the degree of surface energy of the layer containing the block copolymer It is determined as appropriate.
Among the structural units (Tc1), it is preferable to use the structural unit represented by the chemical formula (Tc1-2) or the structural unit represented by the chemical formula (Tc1-3).
The proportion of the structural unit (Tc1) in the polymer compound is preferably 10 to 90 mol%, more preferably 30 to 80 mol%, and more preferably 40 to 80 mol% with respect to all the structural units constituting the polymer compound. Further preferred.
By setting the proportion of the structural unit (Tc1) within the above preferred range, the surface energy of the layer containing the block copolymer can be easily maintained at an appropriate height during phase separation.

In the present invention, the topcoat material contains an organic solvent component (S).
<Organic solvent component (S)>
In the present invention, the organic solvent component (hereinafter sometimes referred to as “component (S)”) contains water and alcohol, and the blending amount of the water is 0% of the blending amount of the alcohol. .5 times or more.
The blending ratio of water and alcohol may be such that the blending amount of water is the same as the blending amount of alcohol, and the blending amount of water is preferably three times or more of the blending amount of alcohol.

In this invention, it does not specifically limit as alcohol which (S) component contains, It can select suitably.
In the present invention, for example, a water-soluble alcohol is preferable, and more specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, 3-methoxy-1-propanol, 3-methoxy-3-methylbutanol. , T-butanol.
In the present invention, one or more of the above may be appropriately selected and used. In the present invention, it is preferable to select methyl alcohol, ethyl alcohol or isopropyl alcohol.

The polymer compound used for the topcoat material (1) may have a structural unit other than the structural unit (Tc1).
Examples of the structural unit other than the structural unit (Tc1) include a structural unit (Tc2) that controls the surface energy of the layer containing the block copolymer, and a structural unit (Tc3) that adjusts the glass transition temperature (Tg).

・ Structural unit (Tc2)
The structural unit (Tc2) is a structural unit that controls the surface energy of the layer containing the block copolymer.
By having the structural unit (Tc2), it is possible to control the surface energy of the layer containing the block copolymer so as to have an appropriate height during phase separation.

  The structural unit (Tc2) may be any unit that can adjust the polarity of the polymer compound having the structural unit (Tc1). The structural unit represented by the following general formula (Tc2-1), the general formula (Tc2) -2) and at least one selected from the group consisting of the structural unit represented by formula (Tc2-3) is preferred.

［式中、ｘ１は、０又は１である。Ｒ^１はフッ素原子、又は、フッ素原子もしくは酸素原子を含んでいてもよい炭化水素基を表す。ｘ２は、０〜４の整数である。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を表す。複数のＲはそれぞれ同じであってもよく異なっていてもよい。Ｒ^２は、フッ素原子、又は、フッ素原子もしくは酸素原子を含んでいてもよい炭化水素基を表す。ｙは、０〜３の整数である。Ｒ^３は、置換基で置換されていてもよい炭化水素基を表す。Ｒ^３における置換基は、フッ素原子、又は、フッ素原子もしくは酸素原子を含んでいてもよい炭化水素基である。］

[Wherein x1 is 0 or 1; R ¹ represents a fluorine atom or a hydrocarbon group which may contain a fluorine atom or an oxygen atom. x2 is an integer of 0-4. R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. A plurality of R may be the same or different. R ² represents a fluorine atom or a hydrocarbon group that may contain a fluorine atom or an oxygen atom. y is an integer of 0-3. R ³ represents a hydrocarbon group which may be substituted with a substituent. The substituent in R ³ is a fluorine atom or a hydrocarbon group that may contain a fluorine atom or an oxygen atom. ]

In the formula (Tc2-1), x1 is 0 or 1.
x2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1.

In the formula (Tc2-1), R ¹ represents a fluorine atom, or a hydrocarbon group that may contain a fluorine atom or an oxygen atom. The hydrocarbon group for R ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and is preferably a monovalent aliphatic saturated group. It is more preferably a hydrocarbon group (alkyl group).
More specifically, examples of the alkyl group include a chain aliphatic hydrocarbon group (a linear or branched alkyl group) and an aliphatic hydrocarbon group having a ring in the structure.
The linear alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group or an ethyl group is particularly preferable.
The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms.
Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group is the chain described above. Examples thereof include a group bonded to the terminal of a chain-like aliphatic hydrocarbon group or a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of the chain-like aliphatic hydrocarbon group described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, more preferably 4 to 6 carbon atoms, and may be a polycyclic group or a monocyclic group. . As the monocyclic group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, And tetracyclododecane.

The chain-like aliphatic hydrocarbon group or the cyclic aliphatic hydrocarbon group may contain a fluorine atom or an oxygen atom, respectively. That is, the hydrogen atom of the aliphatic hydrocarbon group may be substituted with a fluorine atom. Alternatively, the methylene group (—CH ₂ —) of the aliphatic hydrocarbon group may be substituted with an oxygen atom (—O—) or a carbonyl group (—C (═O) —).

When the monovalent hydrocarbon group in R ¹ is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a monovalent hydrocarbon group having at least one 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. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent described later.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); an aromatic compound containing two or more aromatic rings A group in which one hydrogen atom is removed from (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl groups such as 2-naphthylethyl group) and the like.
The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may contain a fluorine atom or an oxygen atom. That is, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a fluorine atom. Alternatively, the methylene group (—CH ₂ —) of the aromatic hydrocarbon group may be substituted with an oxygen atom (—O—) or a carbonyl group (—C (═O) —).

In the above formulas (Tc2-2) and (Tc2-3), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The plurality of R may be the same or different.
The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms 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 halogen atoms. 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.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

In the formula (Tc2-2), examples of R ² include the same as R ¹ in the formula (Tc2-1).
y is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and particularly preferably 1.

In the formula (Tc2-3), R ³ represents a hydrocarbon group which may be substituted with a substituent.
Examples of the hydrocarbon group for R ³ include the same hydrocarbon groups as those for R ¹ in the formula (Tc2-1).
The substituent in R ³ is a fluorine atom, or a hydrocarbon group that may contain a fluorine atom or an oxygen atom, and examples thereof include the same groups as those for R ¹ in the formula (Tc2-1).

Specific examples of the structural unit represented by the formula (Tc2-1) are shown below.
In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbon group which may contain a fluorine atom. Examples of the hydrocarbon group for R ¹¹ include the same hydrocarbon groups as those for R ¹ in formula (Tc2-1). In the following chemical formula, the wavy line means both “wedge-type bond” and “dashed-line bond”.

Specific examples of the structural unit represented by the formula (Tc2-2) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.
In the formula, R ¹² represents a hydrogen atom or a hydrocarbon group which may contain a fluorine atom. Examples of the hydrocarbon group for R ¹² include the same hydrocarbon groups as those for R ¹ in the formula (Tc2-1).

Specific examples of the structural unit represented by the formula (Tc2-3) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.
In the formula, R ¹³ represents a hydrogen atom or a hydrocarbon group which may contain a fluorine atom. As the hydrocarbon group for R ^13, the same hydrocarbon groups as those for R ¹ in formula (Tc2-1) can be used.

The structural unit (Tc2) possessed by the polymer compound may be one type or two or more types.
Among the structural units (Tc2), the structural unit represented by the general formula (Tc2-1), the structural unit represented by the general formula (Tc2-2), and the general formula (Tc2-3) It is preferable to use at least one selected from the group consisting of structural units,
It is more preferable to use at least one selected from the group consisting of a structural unit represented by the general formula (Tc2-1) and a structural unit represented by the general formula (Tc2-2).
The proportion of the structural unit (Tc2) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 70 mol%, more preferably from 20 to 60 mol%, based on all the structural units constituting the polymer compound. Further preferred.
By setting the proportion of the structural unit (Tc2) within the above preferred range, the surface energy of the layer containing the block copolymer can be easily controlled.

The polymer compound used for the topcoat material (2) may have a structural unit other than the structural unit (Tc1) and the structural unit (Tc2).
Examples of the structural unit other than the structural unit (Tc1) and the structural unit (Tc2) include a structural unit (Tc3) that adjusts the glass transition temperature (Tg).

In the topcoat material (2), the polymer compound having the structural unit (Tc1) and the structural unit (Tc2) may be used alone or in combination of two or more.
The polymer compound used for the topcoat material (2) is a copolymer having at least a structural unit (Tc1) and a structural unit (Tc2).
As such a copolymer, specifically, a copolymer having a repeating structure of a structural unit represented by the chemical formula (Tc1-2) and a structural unit represented by the general formula (Tc2-1). A copolymer having a repeating structure of the structural unit represented by the chemical formula (Tc1-2) and the structural unit represented by the general formula (Tc2-2); represented by the chemical formula (Tc1-2); A copolymer having a repeating structure of the structural unit represented by the general formula (Tc2-3); a structural unit represented by the chemical formula (Tc1-2); A copolymer having a repeating structure of a structural unit represented by Tc2-1) and a structural unit represented by the general formula (Tc2-2); a structural unit represented by the chemical formula (Tc1-2) A structural unit represented by the general formula (Tc2-1), and the one A structural unit represented by the formula (Tc2-3) and a copolymer having a repeating structure; a structural unit represented by the chemical formula (Tc1-2), and a general formula (Tc2-2). A copolymer having a repeating structure of a structural unit and the structural unit represented by the general formula (Tc2-3); a structural unit represented by the chemical formula (Tc1-1); and the general formula (Tc2- And a copolymer having a repeating structure of the structural unit represented by 1) and the structural unit represented by the general formula (Tc2-2). Among these, the structural unit represented by the chemical formula (Tc1-1), the structural unit represented by the general formula (Tc2-1), and the structural unit represented by the general formula (Tc2-2) A copolymer having a repeating structure is more preferable.

Below, the suitable specific example of the high molecular compound used for topcoat material (2) is shown.
^Wherein, R ^1, R 2, ^{R 3} and y, the equation (Tc2-1) are respectively similar to ^{R 1,} R 2, ^{R 3} and y in ~ (Tc2-3).
In the formula, R ^1a and R ^1b are each independently the same as R ¹ in the formula (Tc2-1).
R ^2a and R ^2b are each independently the same as R ² in the formula (Tc2-2).
y ₁ and y ₂ are each independently the same as y in the formula (Tc2-2).
R ^3a and R ^3b are each independently the same as R ³ in the formula (Tc2-3).
Further, R ^α is the same as described above.

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the polymer compound used for the top coat material (2) is not particularly limited, and preferably 1000 to 50000. -30000 is more preferable, and 2000-30000 is most preferable. If it exists in the said preferable range, it has sufficient solubility with respect to a solvent.
The molecular weight dispersity (Mw / Mn) of the polymer compound is not particularly limited, and is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and most preferably 1.0 to 4.0. preferable.

The polymer compound is obtained by polymerizing a monomer for deriving each structural unit by known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate. Can do.
The content of the polymer compound in the topcoat material (2) may be adjusted according to the topcoat film thickness to be formed. In the top coat material (2), the concentration of the polymer compound is preferably 0.1 to 15% by mass, more preferably 0.2 to 7% by mass.

(Surface energy control agent)
In addition to the polymer compound having the structural unit (Tc1), the topcoat material (1) has the surface energy of the layer containing the block copolymer in the above-described << method for producing a structure containing a phase separation structure >>. You may contain the surface energy control agent to control.
By containing the surface energy control agent, the surface energy of the layer containing the block copolymer can be controlled to an appropriate height at the time of phase separation.

Examples of the surface energy control agent include a component (crosslinking agent) that forms a chemical bond between polymer compounds in the top coat material and within the polymer compound by heating.
Specific examples of the surface energy control agent include cross-linking agents such as diamine and triamine. Among them, diamine or triamine is more preferably used, and diamine is particularly preferably used.
As the amine, ammonia, trimethylamine, N, N-dimethylethanamine, N-ethyl-N methylethanamine, triethylamine, pyridine, 1-methylpiperidine, tripropylamine, or the like may be employed.

  Specific examples suitable for the surface energy control agent are shown below.

In the topcoat material (1), the surface energy control agent may be used alone or in combination of two or more.
In the topcoat material (1), the content of the surface energy control agent is preferably 2 to 500 parts by mass, more preferably 5 to 300 parts by mass with respect to 100 parts by mass of the polymer compound.
If the content of the surface energy control agent is at least the preferred lower limit, the surface energy of the layer containing the block copolymer can be easily controlled. On the other hand, if it is below the preferable upper limit value, the film formability becomes better.

[Step of phase-separating a layer containing a block copolymer on which a top coat film is formed by thermal annealing]
In the phase separation process, the layer 2 including the block copolymer on which the top coat film 3 is formed is phase-separated by thermal annealing (FIG. 1D).
In the present invention, the thermal annealing specifically heats the support on which the layer containing the block copolymer is formed. The heating temperature is preferably higher than the glass transition temperature of the block copolymer to be used and lower than the thermal decomposition temperature. In this embodiment, the heating temperature is preferably 100 to 300 ° C, more preferably 120 to 280 ° C. The heating time is preferably 0.5 to 1440 minutes, and more preferably 1 to 600 minutes. The heating is preferably performed in a gas having low reactivity such as nitrogen.
Thus, the layer containing the block copolymer is phase-separated by thermal annealing of the layer containing the block copolymer (2a and 2b in FIG. 1 (d)). As a result, a structure having a phase separation structure (preferably a lamellar or cylindrical phase separation structure oriented in a direction perpendicular to the support surface) on the support surface is produced.

[Neutralization film forming process]
In the present invention, before the [step of forming a layer containing a block copolymer], a neutralized film (not shown) containing a surface treatment agent is formed on the support (neutralizing the substrate). ) And [neutralizing film forming step].
The neutralization treatment is a treatment for modifying the substrate surface so as to have an affinity with any block constituting the block copolymer. By performing the neutralization treatment, it is possible to suppress only the phase composed of a specific block from coming into contact with the substrate surface by phase separation. In view of this point, in order to form a phase separation structure (preferably, a lamellar or cylindrical phase separation structure oriented in a direction perpendicular to the substrate surface) by phase separation, a block copolymer is used. Before forming the layer to be included, it is preferable to form a neutralized film on the surface of the substrate in accordance with the type of block copolymer to be used.

Specifically, a thin film (neutralized film) containing a surface treatment agent having affinity with any block constituting the block copolymer is formed on the surface of the support 1. The neutralized film can be formed, for example, by applying a surface treatment agent on the substrate.
Before forming the neutralized film on the support 1, the surface of the support 1 may be washed. By cleaning the surface of the support 1, there may be a case where a subsequent neutralized film can be satisfactorily formed.
As a cleaning method, a conventionally known method can be used, and examples thereof include oxygen plasma treatment, hydrogen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment. As an example, there is a method in which a substrate is immersed in an acid solution such as sulfuric acid / hydrogen peroxide aqueous solution, then washed with water and dried.

The neutralized film can be formed by using a resin composition as a surface treatment agent.
Such a resin composition can be appropriately selected from conventionally known resin compositions used for thin film formation according to the type of block constituting the block copolymer.
The resin composition used as the surface treatment agent may be a heat-polymerizable resin composition or a photosensitive resin composition such as a positive resist composition or a negative resist composition. In addition, a non-polymerizable film formed by applying a compound as a surface treating agent and applying the compound may be used as a neutralized film. For example, a siloxane-based organic monomolecular film formed using phenethyltrichlorosilane, octadecyltrichlorosilane, hexamethyldisilazane, or the like as a surface treatment agent can also be suitably used as the neutralization film.

Examples of such a surface treatment agent include a resin composition containing a resin having all the constituent units of each block constituting the block copolymer, and a constituent unit having high affinity with each block constituting the block copolymer. And a resin composition containing a resin having a polarity close to the average value of the polarities of all the blocks constituting the block copolymer.
For example, when using a block copolymer having a styrene block together with the structural unit (a00-1) or (a00-2), a resin composition containing a resin having methyl methacrylate as a structural unit as a surface treatment agent, It is preferable to use a compound or composition having both a site having a high affinity for the styrene structure and a site having a high affinity for the structural unit (a00-1) or (a00-2).
Sites with high affinity for methyl methacrylate include polar groups such as trimethoxysilyl group, trichlorosilyl group, carboxy group, hydroxyl group, cyano group, and hydroxyalkyl group in which part of the hydrogen atom of alkyl group is substituted with hydroxy group And monomers having a high functional group.

≪Topcoat film formation method≫
The present invention includes a step of forming a layer containing a block copolymer on a support, and a step of applying a topcoat material on the layer containing the block copolymer to form a topcoat film. The coating material contains a polymer compound containing dicarboxylic acid or a salt of dicarboxylic acid and an organic solvent component (S), the organic solvent component (S) contains water and alcohol, and the blending amount of the water Is a method of forming a topcoat film, which is 0.5 times or more the blending amount of the alcohol.
[Step of forming a layer containing a block copolymer on a support], [Step of forming a topcoat film by applying a topcoat material on a layer containing a block copolymer], and description of the topcoat material used Same as above.

The topcoat material used in the method for producing a phase separation structure or the method for forming a topcoat film of the present invention is excellent in film formability. The reason is guessed as follows.
In the present invention, as the organic solvent component of the topcoat material, the surface tension of the topcoat material can be lowered by setting the mixing ratio of water and alcohol within a predetermined range, and when the surface of the block copolymer is applied. It is considered that the film is hardly repelled and can be excellent in film formability.

≪Optional process≫
And a step of selectively removing a phase composed of at least one block from the structure including the phase separation structure manufactured by the method for manufacturing the structure including the phase separation structure according to the present invention. May be. Specifically, for example, as shown in FIG. 2, the top coat film 3 and the phase 2 a are selectively removed from the structure 4 (FIG. 2A) by an etching method, and a pattern is formed on the support 1. May be formed (FIG. 2B).

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

On the silicon substrate, the neutralization film composition shown below adjusted to a concentration of 0.5 to 1.0% by mass using PGMEA as a neutralization film was applied using a spinner, 230 ° C., By baking for 1 minute and drying, a layer made of a neutralized film having a thickness of 5 nm was formed on the substrate.
Spin coating (rotation) of a PGMEA solution containing BCP and propylene glycol monomethyl ether acetate (PGMEA) shown below and having a solid content concentration of 1.5% by mass on a neutralized film to a film thickness of 15 nm Number: 1500 rpm, 60 seconds), and a baking process was performed at 110 ° C. for 60 seconds to form a BCP layer having a thickness of 15 nm.
On the BCP layer, the TC material (TC-B shown below) was dissolved in the mixed solvent shown in Table 1 below (Examples 1 to 5 and Comparative Examples 1 to 6) at the solid content concentration shown in Table 1 below. The top coat film having a film thickness of 50 nm was formed, and the film formability of the top coat film was tested. The film forming property evaluation results are also shown in Table 1.

In the above table, each abbreviation indicates the following, and the compounding ratio is a weight ratio.
IPA: isopropyl alcohol MeOH: methanol EtOH: ethanol

  As shown in Table 1, those using the top coat material of the present invention were excellent in film formability.

DESCRIPTION OF SYMBOLS 1 Support body 2 Layer 3 Topcoat film | membrane 4 Structure

Claims (3)

Forming a layer comprising a block copolymer on a support;
Applying a topcoat material on the layer containing the block copolymer to form a topcoat film;
And a step of phase-separating the layer containing the block copolymer formed with the topcoat film by thermal annealing,
The top coat material contains a polymer compound containing dicarboxylic acid or a dicarboxylic acid salt and an organic solvent component (S), and the organic solvent component (S) contains water and alcohol, A method for producing a structure including a phase separation structure, wherein the blending amount is 0.5 to 3 times the blending amount of the alcohol by weight ratio.   The manufacturing method of the structure containing the phase-separated structure of Claim 1 whose said alcohol is methyl alcohol, ethyl alcohol, or isopropyl alcohol. Forming a layer comprising a block copolymer on a support;
Applying a topcoat material on the layer containing the block copolymer to form a topcoat film;
Including
The top coat material contains a polymer compound containing dicarboxylic acid or a dicarboxylic acid salt and an organic solvent component (S), and the organic solvent component (S) contains water and alcohol, The topcoat film forming method, wherein the blending amount is 0.5 to 3 times the blending amount of the alcohol.

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