Resin composition for phase separation structure formation, and method for manufacturing structure including phase separation structure

Abstract

To provide a resin composition for phase separation structure formation which can improve process margin, and a method for manufacturing a structure including a phase separation structure which uses the same.SOLUTION: A resin composition for phase separation structure formation contains a block copolymer, and a homopolymer, wherein the block copolymer has a first block and a second block, the first block and the homopolymer are each independently constituted of a polymer composed of a repeated structure of a constitutional unit represented by a formula (b1), and at least one terminal of the main chain of the homopolymer has a specific structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition for forming a phase separation structure and a method for manufacturing a structure including the phase separation structure.

Background Art

[0002] In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), technologies for processing more delicate structures have been demanded. In response to such demands, development of a technology for forming a finer pattern has been carried out by utilizing a phase separation structure formed by self-organization of a block copolymer in which blocks that are incompatible with each other are bonded (see, for example, Patent Document 1).

[0003] The above block copolymer separates (phase separates) in microscopic regions due to repulsion between blocks that are incompatible with each other, and by performing heat treatment or the like, a structure having a regular periodic structure is formed. Specific examples of this periodic structure include cylinders (columnar), lamellae (plate-like), spheres (spherical), and the like.

[0004] In order to utilize the phase separation structure of the block copolymer, it is essential to form a self-organized nanostructure formed by microphase separation only in a specific region and to arrange it in a desired direction. In order to achieve these position control and orientation control, processes such as graphoepitaxy for controlling the phase separation pattern by a guide pattern and chemical epitaxy for controlling the phase separation pattern by differences in the chemical state of the substrate have been proposed (see, for example, Non-Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In a method of forming a pattern using a phase separation structure, for one pitch, it is necessary to prepare a block copolymer having a period (L0) of a corresponding structure. Therefore, it is necessary to individually prepare block copolymers for designs of a plurality of pitches. However, if one block copolymer can be used for a plurality of pitches, the process margin will be greatly expanded.

[0008] In order to expand the process margin, a resin composition for forming a phase separation structure to which a homopolymer such as polystyrene or polymethyl methacrylate is added in addition to the block copolymer has been adopted, but the pitch difference before and after the addition has hardly expanded.

[0009] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition for forming a phase separation structure capable of improving the process margin, and a method for manufacturing a structure including the phase separation structure using the same.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a homopolymer having a predetermined structure at at least one end in addition to the block copolymer, and have completed the present invention. Specifically, the present invention provides the following.

[0011] [1] A resin composition for forming a phase separation structure containing a block copolymer and a homopolymer, The block copolymer has a first block and a second block, The first block and the homopolymer are each independently composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). A resin composition for forming a phase separation structure, wherein at least one end of the main chain of the homopolymer has Structure I represented by the following formula (b2-I) or Structure II represented by the following formula (b2-II). [Chemical formula] (In formula (b1), R b1 is a hydrogen atom or a methyl group, R 1 is an oxygen atom or an alkyl group which may have a silicon atom, n is an integer of 0 or more and 5 or less, and when n is an integer of 2 or more, a plurality of R 1 may be the same or different from each other.) [Chemical formula] (In formula (b2-I) and formula (b2-II), R b1 , R 1 , and n are the same as these in formula (b1), R 2 is an alkylene group, X is a group represented by -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-, R 3 is a hydrogen atom or a monovalent organic group, the monovalent organic group as R 3 does not have a proton acidic group and does not have two or more groups represented by -Y-H, Y is a Group 16 element of the periodic table, and the group represented by -X-R 3 is not a carboxy group, and * is a bond.)

[0012] [2] The resin composition for forming a phase separation structure according to [1], wherein X is a group represented by -O-.

[0013] [3] The resin composition for forming a phase separation structure according to [1] or [2], wherein R 3 is a hydrogen atom, an alkyl group, or a cyclic ether group.

[0014] [4] The amount of the homopolymer is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the mass of the block copolymer, and the resin composition for forming a phase separation structure according to any one of [1] to [3].

[0015] [5] The number average molecular weight of the block copolymer is 20,000 or more and 200,000 or less, and the resin composition for forming a phase separation structure according to any one of [1] to [4].

[0016] [6] The number average molecular weight of the homopolymer is 1,000 or more and 10,000 or less, and the resin composition for forming a phase separation structure according to any one of [1] to [5].

[0017] [7] The ratio of the number of moles of the structural unit of the first block to the total of the number of moles of the structural unit of the first block and the number of moles of the structural unit of the second block is 20 mol% or more and 80 mol% or less, and the resin composition for forming a phase separation structure according to any one of [1] to [6].

[0018] [8] Coating the support with the resin composition for forming a phase separation structure according to any one of [1] to [7] to form a layer containing a block copolymer, Phase-separating the layer containing the block copolymer, A method for manufacturing a structure having a phase separation structure, comprising:

Advantages of the Invention

[0019] According to the present invention, it is possible to provide a resin composition for forming a phase separation structure capable of improving a process margin, and a method for manufacturing a structure including a phase separation structure using the same.

Brief Description of the Drawings

[0020]

Figure 1

Figure 2

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0022] In this specification, "aliphatic" is a relative concept with respect to aromatic, and means a group, compound, etc. that does not have aromaticity. "Alkyl group" means a linear or branched monovalent saturated hydrocarbon group unless otherwise specified. The same applies to the alkyl group in the alkoxy group. "Cycloalkyl group" means a monocyclic cyclic saturated hydrocarbon group unless otherwise specified. "Alkylene group" means a linear or branched divalent saturated hydrocarbon group unless otherwise specified. "Halogenated alkyl group" means a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. 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" means a group in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms. "Constituent unit" means a monomer unit (monomeric unit) that constitutes a high molecular compound (resin, polymer, copolymer). "Derived constituent unit" means a constituent unit formed by cleavage of an ethylenic double bond or a cyclic ether. When it is described that "it may have a substituent", it includes both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH2-) with a divalent group. "Exposure" means irradiation with radiation in general. The term "α-position (α-carbon atom)" means, unless otherwise specified, the carbon atom to which the side chain of the block copolymer is attached. The "α-carbon atom" of a methyl methacrylate unit means the carbon atom to which the carbonyl group of methacrylic acid is attached. The "α-carbon atom" of a styrene unit means the carbon atom to which the benzene ring is attached. The "number average molecular weight" (Mn) and the "weight average molecular weight" (Mw) mean, unless otherwise specified, the number average molecular weight and the weight average molecular weight in terms of standard polystyrene conversion determined by gel permeation chromatography (GPC) measurement. When the value of Mn or Mw is given with the unit (g / mol -1 ), the value represents the molar mass. In this specification, depending on the structure represented by a chemical formula, there may be an asymmetric carbon, and enantiomers or diastereomers may exist. In that case, those isomers are represented by one formula. Those isomers may be used alone or as a mixture.

[0023] In this specification, the "period of the structure" means the period of the phase structure observed when the structure of the phase-separated structure is formed, and refers to the sum of the lengths of each phase that is incompatible with each other. When the phase-separated structure forms a cylinder structure perpendicular to the substrate surface, the period of the structure (L0) is the center-to-center distance (pitch) between two adjacent cylinder structures.

[0024] It is known that the period of the structure (L0) is determined by the degree of polymerization N and the intrinsic polymerization characteristics such as the Flory-Huggins interaction parameter χ. That is, the larger the product "χ·N" of χ and N, the greater the mutual repulsion between different blocks in the block copolymer. Therefore, when χ·N>10.5 (hereinafter referred to as the "strength separation limit point"), the repulsion between different types of blocks in the block copolymer is large, and the tendency of phase separation to occur becomes strong. And at the strength separation limit point, the period of the structure is approximately N 2 / 3 ·χ 1 / 6As a result, the relationship of the following formula (cy) holds. That is, the period of the structure is proportional to the degree of polymerization N, which correlates with the molecular weight and the molecular weight ratio between different blocks.

[0025] L0 ∝ a·N 2 / 3 ·χ 1 / 6 ···(cy) [In the formula, L0 represents the period of the structure. a is a parameter indicating the size of the monomer. N represents the degree of polymerization. χ is an interaction parameter, and the larger this value is, the higher the phase separation performance means.]

[0026] Therefore, by adjusting the composition and total molecular weight of the block copolymer, the period (L0) of the structure can be adjusted.

[0027] ≪Resin Composition for Forming Phase Separation Structure≫ The resin composition for forming a phase separation structure contains a block copolymer and a homopolymer. The block copolymer has a first block and a second block. The first block and the homopolymer are each independently composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). At least one end of the main chain of the homopolymer has a structure I represented by the following formula (b2-I) or a structure II represented by the following formula (b2-II).

Chemical formula

Chemical formula

[0028] <Block copolymer> The block copolymer has a first block and a second block.

[0029] [First block] The first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). [Chemical formula] (In formula (b1), R b1 is a hydrogen atom or a methyl group, R 1 is an oxygen atom or an alkyl group which may have a silicon atom, n is an integer of 0 or more and 5 or less, and when n is an integer of 2 or more, a plurality of R 1 may be the same or different from each other.)

[0030] R 1 As the alkyl group which may have an oxygen atom and / or a silicon atom in, an alkyl group which may be interrupted by an oxygen atom and may be substituted by an alkylsilyl group is preferable. Specifically, an alkyl group, an alkylsilyl group, an alkylsilylalkyl group, an alkylsilyloxy group, an alkylsilyloxyalkyl group, an alkoxy group and the like can be mentioned.

[0031] R 1 Examples of the alkyl group in include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.

[0032] As the alkylsilyl group, a trialkylsilyl group is preferred. Specifically, a trimethylsilyl group and the like can be mentioned. As the alkylsilylalkyl group, a trialkylsilylalkyl group is preferred. Specifically, a trimethylsilylmethyl group, a 2-trimethylsilylethyl group, a 3-trimethylsilyl-n-propyl group and the like can be mentioned. As the alkylsilyloxy group, a trialkylsilyloxy group is preferred. Specifically, a trimethylsilyloxy group and the like can be mentioned. As the alkylsilyloxyalkyl group, a trialkylsilyloxyalkyl group is preferred. Specifically, a trimethylsilyloxymethyl group, a 2-trimethylsilyloxyethyl group, a 3-trimethylsilyloxy-n-propyl group and the like can be mentioned. As the alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and the like can be mentioned.

[0033] R 1 The total number of carbon atoms of the alkyl group, which may be interrupted by an oxygen atom and may be substituted with an alkylsilyl group in R, is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

[0034] As n, an integer of 0 or more and 3 or less is preferred, 0 or 1 is more preferred, and 0 is still more preferred.

[0035] 〔Second block〕 The second block is preferably composed of a polymer having a repeating structure of a structural unit derived from (α-substituted) acrylic acid, a polymer having a repeating structure of a structural unit derived from (α-substituted) acrylic acid ester, or a polymer having a repeating structure of a structural unit of siloxane or a derivative thereof, and more preferably composed of a polymer having a repeating structure of a structural unit derived from (α-substituted) acrylic acid ester.

[0036] [Constituent unit derived from (α-substituted) acrylic acid ester] In the present specification, the "(α-substituted) acrylic acid ester" includes an acrylic acid ester and an acrylic acid derivative in which a hydrogen atom bonded to the carbon atom at the α-position in the acrylic acid ester is substituted with a substituent. Examples of the substituent in the (α-substituted) acrylic acid ester include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the like. Among them, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable.

[0037] As the (α-substituted) acrylic acid ester, a (α-substituted) acrylic acid alkyl ester is preferable. The number of carbon atoms of the alkyl group in the (α-substituted) acrylic acid alkyl ester is preferably 1 to 10, and more preferably 1 to 5. Specific examples of the (α-substituted) acrylic acid ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, and propyltrimethoxysilane acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, benzyl methacrylate, anthracene methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethane methacrylate, and propyltrimethoxysilane methacrylate.

[0038] Among the above, as the (α-substituted) acrylate ester, an alkyl acrylate ester or an alkyl methacrylate ester is preferable, methyl acrylate, ethyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate are more preferable, and methyl methacrylate is even more preferable.

[0039] The structural unit derived from the (α-substituted) acrylate ester is preferably a structural unit represented by the following formula (b3).

Chemical formula

[0040] R b3 The number of carbon atoms of the alkyl group in is preferably 1 to 5, more preferably 1 to 3. The alkyl group in R 2 is preferably linear. Examples of the alkyl group in R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, etc. Among them, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group is more preferable.

[0041] R b2 Examples of the alkyl group having 1 to 5 carbon atoms in include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a tert-pentyl group, etc. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.

[0042] R b2 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group, from the viewpoint of easy availability in industry.

[0043] [Constituent unit derived from (α-substituted) acrylic acid] In the present specification, “(α-substituted) acrylic acid” includes acrylic acid and acrylic acid derivatives in which the hydrogen atom bonded to the α-position carbon atom in acrylic acid is substituted with a substituent.

[0044] Specific examples of (α-substituted) acrylic acid include acrylic acid and methacrylic acid.

[0045] [Constituent unit of siloxane or its derivative] Specific examples of siloxane or its derivative include dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

[0046] In the block copolymer, the ratio of the number of moles of the constituent units of the first block to the total number of moles of the constituent units of the first block and the second block is preferably 20 mol% or more and 80 mol% or less. The ratio of the number of moles of the constituent units of the first block is more preferably 30 mol% or more, even more preferably 45 mol% or more, and particularly preferably 55 mol% or more. Also, the ratio of the number of moles of the constituent units of the first block is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

[0047] In addition to the first block and the second block, the block copolymer may have other blocks. In a preferred embodiment, the block copolymer is a diblock copolymer composed of the first block and the second block.

[0048] The number average molecular weight (Mn) of the block copolymer is not particularly limited, but is preferably 10,000 or more and 300,000 or less, more preferably 15,000 or more and 250,000 or less, and even more preferably 20,000 or more and 200,000 or less. The molecular weight distribution (Mw / Mn) of each block constituting the block copolymer is preferably 1.0 or more and 1.5 or less, more preferably 1.0 or more and 1.4 or less, and even more preferably 1.0 or more and 1.3 or less.

[0049] <Homopolymer> The homopolymer is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). At least one end of the main chain of the homopolymer has a structure I represented by the following formula (b2-I) or a structure II represented by the following formula (b2-II).

Chemical formula

Chemical formula

[0050] In the homopolymer, R in formula (b1) b1 , R 1 , and the preferred embodiments of n are the same as R b1 , R 1 , and n in formula (b1) in the first block.

[0051] It is preferable that at least one end of the main chain of the homopolymer has a structure II represented by the following formula (b2-II).

[0052] R 2 The number of carbon atoms of the alkylene group in is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 3 or less. R 2 The alkylene group in is preferably linear. R 2 Examples of the alkylene group in include a methylene group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and the like. Among them, a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are preferable, and an ethane-1,2-diyl group is more preferable.

[0053] X is preferably a group represented by -O-.

[0054] R 3 The number of carbon atoms of the monovalent organic group in is preferably 1 or more and 30 or less, more preferably 1 or more and 20 or less, still more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. R 3Examples of the monovalent organic group include a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. Among them, a chain hydrocarbon group and a heterocyclic group are preferable.

[0055] As the chain hydrocarbon group, an alkyl group is preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. Among them, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group is more preferable. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthalenyl group, and an anthracenyl group. Examples of the hetero element contained in the heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. As the heterocyclic group, an oxygen-containing heterocyclic group is preferable, and a cyclic ether group is more preferable.

[0056] R 3 is preferably a hydrogen atom, a chain hydrocarbon group, or a heterocyclic group, and more preferably a hydrogen atom, an alkyl group, or a cyclic ether group.

[0057] The number average molecular weight (Mn) of the homopolymer is not particularly limited, but is preferably 500 or more and 50,000 or less, more preferably 800 or more and 20,000 or less, and even more preferably 1,000 or more and 10,000 or less. The molecular weight distribution (Mw / Mn) of the homopolymer is preferably 1.0 or more and 1.5 or less, more preferably 1.0 or more and 1.4 or less, and even more preferably 1.0 or more and 1.3 or less.

[0058] The amount of the homopolymer is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, and even more preferably 5 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the block copolymer.

[0059] [Method for Producing Homopolymer] The homopolymer can be synthesized by living anionic polymerization or the like. For example, when synthesizing polystyrene, styrene is polymerized in a suitable solvent using an initiator and then treated with a terminator. However, -R 2 -X-R 3 By using an initiator having a group represented by, the above structure I can be introduced at the initiation end of polystyrene. Also, -R 2 -X-R 3 By using a terminator having a group represented by, the above structure II can be introduced at the termination end of polystyrene.

[0060] <Organic Solvent Component> The resin composition for forming a phase-separated structure preferably contains an organic solvent. As the organic solvent component, any organic solvent can be used as long as it can dissolve each component to be used and form a uniform solution. Conventionally, any organic solvent selected from known organic solvents as the solvent of a composition mainly composed of a resin can be used.

[0061] Examples of the organic solvent component include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; monoacetates of polyhydric alcohols such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, or monobutyl ether of the polyhydric alcohols or the monoacetates of the polyhydric alcohols, or compounds having an ether bond such as monophenyl ether, i.e., derivatives of polyhydric alcohols [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, and esters other than the monoacetates of polyhydric alcohols and the derivatives of the polyhydric alcohols mentioned above, such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, and mesitylene. The organic solvent component may be used alone or as a mixed solvent of two or more kinds. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0062] The organic solvent component contained in the resin composition for forming a phase separation structure is not particularly limited. The organic solvent component is appropriately set according to the coating film thickness so that the concentration of the resin composition for forming a phase separation structure is a coatable concentration. The organic solvent component is generally used so that the solid content concentration of the resin composition for forming a phase separation structure is in the range of 0.2% by mass or more and 70% by mass or less, preferably 0.2% by mass or more and 50% by mass or less.

[0063] <Optional component> The resin composition for forming a phase separation structure may contain optional components other than the above-described block copolymer, homopolymer, and organic solvent component. Examples of the optional component include other resins, surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, sensitizers, base proliferators, basic compounds, and the like.

[0064] ≪Method for manufacturing a structure including a phase separation structure≫ The method for manufacturing a structure including a phase separation structure includes applying a resin composition for forming a phase separation structure on a support to form a layer containing a block copolymer (hereinafter referred to as "step (i)"), and phase-separating the layer containing the block copolymer (hereinafter referred to as "step (ii)"). Hereinafter, the method for manufacturing a structure including such a phase separation structure will be specifically described with reference to FIG. 1. However, the method for manufacturing a structure including a phase separation structure is not limited to the embodiment specifically shown in FIG. 1.

[0065] FIG. 1 shows an example of an embodiment of the method for manufacturing a structure including a phase separation structure. In the embodiment shown in FIG. 1, first, a primer is applied on a support 41 to form a primer layer 42 (FIG. 1(I)). Next, a resin composition for forming a phase separation structure is applied on the primer layer 42 to form a layer containing a block copolymer (BCP layer) 43 (FIG. 1(II); the above is step (i)). Next, heating and annealing are performed to phase-separate the BCP layer 43 into phase 43a and phase 43b (FIG. 1(III); step (ii)). According to the manufacturing method of such an embodiment, that is, the manufacturing method having steps (i) and (ii), a structure 43' including a phase separation structure is manufactured on a support 41 on which an undercoat layer 42 is formed.

[0066] <Step (i)> In step (i), a resin composition for forming a phase separation structure is applied on the support 41 to form a BCP layer 43. In the embodiment shown in FIG. 1, first, an undercoat agent is applied on the support 41 to form an undercoat layer 42. By providing the undercoat layer 42 on the support 41, the hydrophilic-hydrophobic balance between the surface of the support 41 and the layer containing the block copolymer (BCP layer) 43 can be achieved. That is, when the undercoat layer 42 contains a resin component having a structural unit constituting the first block, the adhesion between the phase composed of the first block in the BCP layer 43 and the support 41 is enhanced. When the undercoat layer 42 contains a resin component having a structural unit constituting the second block, the adhesion between the phase composed of the second block in the BCP layer 43 and the support 41 is enhanced. Accordingly, due to the phase separation of the BCP layer 43, a phase separation structure oriented in the direction perpendicular to the surface of the support 41 is easily formed.

[0067] Undercoat agent: As the undercoat agent, a resin composition can be used. The resin composition for the undercoat agent can be appropriately selected from conventionally known resin compositions used for thin film formation according to the types of blocks constituting the block copolymer. The resin composition for the undercoat agent may be, for example, a thermopolymerizable resin composition, or a photosensitive resin composition such as a positive resist composition or a negative resist composition. Alternatively, a compound may be used as a surface treatment agent, and a non-polymerizable film formed by applying the compound may be used as the undercoat layer. For example, a siloxane-based organic monolayer film formed using phenethyltrichlorosilane, octadecyltrichlorosilane, hexamethyldisilazane, etc. as the surface treatment agent can also be suitably used as the undercoat layer.

[0068] Examples of such resin compositions include resin compositions containing a resin having both the structural units constituting the first block and the second block, resin compositions containing a resin having both structural units highly compatible with each block constituting the block copolymer, and the like. As the resin composition for the primer, for example, a composition containing a resin having both styrene and methyl methacrylate as structural units, or a compound or composition containing both a site highly compatible with styrene such as an aromatic ring and a site highly compatible with methyl methacrylate (a highly polar functional group or the like) is preferably used. Examples of the resin having both styrene and methyl methacrylate as structural units include a random copolymer of styrene and methyl methacrylate, an alternating polymer of styrene and methyl methacrylate (a polymer in which each monomer is copolymerized alternately), and the like. Examples of the composition containing both a site highly compatible with styrene and a site highly compatible with methyl methacrylate include, for example, a composition containing a resin obtained by polymerizing, as monomers, at least a monomer having an aromatic ring and a monomer having a highly polar functional group. Examples of the monomer having an aromatic ring include aryl groups obtained by removing one hydrogen atom from the ring of an aromatic hydrocarbon, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or heteroaryl groups in which some of the carbon atoms constituting the ring of these groups are substituted with heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of the monomer having a highly polar functional group include monomers having a trimethoxysilyl group, a trichlorosilyl group, an epoxy group, a glycidyl group, a carboxy group, a hydroxy group, a cyano group, a hydroxyalkyl group in which some of the hydrogen atoms of an alkyl group are substituted with hydroxy groups, and the like. In addition, examples of the compound containing both a site having a high affinity for styrene and a site having a high affinity for methyl methacrylate include compounds containing both an aryl group such as phenethyltrichlorosilane and a highly polar functional group, and compounds containing both an alkyl group such as an alkylsilane compound and a highly polar functional group.

[0069] The resin composition for the undercoat can be produced by dissolving the aforementioned resin in a solvent. Such a solvent may be any solvent that can dissolve each component to be used and form a uniform solution. For example, solvents similar to the organic solvent components exemplified in the description of the resin composition for forming a phase separation structure can be mentioned.

[0070] The type of the support 41 is not particularly limited as long as the resin composition can be coated on its surface. For example, substrates made of inorganic substances such as silicon, metals (copper, chromium, iron, aluminum, etc.), glass, titanium oxide, silica, mica, etc.; substrates made of oxides such as SiO2; substrates made of nitrides such as SiN; substrates made of oxynitrides such as SiON; substrates made of organic substances such as acrylic resin, polystyrene, cellulose, cellulose acetate, phenolic resin, etc. Among these, a silicon substrate (Si substrate) or a metal substrate is preferable, an Si substrate or a copper substrate (Cu substrate) is more preferable, and an Si substrate is particularly preferable. The size and shape of the support 41 are not particularly limited. The support 41 does not necessarily have a smooth surface, and substrates of various shapes can be appropriately selected. For example, substrates having a curved surface, flat plates with an uneven surface, substrates in the shape of flakes, etc. can be mentioned.

[0071] An inorganic and / or organic film may be provided on the surface of the support 41. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC). The inorganic film can be formed, for example, by coating an inorganic antireflection film composition such as a silicon-based material on the support and then performing firing or the like. The organic film can be formed, for example, by applying an organic film-forming material in which a resin component or the like constituting the film is dissolved in an organic solvent onto a substrate using a spinner or the like, and preferably baking it under heating conditions of 200°C or higher and 300°C or lower, preferably for 30 seconds or longer and 300 seconds or shorter, more preferably for 60 seconds or longer and 180 seconds or shorter. This organic film-forming material does not necessarily require sensitivity to light or electron beams like a resist film, and may or may not have sensitivity. Specifically, resists and resins generally used in the manufacture of semiconductor elements and liquid crystal display elements can be used. Also, by etching the organic film using a pattern made of a block copolymer formed by processing the BCP layer 43, the pattern can be transferred onto the organic film to form an organic film pattern. The organic film-forming material is preferably a material that can form an organic film that can be etched, particularly dry-etched. Among them, it is preferably a material that can form an organic film that can be etched such as oxygen plasma etching. Such an organic film-forming material may be a material conventionally used for forming organic films such as organic BARC. For example, the ARC series manufactured by Nissan Chemical Industries, Ltd., the AR series manufactured by Rohm and Haas, the SWK series manufactured by Tokyo Ohka Kogyo Co., Ltd., etc. can be mentioned.

[0072] The method for applying the underlayer agent onto the support 41 to form the underlayer agent layer 42 is not particularly limited and can be formed by a conventionally known method. For example, the underlayer agent can be applied onto the support 41 by a conventionally known method such as spin coating or using a spinner to form a coating film, and the underlayer agent layer 42 can be formed by drying. As a method for drying the coating film, it is sufficient if the solvent contained in the underlayer agent can be volatilized, and examples include baking. At this time, the baking temperature is preferably 80°C or higher and 300°C or lower, more preferably 180°C or higher and 270°C or lower, and even more preferably 220°C or higher and 250°C or lower. The baking time is preferably 30 seconds or longer and 600 seconds or shorter, and more preferably 60 seconds or longer and 600 seconds or shorter. The thickness of the primer layer 42 after the coating film is dried is preferably about 10 nm or more and 100 nm or less, and more preferably about 40 nm or more and 90 nm or less.

[0073] Before forming the primer layer 42 on the support 41, the surface of the support 41 may be washed in advance. By washing the surface of the support 41, the coatability of the primer is improved. As the cleaning treatment method, conventionally known methods can be used, such as oxygen plasma treatment, ozone oxidation treatment, acid-base treatment, chemical modification treatment, etc.

[0074] After forming the primer layer 42, if necessary, the primer layer 42 may be rinsed with a rinse liquid such as a solvent. By this rinsing, uncrosslinked portions in the primer layer 42 are removed, so the affinity with at least one block constituting the block copolymer is improved, and a phase separation structure composed of a cylinder structure oriented in the direction perpendicular to the surface of the support 41 is likely to be formed. The rinse liquid only needs to be able to dissolve the uncrosslinked portion, and solvents such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), or commercially available thinner liquids can be used. Also, after this cleaning, post-baking may be performed to volatilize the rinse liquid. The temperature condition of this post-baking is preferably 80°C or more and 300°C or less, and more preferably 100°C or more and 270°C or less. The baking time is preferably 30 seconds or more and 500 seconds or less, and more preferably 60 seconds or more and 240 seconds or less. The thickness of the primer layer 42 after such post-baking is preferably about 1 nm or more and 10 nm or less, and more preferably about 2 nm or more and 7 nm or less.

[0075] Next, a layer (BCP layer) 43 containing a block copolymer is formed on the primer layer 42. As a method for forming the BCP layer 43 on the underlayer 42, there is no particular limitation. For example, a method of applying the resin composition for forming a phase separation structure of the above-described embodiment on the underlayer 42 to form a coating film and drying it by a conventionally known method such as spin coating or using a spinner can be mentioned.

[0076] The thickness of the BCP layer 43 only needs to be sufficient for phase separation to occur. Considering the type of the support 41, or the structural period size of the phase separation structure to be formed or the uniformity of the nanostructures, etc., it is preferably 20 nm or more and 100 nm or less, and more preferably 20 nm or more and 80 nm or less. For example, when the support 41 is a Si substrate, the thickness of the BCP layer 43 is preferably adjusted to 10 nm or more and 100 nm or less, and more preferably 20 nm or more and 80 nm or less.

[0077] <Step (ii)> In step (ii), the BCP layer 43 formed on the support 41 is phase-separated. By heating the support 41 after step (i) and performing an annealing treatment, a phase separation structure is formed such that at least a part of the surface of the support 41 is exposed by selective removal of the block copolymer. That is, a structure 43' including a phase separation structure phase-separated into a phase 43a and a phase 43b is manufactured on the support 41. The temperature condition of the annealing treatment is preferably performed at a temperature equal to or higher than the glass transition temperature of the block copolymer used and lower than the thermal decomposition temperature. For example, when the block copolymer is a polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer (weight average molecular weight of 5000 or more and 100000 or less), it is preferably 180°C or more and 270°C or less. The heating time is preferably 30 seconds or more and 3600 seconds or less. Also, the annealing treatment is preferably performed in a gas with low reactivity such as nitrogen.

[0078] <Optional step> The manufacturing method of the structure including the phase separation structure is not limited to the above-described embodiment, and may have steps (optional steps) other than steps (i) and (ii).

[0079] Examples of such an arbitrary step include a step of selectively removing a phase composed of at least one of the first block and the second block constituting the block copolymer from the BCP layer 43 (hereinafter referred to as "step (iii)"), a step of forming a guide pattern, and the like.

[0080] ·Regarding step (iii) In step (iii), a phase composed of at least one of the first block and the second block constituting the block copolymer is selectively removed from the BCP layer formed on the undercoat layer 42. Thereby, a fine pattern (polymer nanostructure) is formed.

[0081] Examples of the method of selectively removing the phase composed of the blocks include a method of performing oxygen plasma treatment on the BCP layer, a method of performing hydrogen plasma treatment, and the like. For example, after phase-separating the BCP layer containing the block copolymer, by performing oxygen plasma treatment, hydrogen plasma treatment, or the like on the BCP layer, the phase composed of the first block is not selectively removed, and the phase composed of the second block is selectively removed.

[0082] FIG. 2 shows an exemplary embodiment of step (iii). In the embodiment shown in FIG. 2, by performing oxygen plasma treatment on the structure 43' manufactured on the support 41 in step (ii), the phase 43a is selectively removed, and a pattern (polymer nanostructure) composed of the separated phase 43b is formed. In this case, the phase 43b is the phase composed of the first block, and the phase 43a is the phase composed of the second block.

[0083] The support 41 on which the pattern is formed by phase separation of the BCP layer 43 composed of the block copolymer as described above can be used as it is, or the shape of the pattern (polymer nanostructure) on the support 41 can also be changed by further heating. The temperature condition for heating is preferably equal to or higher than the glass transition temperature of the block copolymer to be used and lower than the thermal decomposition temperature. Further, the heating is preferably carried out in a gas with low reactivity such as nitrogen.

[0084] ·Regarding the guide pattern formation step In the method for producing a structure including a phase separation structure, a step of providing a guide pattern on the underlayer agent layer (guide pattern formation step) may be included between the above-described step (i) and step (ii). Thereby, it becomes possible to control the arrangement 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 when no guide pattern is provided, by providing a groove structure of a resist film on the surface of the underlayer agent layer, a phase separation structure oriented along the grooves can be obtained. Based on such a principle, a guide pattern may be provided on the underlayer agent layer 42. Further, when the surface of the guide pattern has an affinity with any of the blocks constituting the block copolymer, a phase separation structure composed of a cylinder structure oriented in a direction perpendicular to the surface of the support is likely to be formed.

[0085] The guide pattern can be formed using, for example, a resist composition. The resist composition for forming the guide pattern can be appropriately selected from a resist composition generally used for forming a resist pattern and its modified products, a composition having an affinity with any of the blocks constituting the block copolymer. As the resist composition, either a positive resist composition for forming a positive pattern in which the exposed portion of the resist film is dissolved and removed or a negative resist composition for forming a negative pattern in which the unexposed portion of the resist film is dissolved and removed may be used, but a negative resist composition is preferred. As the negative resist composition, for example, a resist composition containing an acid generator and a base material component whose solubility in a developer containing an organic solvent decreases due to the action of an acid, and the base material component contains a resin component having a structural unit that decomposes due to the action of an acid and increases in polarity is preferred. After the BCP composition is poured onto the primer layer on which the guide pattern is formed, an annealing process is performed to cause phase separation. Therefore, as the resist composition for forming the guide pattern, a composition capable of forming a resist film excellent in solvent resistance and heat resistance is preferable.

Example

[0086] The present invention will be described in more detail based on the examples, but the present invention is not limited by these examples.

[0087] The block copolymer (BCP) used in the examples is a block copolymer of a block made of polystyrene (PS) and a block made of polymethyl methacrylate (PMMA). Table 1 and Table 2 show the number average molecular weight (Mn) of each BCP and the ratio of the number of moles of the PS structural unit to the total number of moles of each structural unit.

[0088] Hereinafter, the homopolymers used in the examples will be described.

[0089] <Synthesis of Homopolymer 1 (HP1)> Under an argon atmosphere, 323 mg (7.61 mmol) of lithium chloride (LiCl) and 150 g of tetrahydrofuran (THF) were placed in a Schlenk tube and cooled to -78 °C. After dehydrating and degassing the inside of the tube, 7.5 mL (a 2.65 mol / L hexane-cyclohexane mixed solution, 8.47 mmol) of sec-BuLi was added as an anionic polymerization initiator under an argon atmosphere. Subsequently, 16.5 mL (143.54 mmol) of styrene was added, and stirring was carried out at -78 °C for 30 minutes. After stirring, 0.62 mL (47.85 mmol) of compound A-1 was added, and stirring was carried out at -40 °C for 120 minutes. Then, the temperature of the reaction solution was raised to room temperature. An operation was performed to drop the obtained reaction polymerization solution into a large amount of methanol to precipitate the polymer, and a white powder was precipitated. The precipitated white powder was washed with a large amount of methanol and then washed with a large amount of pure water and dried to obtain 13.22 g (yield 89.0%) of precursor 1. For precursor 1, the number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,100, and the molecular weight distribution (Mw / Mn) was 1.07.

[0090] Into a three-necked flask equipped with a thermometer, a reflux tube, and a nitrogen inlet tube, 4.52 g of precursor 1 and THF (adjusted so that precursor 1 is 10% by mass) were placed, 450 mg (10 parts by mass with respect to 100 parts by mass of the mass of precursor 1) of p-TSA (p-toluenesulfonic acid monohydrate) was added, and after stirring for 20 minutes, stirring was carried out at 40 °C for 6 hours. The reaction solution was returned to room temperature, and an operation was performed to drop the obtained reaction solution into a large amount of methanol (or hexane, etc.) to precipitate the polymer, and a white powder was precipitated. The precipitated white powder was washed with a large amount of methanol (or hexane, etc.) and then washed with a large amount of pure water and dried to obtain 4.29 g (yield 95.0%) of homopolymer 1 (HP1). The number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,000, and the molecular weight distribution (Mw / Mn) was 1.07. In the following reaction formula, n1 is the repeating number of styrene units.

[0091]

Chemical formula

[0092] Similarly, HP1 with a number average molecular weight (Mn) of 3,000 and a molecular weight dispersity (Mw / Mn) of 1.07; HP1 with a number average molecular weight (Mn) of 4,000 and a molecular weight dispersity (Mw / Mn) of 1.07; and HP1 with a number average molecular weight (Mn) of 5,000 and a molecular weight dispersity (Mw / Mn) of 1.07 were each obtained.

[0093] <Synthesis of Homopolymer 2 (HP2)> The precursor 1 obtained by the same method as the synthesis of HP1 was used as homopolymer 2 (HP2). The number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,000, and the molecular weight dispersity (Mw / Mn) was 1.07.

[0094] <Synthesis of Homopolymer 3 (HP3)> In the synthesis of HP1, instead of adding Compound A-1, Compound A-2 (2-bromoethyl methyl ether) was added, and after stirring at -40 °C for 120 minutes, the temperature of the reaction solution was raised to room temperature. The obtained reaction polymerization solution was dropped into a large amount of methanol to precipitate the polymer, and a white powder was precipitated. The precipitated white powder was washed with a large amount of methanol and then washed with a large amount of pure water and dried to obtain homopolymer 3 (HP3). The number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,000, and the molecular weight dispersity (Mw / Mn) was 1.09. In the following reaction formula, n1 is the repeating number of styrene units.

[0095]

Chemical formula

[0096] <Synthesis of Homopolymer 4 (HP4)> Instead of introducing Compound A-1, a homopolymer 4 (HP4) was obtained in the same manner as the synthesis of HP1, except that Compound A-3 was introduced. The number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,000, and the molecular weight dispersity (Mw / Mn) was 1.08. In the following reaction formula, n1 is the repeating number of styrene units.

[0097]

Chemical formula

[0098] <Homopolymer 5 (HP5)> The following polystyrene was used as homopolymer 5 (HP5). The number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement was 2,000. In the following reaction formula, n1 is the repeating number of styrene units.

Chemical formula

[0099] <Measurement of molar ratio of constituent units of each block> An NMR apparatus (manufactured by Bruker, equipped with a CryoProbe) was used. 1 By 1H-NMR measurement (600 MHz, deuterated acetone), the integral ratio value (area ratio) was measured from the chemical shifts of the constituent units of each block of the block copolymer, and the molar ratio of the constituent units of each block was calculated.

[0100] <Preparation of resin composition for forming phase separation structure and production of structure including phase separation structure> Each BCP shown in Table 1 and Table 2, each HP, and propylene glycol monomethyl ether were mixed and dissolved to prepare a resin composition for forming a phase separation structure (solid content concentration of about 1.4% by mass) for each example. The addition amount indicates the addition amount (parts by mass) of HP with respect to 100 parts by mass of BCP.

[0101] Using the resin composition for forming a phase separation structure of each example, a structure including a phase separation structure was formed by the following steps (1) to (3), and then a hole pattern was formed by step (4).

[0102] Step (1): A 12-inch silicon wafer substrate was baked at 150 °C for 60 seconds. On the baked substrate, a resin composition for an underlayer agent (a copolymer of polystyrene / polymethyl methacrylate / poly(2-hydroxyethyl methacrylate), composition ratio (mass ratio): polystyrene / polymethyl methacrylate / poly(2-hydroxyethyl methacrylate)=82 / 12 / 6) prepared in a 2 mass% propylene glycol monomethyl ether acetate (PGMEA) solution was applied using a spinner (1500 rpm) under a nitrogen atmosphere, and dried by baking at 250 °C for 300 seconds to form an underlayer agent layer with a film thickness of 60 nm on the substrate.

[0103] Step (2): Next, the portions of the underlayer agent layer other than the portion in close contact with the substrate were rinsed with a solvent OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 34 seconds and then baked at 100 °C for 60 seconds. After spin-coating the resin composition for forming a phase separation structure of each example on the underlayer agent layer, it was soft-baked at 90 °C for 60 seconds for drying to form a resin composition layer with a film thickness of 43 nm.

[0104] Step (3): This substrate was heated and annealed at 250 °C for 15 minutes under a nitrogen atmosphere to form a phase separation structure (cylinder structure).

[0105] Step (4): The substrate on which the phase separation structure was formed was irradiated with ultraviolet rays (λ172 nm, 160 mJ) under a nitrogen atmosphere using CLEAN TRACK LITHIUS Pro-Z (manufactured by Tokyo Electron Limited). Then, development was performed with isopropyl alcohol to selectively remove the phase made of PMMA and form a hole pattern.

[0106] [Evaluation of aperture ratio] For each of the formed hole patterns, image analysis was performed using image analysis software (DSA-APPS, manufactured by Hitachi High-Technologies Corporation), and the aperture ratio (%) of each hole pattern was determined. The aperture ratio was defined as the ratio of the proportion of well-formed circular holes, and the evaluation was carried out according to the following criteria. The results are shown in Tables 1 and 2. ○: More than 100% of the aperture ratio of Reference Example 1 △: More than 97% and less than or equal to 100% of the aperture ratio of Reference Example 1 ×: 97% or less of the aperture ratio of Reference Example 1

[0107] [Evaluation of Pitch] For each of the formed hole patterns, image analysis was performed using image analysis software (DSA-APPS, manufactured by Hitachi High-Technologies Corporation), and the average value of the pitch was determined from each circular hole in the 1350 nm-angle image. In Table 1, the difference from the pitch of Reference Example 1 was shown. In Table 2, the pitch was evaluated using a resin composition for forming a phase separation structure that contains the same BCP but does not contain HP, and the difference from that pitch was shown. The larger the pitch difference, the wider the process margin.

[0108]

Table 1

[0109]

Table 2

[0110] As shown in Table 1, it was found that in the examples using a resin composition containing a homopolymer having a predetermined structure at at least one end in addition to the BCP, the pitch difference was significantly enlarged. Also, it was found that in any of the examples, an aperture ratio comparable to that of Reference Example 1 was obtained. Therefore, it can be seen that the resin composition for forming a phase separation structure in the examples can improve the process margin.

Claims

1. A resin composition for forming a phase-separated structure, comprising a block copolymer and a homopolymer, wherein the block copolymer has a first block and a second block, the first block and the homopolymer are each independently composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), A resin composition for forming a phase-separated structure, wherein at least one end of the main chain of the homopolymer has Structure I represented by the following formula (b2-I) or Structure II represented by the following formula (b2-II). 【Chemical Formula 1】 (In formula (b1), R ｂ１ is a hydrogen atom or a methyl group, and R １ is an alkyl group which may have an oxygen atom or a silicon atom, n is an integer of 0 or more and 5 or less, and when n is an integer of 2 or more, a plurality of R １ may be the same or different from each other.) 【Chemical 2】 (In formula (b2-I) and formula (b2-II), R ｂ１ , R １ , and n are the same as these in the above formula (b1), R ２ is an alkylene group, X is a group represented by -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-, R ３ is a hydrogen atom or a monovalent organic group, the monovalent organic group as R ３ has no proton acidic group and does not have two or more groups represented by -Y-H, Y is an element of Group 16 of the periodic table, and the group represented by -X-R ３ is not a carboxy group, and * is a bond.)

2. The resin composition for forming a phase-separated structure according to Claim 1, wherein X is a group represented by -O-.

3. Said R ３ The resin composition for forming a phase separation structure according to claim 1, wherein R is a hydrogen atom, an alkyl group, or a cyclic ether group.

4. The resin composition for forming a phase-separated structure according to Claim 1, wherein the amount of the homopolymer is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the mass of the block copolymer.

5. The resin composition for forming a phase-separated structure according to Claim 1, wherein the number average molecular weight of the block copolymer is 20,000 or more and 200,000 or less.

6. The resin composition for forming a phase-separated structure according to Claim 1, wherein the number average molecular weight of the homopolymer is 1,000 or more and 10,000 or less.

7. The resin composition for forming a phase-separated structure according to Claim 1, wherein the ratio of the number of moles of the structural unit of the first block to the total of the number of moles of the structural units of the first block and the second block is 20 mol% or more and 80 mol% or less.

8. Applying the resin composition for forming a phase-separated structure according to any one of Claims 1 to 7 onto a support to form a layer containing a block copolymer; Phase-separating the layer containing the block copolymer; A method for manufacturing a structure having a phase-separated structure, comprising:

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