Resin composition for forming phase-separated structure, method for producing structure having phase-separated structure, and block copolymer

Abstract

To provide a resin composition for forming a phase-separated structure capable of forming a phase-separated structure having an excellent vertical orientation, a method for producing a structure having a phase-separated structure using the same, and a block copolymer for use in the resin composition for forming a phase-separated structure.SOLUTION: In a resin composition for forming a phase-separated structure, a first block comprises a polymer having a repeating structure of a constituent unit represented by the formula (b1) in the figure, and a second block comprises a random copolymer having a structure in which a constituent unit represented by the formula (b2a) in the figure and a constituent unit represented by the formula (b2b) in the figure are randomly arranged, where the ratio of the volume of the first block is from 20 vol.% to 80 vol% inclusive.SELECTED DRAWING: None

Description

Technical Field

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

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, technologies for forming finer patterns have been developed by utilizing phase separation structures formed by self-organization of block copolymers in which blocks that are mutually incompatible are bonded to each other (see, for example, Patent Document 1). In order to utilize the phase separation structure of a block copolymer, it is essential to form a self-organized nanostructure formed by microphase separation only in a specific region and to align it in a desired direction. In order to achieve these position control and orientation control, processes such as graphoepitaxy that controls the phase separation pattern by a guide pattern and chemical epitaxy that controls the phase separation pattern by differences in the chemical state of the substrate have been proposed (see, for example, Non-Patent Document 1).

[0003] A block copolymer forms a structure having a regular periodic structure by phase separation. The "period of the structure" means the period of the phase structure observed when a structure of the phase separation structure is formed, and refers to the sum of the lengths of each phase that is mutually incompatible. When the phase separation structure forms a cylinder structure perpendicular to the substrate surface, the period (L0) of the structure is the center-to-center distance (pitch) between two adjacent cylinder structures.

[0004] The period (L0) of the structure is known to be 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 stronger. And at the strength separation limit point, the period of the structure is approximately N 2 / 3 ·χ 1 / 6 and the relationship of the following formula (1) holds. That is, the period of the structure is proportional to the degree of polymerization N that correlates with the molecular weight and the molecular weight ratio between different blocks.

[0005] L0 ∝ a·N 2 / 3 ·χ 1 / 6 ···(1) [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 the interaction parameter, and the larger this value is, the higher the phase separation performance means.]

[0006] Therefore, by adjusting the composition and total molecular weight of the block copolymer, the period (L0) of the structure can be adjusted. The periodic structure formed by the block copolymer changes to a cylinder (columnar), lamella (plate-like), sphere (spherical) with the volume ratio of the polymer components, etc., and its period is known to depend on the molecular weight. Therefore, in order to form a structure with a relatively large period (L0) using the phase separation structure formed by the self-organization of the block copolymer, a method of increasing the molecular weight of the block copolymer can be considered.

[0007] In addition, a method using a block copolymer having a larger interaction parameter (χ) than a block copolymer having a block of styrene and a block of methyl methacrylate, which is a general-purpose block copolymer, can be considered. For example, Non-Patent Document 2 proposes a block copolymer composed of a block of styrene and a block of 2-hydroxy-3-(2,2,2-trifluoroethylsulfanyl)propyl methacrylate.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Non-Patent Documents

[0009]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] In order to form a fine pattern by utilizing the phase separation structure formed by the self-organization of the block copolymer, it is preferable that the phase separation structure formed by the block copolymer has perpendicular orientation. However, it is difficult to form a phase separation structure having perpendicular orientation with the block copolymer described in Non-Patent Document 2.

[0011] 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 forming a phase separation structure excellent in vertical alignment, a method for manufacturing a structure including the phase separation structure using the same, and a block copolymer used in the resin composition for forming the phase separation structure.

Means for Solving the Problems

[0012] 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 predetermined block copolymer, and have completed the present invention. Specifically, the present invention provides the following.

[0013] A first aspect is a resin composition for forming a phase separation structure containing a block copolymer having a first block and a second block, wherein the first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), the second block is composed of a random copolymer having a structure in which a structural unit represented by the following formula (b2a) and a structural unit represented by the following formula (b2b) are randomly arranged, and a ratio of a volume of the first block to a total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less, which is a resin composition for forming a phase separation structure.

Chemical Formula

[0014] A second aspect is to apply the resin composition for forming a phase separation structure of the first aspect on a support to form a layer containing the block copolymer, phase-separating the layer containing the block copolymer, and is a method for producing a structure having a phase separation structure.

[0015] A third aspect is a block copolymer having a first block and a second block, wherein the first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), the second block is composed of a random copolymer having a structure in which a structural unit represented by the following formula (b2a) and a structural unit represented by the following formula (b2b) are randomly arranged, and is a block copolymer in which the ratio of the volume of the first block to the total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less. [Chemical formula] (In formula (b1), R 1 is an alkyl group which may have an oxygen atom and / 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, and R b1is a hydrogen atom or a methyl group. In formula (b2a), R 2 is a hydroxy group, a mercapto group, an alkoxy group, or an alkylthio group, and R 3 is an oxygen atom, -NH-, or -NR 4 -optionally interrupted by - and may have a hydroxy group, and is an alkylene group having 1 to 10 carbon atoms, and R 4 is an alkyl group having 1 to 6 carbon atoms, In formula (b2a) and formula (b2b), R b2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and a plurality of R b2 may be the same or different. )

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a resin composition for forming a phase separation structure capable of forming a phase separation structure excellent in vertical alignment, a method for producing a structure including the phase separation structure using the same, and a block copolymer used in the resin composition for forming the phase separation structure.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0018] 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.

[0019] In this specification, "aliphatic" is a relative concept with respect to aromatic, and means a group, compound, etc. that do not have aromaticity. "Alkyl group" means a monovalent saturated hydrocarbon group that is linear or branched, unless otherwise specified. The same applies to the alkyl group in an alkoxy group. "Cycloalkyl group" means a monocyclic cyclic saturated hydrocarbon group, unless otherwise specified. "Alkylene group" means a divalent saturated hydrocarbon group that is linear or branched, unless otherwise specified. "Halogenated alkyl group" means a group in which some or all of the hydrogen atoms of an 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 an 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 as "optionally having 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. "α-position (α-carbon atom)" means the carbon atom to which the side chain of a block copolymer is attached, unless otherwise specified. 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. "Number average molecular weight" (Mn) means the number average molecular weight in terms of standard polystyrene measured by size exclusion chromatography, unless otherwise specified. "Weight average molecular weight" (Mw) means the weight average molecular weight in terms of standard polystyrene measured by size exclusion chromatography, unless otherwise specified. 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 atom, and enantiomers or diastereomers may exist. In such a case, these isomers are represented by one formula. These isomers may be used alone or as a mixture.

[0020] ≪Resin Composition for Forming Phase Separation Structure≫ The resin composition for forming a phase separation structure contains a block copolymer having a first block and a second block. The first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). The second block is composed of a random copolymer having a structure in which the structural unit represented by the following formula (b2a) and the structural unit represented by the following formula (b2b) are randomly arranged. The ratio of the volume of the first block to the total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less.

[0021]

Chemical Formula

[0022] <Block copolymer> A block copolymer is a polymer in which a plurality of types of blocks (partial constituent components in which the same type of structural units are repeatedly bonded) are bonded. The blocks constituting the block copolymer may be two types or three or more types. The block copolymer has a first block and a second block.

[0023] 〔First block〕 The first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1) (hereinafter also referred to as the structural unit (b1)).

[0024]

Chemical formula

[0025] As the alkyl group which may have an oxygen atom and / or a silicon atom, 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.

[0026] Examples of the alkyl group 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.

[0027] As the alkylsilyl group, a trialkylsilyl group is preferred. Specifically, a trimethylsilyl group etc. may be mentioned. As the alkylsilylalkyl group, a trialkylsilylalkyl group is preferred. Specifically, a trimethylsilylmethyl group, 2-trimethylsilylethyl group, 3-trimethylsilyl-n-propyl group etc. may be mentioned. As the alkylsilyloxy group, a trialkylsilyloxy group is preferred. Specifically, a trimethylsilyloxy group etc. may be mentioned. As the alkylsilyloxyalkyl group, a trialkylsilyloxyalkyl group is preferred. Specifically, a trimethylsilyloxymethyl group, 2-trimethylsilyloxyethyl group, 3-trimethylsilyloxy-n-propyl group etc. may be mentioned. As the alkoxy group, a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group etc. may be mentioned.

[0028] The total number of carbon atoms of the alkyl group which may be interrupted by an oxygen atom and may be substituted by an alkylsilyl group 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.

[0029] n is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and still more preferably 0.

[0030] 〔Second block〕 The second block is composed of a random copolymer having a structure in which a structural unit represented by the following formula (b2a) (hereinafter also referred to as structural unit (b2a)) and a structural unit represented by the following formula (b2b) (hereinafter also referred to as structural unit (b2b)) are randomly arranged.

[0031]

Chemical formula

[0032] (Constituent unit (b2a)) R 2 is preferably a hydroxy group, a mercapto group, or an alkoxy group.

[0033] R 2 The number of carbon atoms of the alkoxy group as R is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1 or 2. R 2 Examples of the alkoxy group as R include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a tert-pentyloxy group, and the like. Among them, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

[0034] R 2 The number of carbon atoms of the alkylthio group as R is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1 or 2. R 2Examples of the alkylthio group as such include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, an n-pentylthio group, an isopentylthio group, a tert-pentylthio group, and the like. Among them, a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group are preferable, and a methylthio group and an ethylthio group are more preferable.

[0035] R 3 As, an oxygen atom, -NH-, or -NR 4 The number of carbon atoms of the alkylene group which may be interrupted by - and may have a hydroxy group is preferably 1 or more and 5 or less, and more preferably 2 or 3. R 4 Specific examples of the alkyl group as such 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, an isopentyl group, a neopentyl group, a tert-pentyl group, and an n-hexyl group. Among them, a methyl group is preferable.

[0036] R 3 The above-mentioned alkylene group as such is preferably not interrupted by an oxygen atom, -NH-, or -NR 4 - and preferably does not have a hydroxy group, and more preferably is not interrupted by an oxygen atom, -NH-, or -NR 4 - and does not have a hydroxy group.

[0037] R 3 When the above-mentioned alkylene group as such has a hydroxy group, R 3 is preferably a group represented by -R 5 (OH)-R 6 -. R 5 is a chain saturated aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms, R 6 is a single bond or an alkylene group, and R 5 As, the number of carbon atoms of the chain saturated aliphatic hydrocarbon group and R 6As a single bond, or the total number of carbon atoms of the alkylene group is 1 or more and 10 or less.

[0038] R 5 Specific examples of the chain saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms as include the following groups. In addition, the group bonded to R 5 is also shown as a group represented by -O-R 5 (OH)-R 6 - is shown as a group represented by. -O-CH(OH)-R 6 - -O-CH2CH(OH)-R 6 - -O-CH(OH)CH2-R 6 - -O-CH2CH2CH(OH)-R 6 - -O-CH2CH(OH)CH2-R 6 - -O-CH(OH)CH2CH2-R 6 - -O-CH(CH3)CH(OH)-R 6 - -O-C(CH3)(OH)CH2-R 6 - -O-CH(CH2OH)CH2-R 6 - -O-CH2C(CH3)(OH)-R 6 - -O-CH2CH(CH2OH)-R 6 - -O-CH(OH)CH(CH3)-R 6 -

[0039] Among these groups, -O-CH(OH)-R 6 - -O-CH2CH(OH)-R 6 - -O-CH2CH2CH(OH)-R 6 - -O-CH(CH3)CH(OH)-R 6 - -O-CH2C(CH3)(OH)-R 6- is preferred, -O-CH2CH(OH)-R 6 - is more preferred.

[0040] R 6 As the alkylene group for R, a linear or branched alkylene group is preferred, and a linear alkylene group is more preferred. R 6 The number of carbon atoms of the alkylene group for R is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and even more preferably 1.

[0041] R 5 The total of the number of carbon atoms of the chain-like saturated aliphatic hydrocarbon group for R and the number of carbon atoms of the single bond or alkylene group for R is preferably 1 or more and 7 or less, more preferably 2 or more and 5 or less, and even more preferably 3. 6

[0042] In formula (b2a), as the alkyl group having 1 to 5 carbon atoms for R, a linear or branched alkyl group having 1 to 5 carbon atoms is preferred. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, etc. can be mentioned. b2 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 preferred.

[0043]

[0044] b2 In formula (b2a), 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. From the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.

[0044] (Constituent unit (b2b)) In formula (b2b), Rb2 is the same as R in formula (b2a). b2 It is the same as above.

[0045] In the second block, the ratio of the number of moles of the structural unit represented by formula (b2a) to the total number of moles of the structural unit represented by formula (b2a) and the number of moles of the structural unit represented by formula (b2b) is preferably 0.90 or less, more preferably 0.30 or less, and even more preferably 0.01 or more and 0.10 or less from the viewpoint of the orientation with respect to the guide pattern.

[0046] In the block copolymer, the ratio of the volume of the first block to the total volume of the first block and the second block is 20% by volume or more and 80% by volume or less. The ratio of the volume of the first block is preferably 30% by volume or more, more preferably 35% by volume or more. Also, the ratio of the volume of the first block is preferably 70% by volume or less, more preferably 65% by volume or less, and even more preferably 60% by volume or less.

[0047] The ratio of the volume of the first block in the total volume of the first block and the second block in the block copolymer can be determined as follows. 1 From the analysis results of 1H NMR, the molar percentages of the first block and the second block in the block copolymer are calculated respectively, and further, from the molecular weights of the respective blocks, the mass percentages of the respective blocks are calculated respectively. By dividing the mass percentage of each block by the density of each block, the volume ratio of each block is calculated, and the volume percentage of the first block in the block copolymer is calculated from the volume ratio. The density of each block can be estimated by the group contribution method (Fedors, R. F. Polym. Eng. Sci. 1974, 14, 147-154.). When the first block is a polystyrene block (PS), 1.05 g / cm³ can be used as the density of PS. -3 When the second block has a structural unit derived from methyl methacrylate, 1.18 g / cm³ can be used as the density of the structure composed of the structural unit.-3 can be used. When the second block has a structural unit derived from 2-hydroxy-3-(2,2,2-trifluoroethylsulfanyl)propyl methacrylate, the density of the structure composed of the structural unit is 1.43 g / cm -3 can be used. Regarding the density of each block, the density described in literature (Polymer Handbook, 4th ed.; Wiley: New York, 2004.) etc. can also be used.

[0048] 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.

[0049] The number average molecular weight (Mn) (polystyrene conversion standard by size exclusion chromatography) of the block copolymer is not particularly limited, but is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, still more preferably 6,000 or more and 40,000 or less, and particularly preferably 8,000 or more and 30,000 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, still more preferably 1.0 or more and 1.3 or less.

[0050] [Manufacturing method of block copolymer] The block copolymer is not particularly limited and can be produced by a known method. For example, it can be produced by a production method similar to the production method described in Japanese Patent No. 7213495.

[0051] [Organic solvent component] The resin composition for forming a phase separation structure preferably contains an organic solvent. As the organic solvent component, any organic solvent may 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.

[0052] 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, and monobutyl ether of the polyhydric alcohols or the monoacetates of the polyhydric alcohols, or derivatives of polyhydric alcohols such as compounds having an ether bond such as monophenyl ether [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 monoacetates of polyhydric alcohols and derivatives of the aforementioned polyhydric alcohols such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; 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 preferable.

[0053] 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. Generally, the organic solvent component is used such 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.

[0054] <Optional component> The resin composition for forming a phase separation structure may contain optional components other than the above-described block copolymer and the 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.

[0055] ≪Method for manufacturing a structure including a phase separation structure≫ The method for manufacturing a structure including a phase separation structure includes a step of 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 a step of 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 according to the second aspect is not limited to the aspect specifically shown in FIG. 1.

[0056] 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 base agent is applied on a support 1 to form a base agent layer 2 (FIG. 1(I)). Next, a resin composition for forming a phase separation structure is applied onto the undercoat layer 2 to form a layer (BCP layer) 3 containing a block copolymer (Fig. 1 (II); the above is step (i)). Next, heating is performed to carry out an annealing treatment to phase-separate the BCP layer 3 into a phase 3a and a phase 3b (Fig. 1 (III); step (ii)). According to the production method of such an embodiment, that is, the production method having step (i) and step (ii), a structure 3' including a phase separation structure is produced on the support 1 on which the undercoat layer 2 is formed.

[0057] <Step (i)> In step (i), a resin composition for forming a phase separation structure is applied onto the support 1 to form the BCP layer 3. In the embodiment shown in Fig. 1, first, an undercoat agent is applied onto the support 1 to form the undercoat layer 2. By providing the undercoat layer 2 on the support 1, the hydrophilic-hydrophobic balance between the surface of the support 1 and the layer (BCP layer) 3 containing a block copolymer can be achieved. That is, when the undercoat layer 2 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 3 and the support 1 is enhanced. When the undercoat layer 2 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 3 and the support 1 is enhanced. Along with this, due to the phase separation of the BCP layer 3, a phase separation structure oriented in the direction perpendicular to the surface of the support 1 is likely to be formed.

[0058] 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 an underlayer agent may be, for example, a thermopolymerizable resin composition, or may be 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 underlayer agent 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 underlayer agent layer.

[0059] Examples of such resin compositions include a resin composition containing a resin having both the structural units constituting the first block and the second block, and a resin composition containing a resin having both the structural units highly compatible with each block constituting the block copolymer. As the resin composition for the underlayer agent, 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, etc.) 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. In addition, 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 at least a monomer having an aromatic ring and a monomer having a highly polar functional group as monomers. Examples of the monomer having an aromatic ring include aryl groups obtained by removing one hydrogen atom from the ring of aromatic hydrocarbons such as phenyl group, biphenyl group, fluorenyl group, naphthyl group, anthryl group, phenanthryl group, or monomers having heteroaryl groups in which some of the carbon atoms constituting the ring of these groups are substituted with heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, etc. Examples of the monomer having a highly polar functional group include monomers having a trimethoxysilyl group, trichlorosilyl group, epoxy group, glycidyl group, carboxy group, hydroxy group, cyano group, hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with hydroxy groups, etc. In addition, examples of the compound containing both a site highly compatible with styrene and a site highly compatible with methyl methacrylate include compounds containing both an aryl group and a highly polar functional group such as phenethyltrichlorosilane, and compounds containing both an alkyl group and a highly polar functional group such as alkylsilane compounds.

[0060] The resin composition for the primer 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.

[0061] The support 1 is not particularly limited in type as long as a resin composition can be applied on its surface. For example, substrates made of inorganic materials 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 materials 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 1 are not particularly limited. The support 1 does not necessarily have to 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.

[0062] An inorganic and / or organic film may be provided on the surface of the support 1. Examples of the inorganic film include an inorganic anti-reflection film (inorganic BARC). Examples of the organic film include an organic anti-reflection film (organic BARC). The inorganic film can be formed, for example, by coating an inorganic anti-reflection 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 on the substrate with 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. Further, by etching an organic film using a pattern made of a block copolymer formed by processing the BCP layer 3, the pattern can be transferred to the organic film to form an organic film pattern. Therefore, the material for forming the organic film 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 a material for forming an organic film may be a material conventionally used for forming an organic film such as an organic BARC. For example, the ARC series manufactured by Nissan Chemical Industries, Ltd., the AR series manufactured by Rohm and Haas, and the SWK series manufactured by Tokyo Ohka Kogyo Co., Ltd. can be mentioned.

[0063] The method for forming the underlayer 2 by applying the underlayer agent on the support 1 is not particularly limited and can be formed by a conventionally known method. For example, the underlayer agent can be applied on the support 1 by a conventionally known method such as spin coating or using a spinner to form a coating film, and the underlayer 2 can be formed by drying. As the drying method of the coating film, it is sufficient if the solvent contained in the underlayer agent can be volatilized, and examples include a baking method. 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 underlayer 2 after drying the coating film 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.

[0064] Before forming the underlayer 2 on the support 1, the surface of the support 1 may be washed in advance. By washing the surface of the support 1, the coatability of the underlayer agent is improved. As the cleaning treatment method, a conventionally known method can be used, and examples include oxygen plasma treatment, ozone oxidation treatment, acid-base treatment, and chemical modification treatment.

[0065] After forming the underlayer 2, if necessary, the underlayer 2 may be rinsed with a rinse liquid such as a solvent. By this rinsing, uncrosslinked portions in the underlayer 2 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 a direction perpendicular to the surface of the support 1 is likely to be formed. Note that 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 the cleaning, post-baking may be performed to volatilize the rinse liquid. The temperature condition for this post-baking is preferably 80°C or higher and 300°C or lower, more preferably 100°C or higher and 270°C or lower. The baking time is preferably 30 seconds or longer and 500 seconds or shorter, more preferably 60 seconds or longer and 240 seconds or shorter. The thickness of the underlayer 2 after such post-baking is preferably about 1 nm or more and 10 nm or less, more preferably about 2 nm or more and 7 nm or less.

[0066] Next, a layer (BCP layer) 3 containing a block copolymer is formed on the underlayer 2. The method for forming the BCP layer 3 on the underlayer 2 is not particularly limited. For example, a method of applying the resin composition for forming a phase separation structure of the above-described embodiment on the underlayer 2 to form a coating film and drying it by a conventionally known method such as spin coating or using a spinner can be mentioned.

[0067] The thickness of the BCP layer 3 only needs to be sufficient for phase separation to occur. Considering the type of the support 1, or the structural period size of the phase separation structure to be formed or the uniformity of the nanostructure, etc., it is preferably 20 nm or more and 100 nm or less, more preferably 30 nm or more and 80 nm or less. For example, when the support 1 is a Si substrate, the thickness of the BCP layer 3 is preferably adjusted to 10 nm or more and 100 nm or less, more preferably 30 nm or more and 80 nm or less.

[0068] <Step (ii)> In Step (ii), the BCP layer 3 formed on the support 1 is phase-separated. By heating the support 1 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 1 is exposed by selective removal of the block copolymer. That is, a structure 3' including a phase-separated structure phase-separated into a phase 3a and a phase 3b is manufactured on the support 1. The temperature condition for the annealing treatment is preferably 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 higher and 270°C or lower. 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.

[0069] <Optional Step> The method for manufacturing a structure including a phase-separation structure is not limited to the above-described embodiment, and may have steps (optional steps) other than Steps (i) and (ii).

[0070] Examples of such optional steps include a step of selectively removing a phase composed of at least one kind of block among the first block and the second block constituting the block copolymer in the BCP layer 3 (hereinafter referred to as "Step (iii)"), a guide pattern formation step, and the like.

[0071] ·Regarding Step (iii) In Step (iii), a phase composed of at least one kind of block among the first block and the second block constituting the block copolymer in the BCP layer formed on the undercoat layer 2 is selectively removed. Thereby, a fine pattern (polymer nanostructure) is formed.

[0072] As a method for selectively removing a phase composed of blocks, there may be mentioned 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 (b1) is not selectively removed, and the phase composed of the second block (b2) is selectively removed.

[0073] Figure 2 shows an example of an embodiment of step (iii). In the embodiment shown in Figure 2, by performing oxygen plasma treatment on the structure 3' manufactured on the support 1 in step (ii), the phase 3a is selectively removed, and a pattern (polymer nanostructure) composed of the separated phase 3b is formed. In this case, the phase 3b is the phase composed of the first block, and the phase 3a is the phase composed of the second block.

[0074] The support 1 on which a pattern is formed by phase separation of the BCP layer 3 composed of the block copolymer as described above can be used as it is, but by further heating, the shape of the pattern (polymer nanostructure) on the support 1 can also be changed. The temperature condition for heating is preferably equal to or higher than the glass transition temperature of the block copolymer used and lower than the thermal decomposition temperature. Further, the heating is preferably performed in a gas with low reactivity such as nitrogen.

[0075] ·Regarding the guide pattern formation step In the method for manufacturing a structure including a phase-separated structure, a step of providing a guide pattern on the underlayer (guide pattern formation step) may be provided between the above-described steps (i) and (ii). Thereby, it becomes possible to control the array structure of the phase-separated 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 undercoat 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 undercoat layer 2. 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.

[0076] The guide pattern can be formed using, for example, a resist composition. The resist composition for forming the guide pattern can generally be appropriately selected from resist compositions and modified products thereof that are generally used for forming resist patterns and are compositions having an affinity with any of the blocks constituting the block copolymer. As the resist composition, it may be either a positive resist composition that forms a positive pattern in which the exposed portion of the resist film is dissolved and removed or a negative resist composition that forms a negative pattern in which the unexposed portion of the resist film is dissolved and removed, but a negative resist composition is preferred. As the negative resist composition, for example, it contains 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. A resist composition containing the above is preferred. After the BCP composition is poured onto the undercoat layer on which the guide pattern is formed, an annealing treatment is performed to cause phase separation. Therefore, the resist composition for forming the guide pattern is preferably a composition capable of forming a resist film excellent in solvent resistance and heat resistance. ≪Block Copolymer≫ The block copolymer has a first block and a second block. The first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1). The second block is composed of a random copolymer having a structure in which the structural unit represented by the following formula (b2a) and the structural unit represented by the following formula (b2b) are randomly arranged. The ratio of the volume of the first block to the total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less.

[0077] [Chemical formula] (In formula (b1), R 1 is an alkyl group which may have an oxygen atom and / 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, and R b1 is a hydrogen atom or a methyl group. In formula (b2a), R 2 is a hydroxy group, a mercapto group, an alkoxy group, or an alkylthio group, R 3 is an alkylene group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom, -NH-, or -NR 4 - and may have a hydroxy group, and R 4 is an alkyl group having 1 to 6 carbon atoms. In formula (b2a) and formula (b2b), R b2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and a plurality of R b2 may be the same or different from each other.)

[0078] A preferred embodiment of the block copolymer is the same as the block copolymer contained in the resin composition for forming a phase separation structure.

[0079] As described above, the present inventors provide the following (1) to (7). (1) A resin composition for forming a phase separation structure containing a block copolymer having a first block and a second block, wherein the first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), the second block is composed of a random copolymer having a structure in which a structural unit represented by the following formula (b2a) and a structural unit represented by the following formula (b2b) are randomly arranged, and a resin composition for forming a phase separation structure, wherein a ratio of a volume of the first block to a total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less.

Chemical formula

Examples

[0080] The present invention will be described in more detail based on the examples, but the present invention is not limited by these examples.

[0081] Hereinafter, the block copolymers used in the examples and comparative examples will be described. BCP(A1): A block copolymer composed of a block made of polystyrene and a block made of a random copolymer of 2-hydroxy-3-(2,2,2-trifluoroethylsulfanyl)propyl methacrylate (HFMA) and methyl methacrylate (prepared with reference to the examples of JP-A-2022-20519) BCP(B1) to BCP(B4): Block copolymers composed of a block made of polystyrene and a block made of a random copolymer of 2-methoxyethyl methacrylate and methyl methacrylate BCP(C1) to BCP(C3): Block copolymer of a block made of polystyrene and a block made of a random copolymer of 2-(methylthio)ethyl methacrylate and methyl methacrylate BCP(D1) to BCP(D3): Block copolymer of a block made of polystyrene and a block made of a random copolymer of 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate BCP(E1) to BCP(E3): Block copolymer of a block made of polystyrene and a block made of a random copolymer of 2-hydroxypropyl methacrylate and methyl methacrylate

[0082] <Measurement of the volume of each block> The mole % of each block in the block copolymer 1 was calculated from the results of 1H NMR analysis, and further, the mass % of each block was calculated. Next, the volume ratio of each block was calculated by dividing the mass % of each block by the density of each block. From the said volume ratio, the ratio of the volume of the polystyrene block in the total volume of the block copolymer was calculated. The density of each block was estimated by the group contribution method (Fedors, R. F. Polym. Eng. Sci. 1974, 14, 147 - 154.). As the density of the polystyrene block, 1.05 g / cm -3 was used. As the density of the structure composed of the structural units derived from methyl methacrylate, 1.18 g / cm -3 was used. As the density of the structure composed of the structural units derived from 2-hydroxy-3-(2,2,2-trifluoroethylsulfanyl)propyl methacrylate, 1.43 g / cm -3 was used (BCP(A1)). In BCP(B1) to BCP(B4), BCP(C1) to BCP(C3), BCP(D1) to BCP(D3), and BCP(E1) to BCP(E3), as the density of the structure composed of the structural units corresponding to the structural unit (b2a), all 1.18 g / cm -3 was used.

[0083] The number average molecular weight (Mn), dispersity (PDI = Mw / Mn), and the ratio of the volume of the polystyrene block (PS) to the total volume of the block copolymer (volume %) of each block copolymer are summarized in Table 1. Also, the ratios (x:y:z) of the number of moles of the structural unit (b1), the number of moles of the structural unit (b2a), and the number of moles of the structural unit (b2b) to the total number of moles of each structural unit of each block copolymer, and the ratio of the number of moles of the structural unit (b2a) to the total number of moles of the structural unit (b2a) and the structural unit (b2b) (y / (y + z)) are summarized in Table 2.

[0084]

Table 1

[0085] <Preparation of a resin composition for forming a phase separation structure and production of a structure including the phase separation structure> Each BCP shown in Table 2 was mixed with propylene glycol monomethyl ether acetate and dissolved to prepare a resin composition for forming a phase separation structure (solid content concentration: 0.8% by mass) for each example.

[0086] After forming a guide pattern with the resist composition, a structure including a phase separation structure was obtained by a production method having the following steps (i) and (ii) using the resin composition for forming a phase separation structure of each of the above examples.

[0087] Formation of guide pattern The organic antireflection film composition "ARC-29A" (trade name, manufactured by Brewer Science) was applied onto a 12-inch silicon wafer using a spinner, and baked at 205 °C for 60 seconds on a hot plate to dry it, thereby forming an organic antireflection film with a film thickness of 89 nm. After spin-coating a neutral film composition solution (underlayer agent) onto the organic antireflection film, it was heated at 250 °C for 600 seconds. As a result, a thin film with a film thickness of 60 nm composed of the neutral film composition was formed on the surface of the substrate. Next, the underlayer agent layer was rinsed with OK73 thinner (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 15 seconds to remove random copolymers such as uncrosslinked portions. After that, it was baked at 100 °C for 60 seconds. A resist film for guide pattern formation was applied onto the film using a spinner, prebaked (PAB) on a hot plate, and dried, thereby forming a resist film for guide pattern formation with a film thickness of 90 nm. An ArF excimer laser (193 nm) was selectively irradiated through a mask pattern using an ArF exposure apparatus XT-1900Gi (manufactured by ASML). Then, post-exposure bake (PEB) treatment was performed, followed by development with butyl acetate and spin-drying. Next, post-bake treatment was performed under the conditions of 100 °C for 1 minute and then 200 °C for 5 minutes to form a guide pattern adjusted to a space dimension four times the d value of the block copolymer used.

[0088] As the neutral film composition solution, the following NL-1 or NL-2 was used. NL-1: A PGMEA solution (copolymer concentration 2.0 mass%) of a copolymer having styrene (St) units, methyl methacrylate (MMA) units, and 2-hydroxyethyl methacrylate (HEMA) units (St / MMA / HEMA = 49 / 46 / 5 (mol%), number average molecular weight 28,000) NL-2: A PGMEA solution (copolymer concentration 2.0 mass%) of a copolymer having styrene (St) units, methyl methacrylate (MMA) units, and 2-hydroxyethyl methacrylate (HEMA) units (St / MMA / HEMA = 70 / 25 / 5 (mol%), number average molecular weight 29,000)

[0089] Step (i): On the undercoat layer, the resin composition of each example was spin-coated so that the film thickness became 30 nm to form a resin composition layer (layer containing a block copolymer).

[0090] Step (ii): The resin composition layer formed on the undercoat layer was pre-baked at 90 °C for 60 seconds in a nitrogen atmosphere, and then annealed at 220 °C for 30 minutes in a nitrogen atmosphere to form a phase-separated structure.

[0091] Step (iii): For the substrate on which the phase-separated structure was formed, oxygen plasma treatment (200 mL / min, 40 Pa, 40 °C, 200 W, 10 seconds) was performed using TCA-3822 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to selectively remove the phase made of PMMA.

[0092] (Evaluation of vertical alignment) The surface (phase-separated state) of the obtained substrate was observed with a length-measuring SEM (scanning electron microscope, trade name: CG6300, manufactured by Hitachi High-Technologies Corporation). As a result of such observation, based on the following evaluation criteria, the phase separation performance was evaluated. The results are shown in Table 2 as "phase vertical alignment". A: Vertical alignment was observed over the entire surface B: Vertical alignment was not partially observed

[0093] (Evaluation of guide alignment) The surface (phase-separated state) of the obtained substrate was observed with a length-measuring SEM (scanning electron microscope, trade name: CG6300, manufactured by Hitachi High-Technologies Corporation). As a result of such observation, based on the following evaluation criteria, the guide alignment was evaluated. The results are shown in Table 2 as "guide alignment". A: A phase-separated structure was formed over the entire surface of the substrate on which the guide pattern was formed B: A phase-separated structure was not formed in a part of the substrate on which the guide pattern was formed

[0094] [Table 2]

[0095] As shown in Tables 1 and 2, it was confirmed that in Examples 1 to 13 containing a predetermined block copolymer, a phase separation structure with good vertical alignment could be formed. In particular, in Examples 5 to 12 where the molar ratio of the constitutional unit (b2a) is 0.10 or less, it was also confirmed that in addition to the vertical alignment, the alignment with respect to the guide pattern is good.

Claims

1. A resin composition for forming a phase separation structure containing a block copolymer having a first block and a second block, wherein the first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), the second block is composed of a random copolymer having a structure in which the structural unit represented by the following formula (b2a) and the structural unit represented by the following formula (b2b) are randomly arranged, A resin composition for forming a phase separation structure, wherein the ratio of the volume of the first block to the total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less. 【Chemical 1】 (In formula (b1), R １ is an alkyl group which may have an oxygen atom and / 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, and R ｂ１ is a hydrogen atom or a methyl group.) In formula (b2a), R ２ is a hydroxy group, a mercapto group, an alkoxy group, or an alkylthio group, and R ３ is an oxygen atom, -NH-, or -NR ４ -, may be interrupted, and is an alkylene group having 1 to 10 carbon atoms which may have a hydroxy group, and R ４ is an alkyl group having 1 to 6 carbon atoms. In formula (b2a) and formula (b2b), R ｂ２ is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and a plurality of R ｂ２ may be the same or different. )

2. The resin composition for forming a phase separation structure according to claim 1, wherein in the second block, the ratio of the number of moles of the structural unit represented by the formula (b2a) to the total of the number of moles of the structural unit represented by the formula (b2a) and the number of moles of the structural unit represented by the formula (b2b) is 0.90 or less.

3. The resin composition for forming a phase separation structure according to claim 2, wherein the ratio is 0.30 or less.

4. The resin composition for forming a phase separation structure according to claim 3, wherein the ratio is 0.01 or more and 0.10 or less.

5. The aforementioned R ２ is a hydroxy group, a mercapto group, or an alkoxy group, and Said R ３ wherein the alkylene group as, an oxygen atom, -NH-, or -NR ４ The resin composition for forming a phase-separated structure according to claim 1, which is not interrupted by-.

6. Applying the resin composition for forming a phase separation structure according to any one of claims 1 to 5 on a support to form a layer containing the block copolymer, Phase-separating the layer containing the block copolymer, A method for manufacturing a structure having a phase separation structure, comprising:

7. A block copolymer having a first block and a second block, wherein the first block is composed of a polymer having a repeating structure of a structural unit represented by the following formula (b1), the second block is composed of a random copolymer having a structure in which the structural unit represented by the following formula (b2a) and the structural unit represented by the following formula (b2b) are randomly arranged, A block copolymer, wherein the ratio of the volume of the first block to the total of the volume of the first block and the volume of the second block is 20% by volume or more and 80% by volume or less. [Chemical 2] (In formula (b1), R １ is an alkyl group which may have an oxygen atom and / 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, and R ｂ１ is a hydrogen atom or a methyl group.) In formula (b2a), R ２ is a hydroxy group, a mercapto group, an alkoxy group, or an alkylthio group, and R ３ is an oxygen atom, -NH-, or -NR ４ -, which may be interrupted and may have a hydroxy group, and is an alkylene group having 1 to 10 carbon atoms, and R ４ is an alkyl group having 1 to 6 carbon atoms. In formula (b2a) and formula (b2b), R ｂ２ is, independently of each other, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and a plurality of R ｂ２ may be the same or different. )

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