Resin composition for forming phase-separated structures, method for producing structures containing phase-separated structures, and block copolymer

Abstract

The present invention provides a resin composition for forming a phase-separated structure that is capable of forming a phase-separated structure with excellent orientation and in-plane uniformity, a method for producing a structure containing a phase-separated structure using the same, and a block copolymer to be used in the resin composition for forming the phase-separated structure. [Solution] A resin composition for forming a phase-separated structure, comprising a block copolymer having three blocks, the first to the third, the third block being located between the first and second blocks, the first block being composed of a polymer consisting of a repeating structure of a structural unit represented by formula (b1), the second block being composed of a polymer consisting of a repeating structure of a structural unit represented by formula (b2), and the third block being composed of a polymer consisting of a repeating structure of a structural unit derived from a monomer having a LogP value higher than the LogP value of methyl methacrylate. TIFF2026077596000021.tif41134

Description

[Technical Field]

[0001] The present invention relates to a resin composition for forming a phase-separated structure, a method for producing a structure containing a phase-separated structure, and a block copolymer. [Background technology]

[0002] In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), there has been a growing demand for technologies to process more delicate structures. In response to such demands, technologies are being developed to form finer patterns by utilizing phase separation structures formed by the self-assembly of block copolymers, in which mutually incompatible blocks are bonded together (see, for example, Patent Document 1).

[0003] The block copolymer described above separates at a microscopic level due to the repulsion between mutually immiscible blocks (phase separation), and by heat treatment or other processes, it forms a structure with a regular periodic structure. Specific examples of this periodic structure include cylinders (columnar), lamellae (plate-like), and spheres (spherical).

[0004] To utilize the phase separation structure of block copolymers, it is essential to form self-assembled nanostructures, which are created by microphase separation, only in specific regions and to align them in a desired direction. To achieve this positional and orientation control, processes such as graphoepitaxy, which controls the phase separation pattern using guide patterns, and chemical epitaxy, which controls the phase separation pattern based on differences in the chemical state of the substrate, have been proposed (see, for example, Non-Patent Document 1).

[0005] Block copolymers form structures with a regular periodic structure through phase separation. The "period of the structure" refers to the period of the phase structure observed when a phase-separated structure is formed, and is the sum of the lengths of each phase that is incompatible with the others. When a phase-separated structure forms a cylinder structure perpendicular to the substrate surface, the period of the structure (L0) is the distance (pitch) between the centers of two adjacent cylinder structures.

[0006] It is known that the period (L0) of the structure is determined by intrinsic polymerization characteristics such as the degree of polymerization N and the Flory-Huggins interaction parameter χ. That is, the greater 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.

[0007] 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.]

[0008] Therefore, by adjusting the composition and total molecular weight of the block copolymer, the period (L0) of the structure can be adjusted. For this reason, in order to form a structure with a relatively large L0 by utilizing the phase separation structure formed by the self-assembly of the block copolymer, a method of increasing the molecular weight of the block copolymer has been considered.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Non-Patent Documents

[0010]

Non-Patent Document 1

[0011] However, simply increasing the molecular weight of the block copolymer can lead to a decrease in the phase separation rate, resulting in a problem where, if you want to orient the copolymer perpendicular or horizontally to the substrate surface, both phases may end up mixed together.

[0012] Furthermore, when using the phase separation structure formed by the self-assembly of block copolymers to create finer patterns, excellent in-plane uniformity of pattern dimensions is required.

[0013] The present invention has been made in view of the above circumstances, and aims to provide a resin composition for forming a phase separation structure that can form a phase separation structure with excellent orientation and in-plane uniformity, a method for producing a structure including a phase separation structure using the same, and a block copolymer to be used in the resin composition for forming the phase separation structure. [Means for solving the problem]

[0014] In order to solve the above problems, the inventors of this invention conducted extensive research and found that the above problems could be solved by using a predetermined block copolymer, and thus completed the present invention. Specifically, the present invention provides the following.

[0015] The first embodiment is a resin composition for forming a phase-separated structure containing a block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of structural units derived from high-LogP monomers. The aforementioned high-LogP monomer has a LogP value higher than that of methyl methacrylate, making it a resin composition for forming phase-separated structures. [ka] (In formula (b1), R 11 R is a hydrogen atom or a methyl group. 12 is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R 21 (This is a hydrogen atom or a methyl group.)

[0016] A second embodiment is a method for manufacturing a structure having a phase-separated structure, comprising: applying a resin composition for forming a phase-separated structure according to the first embodiment onto a support to form a layer containing a block copolymer; and phase-separating the layer containing the block copolymer.

[0017] A third embodiment is a block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of monomer-derived structural units. The aforementioned monomer is a block copolymer whose LogP value is higher than that of methyl methacrylate. [ka] (In formula (b1), R 11is a hydrogen atom or a methyl group. R 12 is a substituent having 1 to 5 carbon atoms. n is an integer of 0 or more and 5 or less. In formula (b2), R 21 is a hydrogen atom or a methyl group.) [Effect of the Invention]

[0018] 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 orientation and in-plane uniformity, a method for producing a structure including the phase separation structure using the same, and a block copolymer used for the resin composition for forming the phase separation structure. [Brief Description of the Drawings]

[0019] [Figure 1] It is a schematic process diagram for explaining an embodiment of a method for producing a structure including a phase separation structure. [Figure 2] It is a diagram for explaining an embodiment of an arbitrary process. [Figure 3] It is a diagram showing examples corresponding to each evaluation criterion of vertical orientation in the examples. [Figure 4] It is a diagram showing examples corresponding to each evaluation criterion of horizontal orientation in the examples. [Modes for Carrying Out the Invention]

[0020] 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.

[0021] [Resin Composition for Forming Phase Separation Structure] The resin composition for forming a phase-separated structure contains a block copolymer having a first block, a second block, and a third block. The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of a structural unit represented by the following formula (b1). The second block is composed of a polymer consisting of a repeating structure of a structural unit represented by the following formula (b2). The third block is composed of a polymer consisting of a repeating structure of a structural unit derived from a high-LogP monomer. The LogP value of the high-LogP monomer is higher than that of methyl methacrylate. [ka] (In formula (b1), R 11 R is a hydrogen atom or a methyl group. 12 is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R 21 (This is a hydrogen atom or a methyl group.)

[0022] The inventors investigated replacing blocks composed of structural units derived from methyl methacrylate, etc., with blocks in which structural units derived from methyl methacrylate, etc., and structural units that reduce the interaction parameter (χ) of the block copolymer are arranged in a disordered manner, in order to improve orientation. It is generally said that the phase separation rate decreases as the interaction parameter increases. Therefore, it is thought that by using a block copolymer with a small interaction parameter, the phase separation rate will improve, and as a result, the orientation will improve. However, when such a block copolymer is used, although it is possible to form a phase separation structure with excellent orientation, there was room for improvement in in-plane heterogeneity.

[0023] In contrast, the resin composition for forming a phase-separated structure according to the first embodiment can form a phase-separated structure with excellent orientation and in-plane uniformity. The reason for obtaining such an effect is presumed to be as follows.

[0024] When selectively removing a phase consisting of blocks in which multiple types of constituent units are arranged in a disordered manner after phase separation of a layer containing a block copolymer, the in-plane uniformity decreases because some of the phase cannot be completely removed due to the non-uniform solubility of the blocks. In contrast, in the resin composition for forming a phase separation structure of the first embodiment, blocks composed of constituent units derived from high-LogP monomers that reduce the interaction parameter (χ) of the block copolymer are placed between blocks composed of constituent units derived from styrene, etc., and blocks composed of constituent units derived from methyl methacrylate, etc., so that the solubility of the blocks is uniform. As a result, it is possible to form a phase separation structure that is excellent in orientation as well as in in-plane uniformity.

[0025] <Block copolymer> [Block 1] The first block is composed of a polymer consisting of a repeating structure of a constituent unit represented by the following formula (b1) (hereinafter also referred to as constituent unit (b1)). [ka] (In formula (b1), R 11 R is a hydrogen atom or a methyl group. 12 (where n is a substituent with 1 to 5 carbon atoms, and n is an integer between 0 and 5.)

[0026] R 12 The number of carbon atoms in the substituent is preferably 1 or more and 3 or less. 12 Examples of substituents include optionally substituted hydrocarbon groups, optionally substituted alkoxy groups, optionally substituted alkylsilyl groups, and optionally substituted alkylsilyloxy groups. Among these, optionally substituted hydrocarbon groups are preferred.

[0027] R 12 Examples of hydrocarbon groups that may have substituents include alkyl groups that may have substituents and cycloalkyl groups that may have substituents. Among these, alkyl groups that may have substituents are preferred.

[0028] R 12 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl groups.

[0029] R 12 Examples of cycloalkyl groups include cyclobutyl groups and cyclopentyl groups.

[0030] R 12 Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and tert-butoxy groups.

[0031] R 12 Examples of alkylsilyl groups include trialkylsilyl groups such as trimethylsilyl groups.

[0032] R 12 Examples of alkylsilyloxy groups include trialkylsilyloxy groups such as trimethylsilyloxy groups.

[0033] R 12 Examples of substituents that the hydrocarbon group, alkoxy group, alkylsilyl group, and alkylsilyloxy group may have include alkoxy groups, alkylsilyl groups, alkylsilyloxy groups, and halogen atoms.

[0034] n is preferably an integer between 0 and 3, more preferably 0 or 1, and even more preferably 0.

[0035] [Second block] The second block is composed of a polymer consisting of a repeating structure of a constituent unit represented by the following formula (b2) (hereinafter also referred to as constituent unit (b2)). [ka] (In formula (b2), R21 (This is a hydrogen atom or a methyl group.)

[0036] [Third block] The third block consists of polymers composed of repeating structures of structural units derived from high-LogP monomers. The LogP value of the high-LogP monomer is higher than that of methyl methacrylate (1.207). Note that "LogP value" refers to the logarithm of the octanol / water partition coefficient (Pow), and in this specification, the LogP values ​​of monomers are calculated using calculation software from Advanced Chemistry Development (ACD / Labs).

[0037] The LogP value of the high-LogP monomer is preferably 1.21 or higher, more preferably 1.21 to 4, even more preferably 1.25 to 4, particularly preferably 1.3 to 4, and most preferably 1.35 to 3.5. The desired effect is more likely to be obtained when the value is within the above range.

[0038] The constituent units derived from high-LogP monomers may be constituent unit (b1) or constituent unit (b2), but it is preferable that they are neither constituent unit (b1) nor constituent unit (b2).

[0039] The constituent units derived from high-LogP monomers are preferably the constituent units represented by the following formula (b3) (hereinafter also referred to as "constituent unit (b3)"). [ka] (In equation (b3), R 31 L is a hydrogen atom or a methyl group. L is a single bond or a divalent linking group. 32 (This refers to an organic group having between 1 and 15 carbon atoms.)

[0040] Examples of divalent linking groups as L include divalent linking groups containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms.

[0041] Examples of divalent linking groups containing heteroatoms include groups represented by -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NR-, -NR-, -NR-C(=NR)-, -S-, -S(=O)2-, and -S(=O)2-O- [wherein R is independently a hydrogen atom or a substituent (e.g., an alkyl group and an acyl group)]. Unless otherwise specified in this specification, the orientation of the divalent group bond is not particularly limited.

[0042] The number of carbon atoms in the alkyl group and acyl group as R is preferably 1 to 10, and more preferably 1 to 5.

[0043] L is a group represented as -C(=O)-O-, where the carbonyl group in -C(=O)-O- is R 31 It is preferable that it is bonded to the carbon atom to which it is bonded.

[0044] R 32 The number of carbon atoms in the organic group is preferably 1 to 10, and more preferably 2 to 8. 32 Examples of organic groups include linear hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, and combinations thereof.

[0045] R 32 This is an alkyl group having 2 to 15 carbon atoms, which may have substituents, or -R 33 -R 34 It is preferable that the group is represented by . Here, R 33 R is a single bond or a methylene group. 34 This is a cyclic alkyl group which may have substituents, an aromatic hydrocarbon group which may have substituents, or a heterocyclic group which may have substituents.

[0046] R 32The number of carbon atoms in the alkyl group is preferably 2 to 10, and more preferably 2 to 8. The alkyl group may be linear or branched. Examples of alkyl groups include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group.

[0047] R 32 Examples of substituents that the alkyl group may have include halogen atoms, alkenyl groups, silicon atom-containing groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0048] Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine atoms. The number of carbon atoms in the alkenyl group as a substituent is preferably 2 to 10. The alkenyl group may be linear or branched. Examples of alkenyl groups include vinyl groups and propenyl groups. Examples of silicon atom-containing groups used as substituents include silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triphenylsilyl group.

[0049] The alicyclic hydrocarbon group used as a substituent may be either a monocyclic or polycyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The number of carbon atoms in the monocycloalkane is preferably 3 to 6. Examples of monocycloalkanes include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred. The number of carbon atoms in the polycycloalkane is preferably 7 to 12. Specific examples of polycycloalkanes include adamantane, norbornane, and isobornane, which are polycycloalkanes having a cross-linked polycyclic skeleton.

[0050] The aromatic hydrocarbon group used as a substituent may be a monocyclic aromatic group, a group formed by the condensation of two or more aromatic hydrocarbon groups, or a group formed by the single bond between two or more aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, and biphenylyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, and more preferably 6 to 10.

[0051] R 34 The number of carbon atoms in the cycloalkyl group is preferably 3 to 10, and more preferably 4 to 8. 34 Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0052] R 34 The aromatic hydrocarbon group may be a monocyclic aromatic group, a group formed by the condensation of two or more aromatic hydrocarbon groups, or a group formed by the single bond between two or more aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, and biphenylyl groups. 34 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 15, and more preferably 6 to 10.

[0053] R 34 The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group, but an aliphatic heterocyclic group is preferred. 34 The number of carbon atoms in the heterocyclic group is preferably 3 to 10, and more preferably 3 to 6. 34 As the heteroatom included in the heterocyclic group, an oxygen atom is preferred. Examples of aliphatic heterocyclic rings that constitute an aliphatic heterocyclic group include tetrahydrofuran rings, pyrrolidine rings, tetrahydrothiophene rings, tetrahydropyran rings, piperidine rings, and thiane rings.

[0054] R 34Examples of substituents that cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups may have include halogen atoms, alkyl groups, alkenyl groups, halogenated alkyl groups, silicon atom-containing groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Preferred embodiments of halogen atoms, alkenyl groups, silicon atom-containing groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups are R 32 This is similar to the substituents that an alkyl group may have.

[0055] The number of carbon atoms in the alkyl group as a substituent is preferably 1 to 10. The alkyl group may be linear or branched.

[0056] Examples of alkyl halides used as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. Fluorinated alkyl groups are preferred as the alkyl halides, and perfluoroalkyl groups are particularly preferred.

[0057] The ratio of moles of constituent units in the first block to the total number of moles of constituent units in the first, second, and third blocks is preferably 10 mol% or more and 80 mol% or less. The ratio of moles of constituent units in the first block is more preferably 20 mol% or more, even more preferably 30 mol% or more, particularly preferably 40 mol% or more, and most preferably 50 mol% or more. Furthermore, the ratio of moles of constituent units in the first block is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

[0058] The ratio of moles of constituent units in the second block to the total number of moles of constituent units in the first block, the second block, and the third block is preferably 10 mol% or more and 80 mol% or less. The ratio of moles of constituent units in the second block is more preferably 15 mol% or more, even more preferably 20 mol% or more, and particularly preferably 25 mol% or more. Furthermore, the ratio of moles of constituent units in the second block is more preferably 70 mol% or less, even more preferably 60 mol% or less, particularly preferably 50 mol% or less, and most preferably 45 mol% or less.

[0059] The ratio of moles of the constituent units of the third block to the sum of the moles of the constituent units of the first block, the second block, and the third block is preferably 0.1 mol% to 20 mol%, as this makes it easier to obtain the desired effect. The ratio of moles of the constituent units of the third block is more preferably 0.5 mol% or more, and even more preferably 1 mol% or more. Furthermore, the ratio of moles of the constituent units of the third block is more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, as this tends to result in excellent orientation and in-plane uniformity.

[0060] The block copolymer may have other blocks in addition to the first block, the second block, and the third block. In a preferred embodiment, the block copolymer is a triblock copolymer composed of the first block, the second block, and the third block.

[0061] The number-average molecular weight (Mn) of the block copolymer is preferably 50,000 to 500,000, more preferably 100,000 to 300,000, even more preferably 100,000 to 200,000, and particularly preferably 120,000 to 180,000, from the standpoint of being able to better exhibit the desired effect. The molecular weight dispersion (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. In this specification, "number-average molecular weight" (Mn) and "weight-average molecular weight" (Mw) refer to the number-average molecular weight and weight-average molecular weight in terms of standard polystyrene, determined by gel permeation chromatography (GPC), unless otherwise specified. The unit (gmol) is used for the value of Mn or Mw. -1 If a parentheses is present, the value represents the molar mass.

[0062] The period (L0) of a structure containing a phase-separated structure produced using a block copolymer is not particularly limited, but may be, for example, 30 nm or more, 40 nm or more, or 50 nm or more. It may also be 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, or 60 nm or less.

[0063] <Homopolymer> The resin composition for forming a phase separation structure preferably contains a homopolymer. This makes it easier to obtain the desired effect, especially in a resin composition for forming a phase separation structure that exhibits a cylinder phase separation structure.

[0064] As the homopolymer, at least one polymer selected from the group consisting of polymer (I) consisting of a repeating structure of the constituent unit represented by formula (b1) above, and polymer (II) consisting of a repeating structure of the constituent unit represented by formula (b2) above, is preferred. The constituent units of polymer (I) and polymer (II) may be the same as or different from the constituent units of the block copolymer.

[0065] Polystyrene is preferred as polymer (I). Polymethyl methacrylate is preferred as polymer (II).

[0066] The number-average molecular weight (Mn) of the homopolymer is preferably 500 to 50,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 5,000.

[0067] The homopolymer content is preferably 10 to 200 parts by mass, more preferably 20 to 160 parts by mass, and even more preferably 30 to 140 parts by mass, based on 100 parts by mass of block copolymer content.

[0068] The content of polymer (I) is preferably 5 to 130 parts by mass, more preferably 15 to 120 parts by mass, and even more preferably 20 to 110 parts by mass, based on 100 parts by mass of the block copolymer. The content of polymer(II) is preferably 5 to 60 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 45 parts by mass, based on 100 parts by mass of the block copolymer.

[0069] <Organic solvent components> The resin composition for forming the phase separation structure preferably contains an organic solvent. Any organic solvent that can dissolve each component used and form a homogeneous solution is acceptable. Conventionally, any organic solvent selected from organic solvents known as solvents for resin-based compositions can be used.

[0070] Examples of organic solvent components 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, and dipropylene glycol monoacetate; derivatives of polyhydric alcohols, for example, monoalkyl ethers of the aforementioned polyhydric alcohols, monoalkyl ethers of the aforementioned polyhydric alcohol monoacetates, monophenyl ethers of the aforementioned polyhydric alcohols, and compounds having ether bonds such as monophenyl ethers of the aforementioned polyhydric alcohol monoacetates (monoalkyl ethers and Examples include monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers. (Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.) Cyclic ethers such as dioxane; esters other than methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and derivatives of the aforementioned polyhydric alcohols; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. The organic solvent components may be used individually or as a mixture of two or more solvents. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0071] 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 thickness so that the concentration of the resin composition for forming a phase separation structure is at a concentration that can be applied. Generally, the organic solvent component is 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.

[0072] <Other ingredients> The resin composition for forming phase-separated structures may contain components other than the block copolymer, homopolymer, and organic solvent components described above. Other components include other resins, surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, sensitizers, base enhancers, and basic compounds.

[0073] ≪Method for manufacturing a structure containing a phase-separated structure≫ A method for manufacturing a structure containing a phase-separated structure includes applying a resin composition for forming a phase-separated structure onto a support to form a layer containing a block copolymer (hereinafter referred to as "step (i)") and separating the layer containing the block copolymer (hereinafter referred to as "step (ii)"). The manufacturing method for a structure including such a phase-separated structure will be described in detail below with reference to Figure 1. However, the manufacturing method for a structure including a phase-separated structure is not limited to the embodiment specifically shown in Figure 1.

[0074] Figure 1 shows an example of one embodiment of a method for manufacturing a structure including a phase-separated structure. In the embodiment shown in Figure 1, first, a primer is applied to the support 41 to form a primer layer 42 (Figure 1(I)). Next, a resin composition for forming a phase-separated structure is applied to the primer layer 42 to form a layer containing a block copolymer (BCP layer) 43 (Figure 1(II); step (i) above). Next, the BCP layer 43 is heated and annealed to separate it into phases 43a and 43b (Figure 1(III); step(ii)). According to the manufacturing method of this 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 a primer layer 42 is formed.

[0075] <Process (i)> In step (i), a resin composition for forming a phase separation structure is applied to the support 41 to form a BCP layer 43. In the embodiment shown in Figure 1, first, a primer is applied to the support 41 to form a primer layer 42. By providing a primer layer 42 on the support 41, a hydrophilic-hydrophobic balance can be achieved between the surface of the support 41 and the layer containing the block copolymer (BCP layer) 43. In other words, if the primer layer 42 contains a resin component having a structural unit that constitutes the first block, the adhesion between the phase of the BCP layer 43 consisting of the first block and the support 41 is improved. If the primer layer 42 contains a resin component having a structural unit that constitutes the second block, the adhesion between the phase of the BCP layer 43 consisting of the second block and the support 41 is improved. Therefore, if the primer layer 42 contains a resin component having both the constituent units of the first block and the constituent units of the second block, the phase separation of the BCP layer 43 makes it easier to form a phase-separated structure oriented perpendicular to the surface of the support 41. Also, if the primer layer 42 contains a resin component having either the constituent units of the first block or the constituent units of the second block, the phase separation of the BCP layer 43 makes it easier to form a phase-separated structure oriented horizontally to the surface of the support 41.

[0076] Primer: A resin composition can be used as a primer. The resin composition for the primer can be appropriately selected from conventionally known resin compositions used for thin film formation, depending on the type of block constituting the block copolymer. The resin composition for the primer may be, for example, a thermopolymerizable resin composition, or a photosensitive resin composition such as a positive-type resist composition or a negative-type resist composition. Alternatively, a compound may be used as a surface treatment agent, and a non-polymerizable film formed by coating the compound may be used as the primer layer. For example, a siloxane-based organic monolayer formed with phenethyltrichlorosilane, octadecyltrichlorosilane, hexamethyldisilazane, etc., as a surface treatment agent can also be suitably used as the primer layer.

[0077] When forming a vertically oriented phase-separated structure, examples of such resin compositions include a resin containing a resin having both the constituent units that make up the first block and the second block, and a resin containing a resin having constituent units that have high affinity for each block that makes up the block copolymer. As a resin composition for a primer, it is preferable to use, for example, a composition containing a resin having both styrene and methyl methacrylate as constituent units, or a compound or composition containing both a part with high affinity for styrene, such as an aromatic ring, and a part with high affinity for methyl methacrylate (such as a highly polar functional group). Resins containing both styrene and methyl methacrylate as constituent units include random copolymers of styrene and methyl methacrylate, and alternating polymers of styrene and methyl methacrylate (polymers in which each monomer is copolymerized alternately). Furthermore, a composition containing both a moiety highly compatible with styrene and a moiety highly compatible with methyl methacrylate is, 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. Examples of monomers having an aromatic ring include aryl groups, such as phenyl groups, biphenyl groups, fluorenyl groups, naphthyl groups, anthryl groups, and phenanthryl groups, which are aromatic hydrocarbon rings with one hydrogen atom removed, 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 monomers having a highly polar functional group include monomers having trimethoxysilyl groups, trichlorosilyl groups, epoxy groups, glycidyl groups, carboxyl groups, hydroxyl groups, cyano groups, and hydroxyalkyl groups, in which some of the hydrogen atoms of an alkyl group are substituted with hydroxyl groups. Other examples of compounds containing both a moiety highly compatible with styrene and a moiety 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.

[0078] When forming a phase-separated structure oriented horizontally, examples of such resin compositions include resin compositions containing a resin having either a constituent unit that constitutes a first block or a second block, or resin compositions containing a resin having any constituent unit that has high affinity with each block constituting the block copolymer.

[0079] The resin composition for the primer can be manufactured by dissolving the aforementioned resin in a solvent. Such a solvent can be any solvent that can dissolve each component used to form a homogeneous solution, and examples include solvents similar to the organic solvent components exemplified in the description of the resin composition for forming a phase separation structure.

[0080] The support 41 is not particularly limited in type, as long as a resin composition can be applied to its surface. Examples include substrates made of inorganic materials such as silicon, metals (copper, chromium, iron, aluminum, etc.), glass, titanium oxide, silica, and mica; substrates made of oxides such as SiO2; substrates made of nitrides such as SiN; substrates made of oxidized nitrides such as SiON; and substrates made of organic materials such as acrylic resin, polystyrene, cellulose, cellulose acetate, and phenolic resin. Among these, silicon substrates (Si substrates) or metal substrates are preferred, Si substrates or copper substrates (Cu substrates) are more preferred, and Si substrates are particularly preferred. The size and shape of the support 41 are not particularly limited. The support 41 does not necessarily need to have a smooth surface, and various shapes of substrates can be appropriately selected. Examples include substrates with curved surfaces, flat plates with uneven surfaces, and substrates in the shape of thin flakes.

[0081] The surface of the support 41 may be provided with an inorganic and / or organic film. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARC). Examples of organic films include organic anti-reflective coatings (organic BARC). Inorganic films can be formed, for example, by coating an inorganic anti-reflective film composition, such as a silicon-based material, onto a support and then firing it. Organic films can be formed, for example, by applying an organic film-forming material, which is obtained by dissolving resin components constituting the film in an organic solvent, onto a substrate using a spinner or the like, and then baking it under heating conditions of preferably 200°C to 300°C, preferably 30 seconds to 300 seconds, and more preferably 60 seconds to 180 seconds. This organic film-forming material does not necessarily need to be sensitive to light or electron beams, like a resist film; it may or may not be sensitive. Specifically, resists and resins commonly used in the manufacture of semiconductor devices and liquid crystal display devices can be used. Furthermore, to form an organic film pattern, it is preferable that the organic film forming material is capable of forming an organic film that can be etched, particularly dry etched, by etching an organic film using a pattern made of block copolymer formed by processing the BCP layer 43. In particular, it is preferable that the material is capable of forming an organic film that can be etched, such as by oxygen plasma etching. Such an organic film forming material may be a material that has been conventionally used to form organic films such as organic BARC. Examples include the ARC series from Nissan Chemical Industries, Ltd., the AR series from Rohm & Haas, and the SWK series from Tokyo Ohka Kogyo Co., Ltd.

[0082] The method for applying the primer onto the support 41 to form the primer layer 42 is not particularly limited and can be formed by conventionally known methods. For example, a primer layer 42 can be formed by applying a primer onto a support 41 using a conventionally known method such as spin coating or using a spinner to form a coating film, and then drying it. The drying method for the coating film can be any method that allows the solvent contained in the primer to volatilize, such as baking. In this case, the baking temperature is preferably 80°C to 300°C, more preferably 180°C to 270°C, and even more preferably 220°C to 250°C. The baking time is preferably 30 seconds to 600 seconds, and more preferably 60 seconds to 600 seconds. The thickness of the primer layer 42 after the coating film has dried is preferably about 10 nm to 100 nm, and more preferably about 40 nm to 90 nm.

[0083] Before forming the primer layer 42 on the support 41, the surface of the support 41 may be pre-cleaned. Cleaning the surface of the support 41 improves the applicability of the primer. Conventional known methods can be used for the cleaning process, such as oxygen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment.

[0084] After forming the primer layer 42, the primer layer 42 may be rinsed with a rinsing solution such as a solvent if necessary. This rinsing removes uncrosslinked portions and other imperfections in the primer layer 42, thereby improving the affinity with at least one block constituting the block copolymer and facilitating the formation of a phase separation structure consisting of a cylinder structure oriented perpendicular to the surface of the support 41. The rinsing solution 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 thinners can be used. Furthermore, after the cleaning, a post-bake may be performed to evaporate the rinse solution. The temperature conditions for this post-bake are preferably 80°C to 300°C, and more preferably 100°C to 270°C. The baking time is preferably 30 seconds to 500 seconds, and more preferably 60 seconds to 240 seconds. The thickness of the primer layer 42 after such post-bake is preferably about 1 nm to 10 nm, and more preferably about 2 nm to 7 nm.

[0085] Next, a layer containing a block copolymer (BCP layer) 43 is formed on top of the primer layer 42. The method for forming the BCP layer 43 on the primer layer 42 is not particularly limited, and includes, for example, a conventionally known method such as using a spin coat or spinner to apply the resin composition for forming the phase separation structure of the above embodiment onto the primer layer 42 to form a coating film and then dry it.

[0086] The thickness of the BCP layer 43 should be sufficient for phase separation to occur. Considering the type of support 41, the structural period size of the formed phase separation structure, or the uniformity of the nanostructure, a thickness of 20 nm to 100 nm is preferred, and a thickness of 20 nm to 80 nm is more preferred. For example, if 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, more preferably to 20 nm or more and 80 nm or less.

[0087] <Process (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-separated structure is formed such that at least a portion of the surface of the support 41 is exposed by selective removal of the block copolymer. That is, a structure 43' containing a phase-separated structure consisting of phase 43a and phase 43b is manufactured on the support 41. The temperature conditions for annealing are preferably above the glass transition temperature of the block copolymer used, but below the thermal decomposition temperature. For example, if the block copolymer is polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer (mass average molecular weight 5000 to 100000), then 180°C to 300°C is preferred. The heating time is preferably 30 seconds to 3600 seconds. Furthermore, the annealing process is preferably carried out in a low-reactivity gas such as nitrogen.

[0088] <Optional process> The method for manufacturing a structure including a phase-separated structure is not limited to the embodiments described above, and may include steps other than steps (i) and (ii) (optional steps).

[0089] Such optional steps include a step of selectively removing a phase consisting of at least one type of block from among the multiple types of blocks constituting the block copolymer from the BCP layer 43 (hereinafter referred to as "step (iii)"), a guide pattern formation step, and the like.

[0090] Regarding process (iii): In step (iii), a phase consisting of at least one type of block from among the multiple types of blocks that make up the block copolymer is selectively removed from the BCP layer formed on the primer layer 42. This forms a fine pattern (polymer nanostructure).

[0091] Methods for selectively removing the block-based phase include treating the BCP layer with oxygen plasma or hydrogen plasma. For example, after phase separation of a BCP layer containing a block copolymer, the BCP layer is subjected to oxygen plasma treatment or hydrogen plasma treatment, thereby selectively removing the phase consisting of the second and third blocks while the phase consisting of the first block is not selectively removed.

[0092] Figure 2 shows an example of one embodiment of process (iii). In the embodiment shown in Figure 2, the structure 43' manufactured on the support 41 in step (ii) is subjected to oxygen plasma treatment, thereby selectively removing phase 43a and forming a pattern (polymer nanostructure) consisting of separated phases 43b. In this case, phase 43b is a phase consisting of a first block, and phase 43a is a phase consisting of a second block and a third block.

[0093] As described above, the support 41, on which a pattern has been formed by the phase separation of the BCP layer 43 made of the block copolymer, can be used as is, but the shape of the pattern (polymer nanostructure) on the support 41 can also be changed by further heating. The heating temperature should preferably be above the glass transition temperature of the block copolymer used, and below its thermal decomposition temperature. Furthermore, heating is preferably carried out in a low-reactivity gas such as nitrogen.

[0094] • Regarding the guide pattern formation process In a method for manufacturing a structure including a phase-separated structure, a step of providing a guide pattern on the primer layer (guide pattern formation step) may be included between the above-described steps (i) and (ii). This makes it possible to control the arrangement structure of the phase-separated structure. For example, even with a block copolymer that forms a random fingerprint-like phase separation structure when no guide pattern is provided, a phase separation structure oriented along the grooves can be obtained by providing a groove structure of the resist film on the surface of the undercoat layer. Guide patterns may be provided on the undercoat layer 42 based on this principle. Furthermore, if the surface of the guide pattern has affinity with any of the blocks constituting the block copolymer, it becomes easier to form a phase separation structure consisting of a cylinder structure oriented perpendicular to the support surface.

[0095] Guide patterns can be formed, for example, using a resist composition. The resist composition for forming the guide pattern can be selected from among resist compositions and modifications thereof commonly used for forming resist patterns, and can be appropriately chosen to have affinity with any of the blocks constituting the block copolymer. The resist composition may be either a positive-type resist composition that forms a positive-type pattern in which the exposed portion of the resist film is dissolved and removed, or a negative-type resist composition that forms a negative-type pattern in which the unexposed portion of the resist film is dissolved and removed, but a negative-type resist composition is preferred. As a negative-type resist composition, for example, a resist composition containing an acid generator and a base component whose solubility in a developer containing an organic solvent is reduced by the action of the acid, and the base component having a resin component whose polarity increases when it decomposes by the action of the acid, is preferred. After the BCP composition is poured onto the primer layer on which the guide pattern has been formed, an annealing treatment is performed to induce phase separation. For this reason, the resist composition used to form the guide pattern is preferably a composition that can form a resist film with excellent solvent resistance and heat resistance.

[0096] As described above, the inventors provide the following (1) to (8). (1) A resin composition for forming a phase-separated structure containing a block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of structural units derived from high-LogP monomers. A resin composition for forming a phase-separated structure, wherein the LogP value of the high-LogP monomer is higher than that of methyl methacrylate. [ka] (In formula (b1), R 11 R is a hydrogen atom or a methyl group. 12 is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R 21 (This is a hydrogen atom or a methyl group.) (2) The resin composition for forming a phase separation structure according to (1), wherein the LogP value of the monomer is 1.3 or more and 4 or less. (3) The resin composition for forming a phase-separated structure according to (1) or (2), wherein the third block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b3). [ka] (In equation (b3), R 31 L is a hydrogen atom or a methyl group. L is a single bond or a divalent linking group. 32 (This refers to an organic group having between 1 and 15 carbon atoms.) (4) L is a group represented by -C(=O)-O-, and the carbonyl group at -C(=O)-O- is R 31 It is bonded to the carbon atom to which it is bonded, R 32 However, alkyl groups having 2 to 15 carbon atoms may have substituents, or -R 33 -R 34 It is a base represented by, R 33 However, it is a single bond or a methylene group, R 34 The resin composition for forming a phase separation structure according to (3), wherein the resin is a cycloalkyl group which may have substituents, an aromatic hydrocarbon group which may have substituents, or a heterocyclic group which may have substituents. (5) A resin composition for forming a phase separation structure according to any one of (1) to (4), wherein the ratio of the number of moles of the constituent units of the third block to the sum of the number of moles of the constituent units of the first block, the number of moles of the constituent units of the second block, and the number of moles of the constituent units of the third block is 0.1 mol% or more and 10 mol% or less. (6) A resin composition for forming a phase-separated structure according to any one of (1) to (5), further containing a homopolymer. (7) Applying a resin composition for forming a phase separation structure according to any one of (1) to (6) onto a support to form a layer containing a block copolymer, The process involves separating the layer containing the aforementioned block copolymer, A method for manufacturing a structure having a phase-separated structure. (8) A block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of monomer-derived structural units. The aforementioned monomer has a LogP value higher than that of methyl methacrylate, forming a block copolymer. [ka] (In formula (b1), R 11 R is a hydrogen atom or a methyl group. 12 is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R 21 (This is a hydrogen atom or a methyl group.) [Examples]

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0098] (Synthesis of BCP(P-01)) Under an argon atmosphere, 0.1 g (2.36 mmol) of lithium chloride and 169 g of tetrahydrofuran (THF) were placed in a Schlenk tube, and the contents of the tube were cooled to -78°C. After dehydrating and degassing the contents of the tube, under an argon atmosphere, 0.16 mL (1.15 mol / L hexane-cyclohexane mixture, 0.19 mmol) of sec-butyllithium (sec-BuLi) was added to the Schlenk tube as an anionic polymerization initiator, followed by 20.0 mL (174 mmol) of compound (A-1). The contents of the tube were then stirred at -78°C for 30 minutes. After stirring, 0.11 mL (0.58 mmol) of diphenylethylene was added to the Schlenk tube, and the contents of the tube were stirred at -78°C for 30 minutes. Furthermore, 0.3 mL (2.6 mmol) of compound (B-1) was added to a Schlenk tube, and the contents of the tube were stirred at -78°C for 90 minutes. Then, 9.12 mL (86 mmol) of compound (C-1) was added to the Schlenk tube, and the contents of the tube were stirred at -78°C for 90 minutes. After stirring, at -78°C, 2 mL (50 mmol) of methanol (MeOH) was added to the Schlenk tube as a polymerization inhibitor to stop the reaction.

[0099] The resulting reaction polymerization solution was added dropwise to a large amount of methanol. The precipitated white powder was washed with a large amount of methanol, and then washed with a large amount of pure water. After washing, it was dried to obtain 24.7 g (yield: 92.1%) of the target product, block copolymer (BCP(P-01)).

[0100] [ka]

[0101] (Combination of BCP(P-02)~(P-05)) BCP(P-02) to BCP(P-05) were synthesized using the same method as BCP(P-01).

[0102] (Combination of BCP(P-06)~(P-10)) Compounds (B-2) to (B-6) were used instead of compound (B-1), and BCP(P-06) to BCP(P-10) were synthesized using the same method as the synthesis of BCP(P-01).

[0103] [ka]

[0104] (BCP(p-1)) As BCP(p-1), a block copolymer having a block made of polystyrene and a block made of polymethyl methacrylate was used.

[0105] (Synthesis of BCP(p-2)) Under an argon atmosphere, 0.1 g (2.36 mmol) of lithium chloride and 169 g of tetrahydrofuran (THF) were placed in a Schlenk tube, and the contents of the tube were cooled to -78°C. After dehydrating and degassing the contents of the tube, under an argon atmosphere, 0.16 mL (1.15 mol / L hexane-cyclohexane mixture, 0.19 mmol) of sec-butyllithium (sec-BuLi) was added to the Schlenk tube as an anionic polymerization initiator, followed by 20.0 mL (174 mmol) of compound (A-1). The contents of the tube were then stirred at -78°C for 30 minutes. After stirring, 0.11 mL (0.58 mmol) of diphenylethylene was added to the Schlenk tube, and the contents of the tube were stirred at -78°C for 30 minutes. Furthermore, a monomer mixture of 0.3 mL (2.6 mmol) of compound (B-1) and 9.12 mL (86 mmol) of compound (C-1) was placed in a Schlenk tube, and the contents of the tube were stirred at -78°C for 90 minutes. After stirring, at -78°C, 2 mL (50 mmol) of methanol was added to the Schlenk tube as a polymerization inhibitor to stop the reaction.

[0106] The same procedure as in the synthesis of BCP(P-01) was performed on the obtained reaction polymerization solution to obtain the target product, block copolymer (BCP(p-2)).

[0107] [ka]

[0108] (Synthesis of BCP(p-3)) By swapping the addition of compounds (B-1) and (C-1) and the reaction order, BCP(p-3) was synthesized in the same manner as the synthesis of BCP(P-01).

[0109] (Synthesis of BCP(p-4)) Using compound (b-1) instead of compound (B-1), BCP(p-4) was synthesized in the same manner as the synthesis of BCP(P-01).

[0110] [ka]

[0111] <Measurement of the molar ratio of the constituent units of each block> Using an NMR spectrometer (Bruker, with CryoProbe) 13 The integral ratio (area ratio) was measured from the chemical shift of the constituent units of each block of the block copolymer using 1C-NMR measurement (600 MHz, deuterated acetone), and the molar ratio of the constituent units of each block was calculated.

[0112] The number-average molecular weight (Mn), molecular weight dispersion (PDI), and molecular weight dispersion of each block copolymer, as determined by gel permeation chromatography, are as follows: 13 Table 1 shows the molar ratios of the constituent units of each block, determined by 13C-NMR measurement. The LogP values ​​were as follows: compound (B-1) 1.716, compound (B-2) 3.754, compound (B-3) 2.481, compound (B-4) 1.399, compound (B-5) 3.179, compound (B-6) 2.527, compound (b-1) 0.739, compound (C-1) 1.207, and compound (A-1) 2.821.

[0113] [Table 1]

[0114] <Preparation of resin composition for forming phase-separated structures> Each example of a resin composition for forming a phase-separated structure was prepared by mixing and dissolving 100 parts by mass of a block copolymer (BCP) of the type shown in Table 2, a homopolymer (HP) of the type and amount (parts by mass) shown in Table 2, and an organic solvent component (propylene glycol monomethyl ether acetate) of the amount (parts by mass) shown in Table 2.

[0115] [Table 2]

[0116] In Table 2, each abbreviation has the following meaning: P-01~P-10: The above BCP(P-01)~(P-10) p-1~p-4: The above BCP(p-1)~(p-4) PS: Polystyrene (number-average molecular weight 2,000, molecular weight dispersion 1.03) PMMA: Polymethyl methacrylate (number-average molecular weight 2,000, molecular weight dispersion 1.03)

[0117] <Manufacturing of structures including phase separation structures (1)> A neutralized film composition solution (primer) prepared in approximately 2.0% by mass of propylene glycol monomethyl ether acetate (PGMEA) solution was applied to a 12-inch silicon wafer using a spinner, and then dried by firing at 250°C for 300 seconds under a nitrogen atmosphere, thereby forming a layer (primer layer) consisting of a neutralized film with a thickness of 60 nm on the substrate. Next, the parts of the neutralized film other than the substrate-adhering portion were removed with OK73 thinner (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and post-bake was performed at 100°C for 60 seconds. After spin-coating each example of the resin composition for forming the phase separation structure onto the layer made up of the neutralized film, a soft bake was performed at 90°C for 60 seconds to form a BCP layer with a thickness of 66 nm. As the neutralization film composition solution, a PGMEA solution of a random copolymer having styrene (St) units, methyl methacrylate (MMA) units, and 2-hydroxyethyl methacrylate (HEMA) units (St / MMA / HEMA = 82 / 12 / 6 (mol%), number average molecular weight 45,600, molecular weight dispersion (PDI) 1.76) was used.

[0118] The formed BCP layer was annealed under a nitrogen atmosphere to create a phase-separated structure in which the cylinder structure was oriented vertically. The annealing temperature and time were 280°C for 15 minutes.

[0119] A substrate with a phase-separated structure was irradiated with ultraviolet light (λ172nm) under a nitrogen atmosphere using CLEAN TRACK LITHIUS Pro-Z (manufactured by Tokyo Electron Limited). Subsequently, development was performed with isopropyl alcohol to selectively remove the phases consisting of the second and third blocks, thereby forming a hole pattern.

[0120] [Measurement of L0 of a structure] For each of the formed patterns, image analysis was performed using image analysis software (DSA-APPS, manufactured by Hitachi High-Tech Corporation) to determine L0 (nm) in the 1350 nm square image. The results are shown in Table 3.

[0121] [Evaluation of vertical orientation] The surface of the obtained substrate (phase separation state) was observed using a measuring SEM (scanning electron microscope, product name CG6300, manufactured by Hitachi High-Tech Technologies, Ltd., acceleration voltage 800 eV, current value 15 pA, frame 256, magnification 100 k (1350 nm square image)). Based on the results of this observation, the phase separation performance was evaluated according to the evaluation criteria below. The results are shown in Table 3 as "vertical orientation." Figure 3 shows specific examples of images showing the phase separation state corresponding to evaluations A to D. (Evaluation Criteria) A: There were five or fewer instances of a structure in which multiple holes were connected horizontally within a single image. B: There were between 6 and 20 instances of a structure in which multiple holes were connected horizontally within a single image. C: There were 21 or more instances of a structure in which multiple holes were connected horizontally within a single image. D: There was a large mix of vertical and horizontal orientation, or the orientation was unoriented.

[0122] [Defect Assessment] For the images of the examples and comparative examples where the vertical orientation result was A, image analysis was performed using image analysis software (DSA-APPS, Hitachi High-Tech Corporation). The number of normal holes (holes surrounded by 6 holes) and defective holes (holes surrounded by 5 or fewer or 7 or more holes) in each image was counted. The defective hole ratio shown in the following formula was calculated, and pattern defects were evaluated based on the evaluation criteria below. The results are shown as "defects" in Table 3. Defect hole percentage (%) = (Number of defective holes / Number of normal holes) × 100 (Evaluation Criteria) A: The above percentage was less than 7% B: The above percentage was between 7% and 10% C: The above percentage was 10% or more

[0123] [Evaluation of In-Plane Uniformity (CDU / CD)] Image analysis was performed on the images obtained from the evaluation of vertical orientation using image analysis software (DSA-APPS, Hitachi High-Tech Corporation). The hole diameters (nm) of 100 holes in the hole pattern were measured, and the average value (CD;nm) was calculated. Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined and defined as "CDU (nm)". The in-plane uniformity index shown in the following formula was calculated, and the in-plane uniformity was evaluated based on the evaluation criteria below. The results are shown in Table 3 as "In-plane Uniformity". In-plane uniformity index (%)=CDU / CD (Evaluation Criteria) A: The above index was less than 10% B: The above index was between 10% and 12%. C: The above index was between 12% and 14%. D: The above index was 14% or higher

[0124] <Manufacturing of structures including phase separation structures (2)> A polystyrene film composition solution (primer) prepared in a propylene glycol monomethyl ether acetate (PGMEA) solution with a concentration of approximately 1.0% by mass was applied to a 12-inch silicon wafer using a spinner, and then dried by firing at 200°C for 120 seconds under air, thereby forming a layer (primer layer) consisting of a polystyrene film with a thickness of 25 nm on the substrate. Next, the parts of the polystyrene film other than the substrate-adhering portion were removed with OK73 thinner (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and post-bake was performed at 100°C for 60 seconds. After spin-coating each example of the resin composition for forming the phase separation structure onto the layer made of the polystyrene film, a soft bake was performed at 90°C for 60 seconds to form a BCP layer with a thickness of 66 nm. As the polystyrene film composition solution, a PGMEA solution of terminally hydroxyl-grouped polystyrene (number-average molecular weight 5,000, molecular weight dispersion (PDI) 1.05) represented by the following formula was used. [ka]

[0125] The formed BCP layer was annealed under a nitrogen atmosphere to create a phase-separated structure in which the cylinder structure was oriented horizontally. The annealing temperature and time were 280°C for 15 minutes.

[0126] A substrate with a phase-separated structure was irradiated with ultraviolet light (λ172nm) under a nitrogen atmosphere using CLEAN TRACK LITHIUS Pro-Z (manufactured by Tokyo Electron Limited). Subsequently, development was performed with isopropyl alcohol to selectively remove the phases consisting of the second and third blocks, thereby forming a hole pattern.

[0127] [Evaluation of horizontal orientation] The surface of the obtained substrate (phase separation state) was observed using a measuring SEM (scanning electron microscope, product name CG6300, manufactured by Hitachi High-Tech Technologies, Ltd., acceleration voltage 800 eV, current value 15 pA, frame 256, magnification 100 k (1350 nm square image)). Based on the results of this observation, the phase separation performance was evaluated according to the evaluation criteria below. The results are shown in Table 3 as "horizontal orientation". Figure 4 shows specific examples of images showing the phase separation state corresponding to evaluations A to D. (Evaluation Criteria) A: Perfect horizontal orientation was observed. B: Partial vertical orientation was observed, with more than 90% being horizontally oriented transverse cylinder structures. C: Partial vertical orientation was observed, with horizontally oriented transverse cylinder structures accounting for more than 50% but less than 90%. D: Partial vertical orientation was observed, with less than 50% of the transverse cylinder structures being horizontally oriented.

[0128] [Table 3]

[0129] As shown in Table 3, Examples 1 to 13, which used the specified block copolymer, exhibited excellent horizontal orientation, vertical orientation, and in-plane uniformity. On the other hand, Comparative Examples 1 to 4, which used other block copolymers, showed inferiority in at least one of the horizontal orientation, vertical orientation, and in-plane uniformity.

Claims

1. A resin composition for forming a phase-separated structure, comprising a block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of structural units derived from high-logP monomers. A resin composition for forming a phase-separated structure, wherein the LogP value of the high-LogP monomer is higher than the LogP value of methyl methacrylate. 【Chemistry 1】 (In formula (b1), R １１ R is a hydrogen atom or a methyl group. １２ n is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R ２１ (This is a hydrogen atom or a methyl group.)

2. The resin composition for forming a phase-separated structure according to claim 1, wherein the LogP value of the monomer is 1.3 or more and 4 or less.

3. The resin composition for forming a phase-separated structure according to claim 1, wherein the third block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b3). 【Chemistry 2】 (In equation (b3), R ３１ L is a hydrogen atom or a methyl group. L is a single bond or a divalent linking group. ３２ (This refers to an organic group having between 1 and 15 carbon atoms.)

4. L is a group represented as -C(=O)-O-, where the carbonyl group in -C(=O)-O- is R ３１ It is bonded to the carbon atom to which it is bonded, R ３２ is an alkyl group having 2 to 15 carbon atoms which may have a substituent, or -R ３３ -R ３４ is a group represented by, R ３３ However, it is a single bond or a methylene group, R ３４ The resin composition for forming a phase separation structure according to claim 3, wherein the group is a cycloalkyl group which may have substituents, an aromatic hydrocarbon group which may have substituents, or a heterocyclic group which may have substituents.

5. The resin composition for forming a phase-separated structure according to claim 1, wherein the ratio of the number of moles of the constituent units of the third block to the sum of the number of moles of the constituent units of the first block, the number of moles of the constituent units of the second block, and the number of moles of the constituent units of the third block is 0.1 mol% or more and 10 mol% or less.

6. The resin composition for forming a phase-separated structure according to claim 1, further containing a homopolymer.

7. A layer containing a block copolymer is formed by applying a resin composition for forming a phase-separated structure according to any one of claims 1 to 6 onto a support, The process involves separating the layer containing the aforementioned block copolymer, A method for manufacturing a structure having a phase-separated structure.

8. A block copolymer having a first block, a second block, and a third block, The third block is located between the first block and the second block. The first block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b1): The second block is composed of a polymer consisting of a repeating structure of constituent units represented by the following formula (b2): The third block is composed of a polymer consisting of repeating structures of monomer-derived structural units. The aforementioned monomer has a LogP value higher than that of methyl methacrylate, forming a block copolymer. 【Transformation 3】 (In formula (b1), R １１ R is a hydrogen atom or a methyl group. １２ n is a substituent having 1 to 5 carbon atoms. n is an integer between 0 and 5. In formula (b2), R ２１ (This is a hydrogen atom or a methyl group.)

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